Title of Invention: Water Repellent Composition, Method for Producing Water Repellent Composition, and Textile Product
Technical field
[0001]
TECHNICAL FIELD The present invention relates to a water repellent composition, a method for producing the water repellent composition, and a textile product, and more particularly, to a water repellent composition, a method for producing the water repellent composition, and the water repellent composition. It relates to textile products that are water repellent treated by
Background technology
[0002]
Conventionally, fluorine-based water repellents containing fluorine compounds are known as water repellents. When this water repellent agent is applied to a substrate such as a textile product, it exhibits good water repellency.
[0003]
On the other hand, in recent years, in consideration of the environmental impact of fluorine, the demand for non-fluorine water repellents that do not contain fluorine compounds is increasing.
[0004]
As such a non-fluorine water repellent, for example, a surface treatment agent containing a non-fluorine polymer, a surfactant, and a liquid medium has been proposed (see Patent Document 1, for example).
prior art documents
patent literature
[0005]
Patent Document 1: Japanese Patent Publication No. 2015-120894
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0006]
In recent years, non-fluorine-based water repellents are required to have further improved water repellency.
[0007]
An object of the present invention is to provide a water repellent composition that is excellent in water repellency, a method for producing the water repellent composition, and a textile product that is water repellent treated with the water repellent composition.
Means to solve problems
[0008]
The present invention [1] comprises a polyurethane resin compound, a non-fluorine water-repellent compound, a surfactant, and a liquid medium, wherein the polyurethane resin compound comprises the following (A) first polyurethane resin compound and the following (B ) a second polyurethane resin compound and at least one selected from the group consisting of the following (C) a third polyurethane resin compound.
(A) a first aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more, a first long-chain active hydrogen compound having both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group, an active hydrogen group and a cationic A first polyurethane resin compound which is a reaction product of a cationic active hydrogen compound having both a group and an acid compound which forms a salt with the cationic group, and wherein the concentration of the hydrocarbon group is 30% or more and 85% or less. .
(B) an isocyanate compound, an alkyl sorbitan having an alkyl group having 12 to 30 carbon atoms, an alkyl citrate having an alkyl group having 12 to 30 carbon atoms, and a pentaerythritol ester having an alkyl group having 12 to 30 carbon atoms A second polyurethane resin compound comprising a reaction product with at least one selected from the group consisting of:
(C) a second aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more and a second long-chain active hydrogen compound having both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group; 3 Polyurethane resin compounds.
[0009]
In the present invention [2], the blending ratio of the non-fluorine water-repellent compound is 0.1 parts by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the total amount of the polyurethane resin compound and the non-fluorine water-repellent compound. , contains the water repellent composition described in [1] above.
[0010]
In the present invention [3], the non-fluorine water-repellent compound is derived from a long-chain aliphatic hydrocarbon group-containing (meth)acrylate represented by the following formula (1) and/or an amide group-containing monomer represented by the following formula (2). It contains the water repellent composition according to the above [1] or [2], which is a polymer containing a structural unit that
[0011]
[Chemical 4]

[0012]
(In formula (1) above, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a linear or branched long-chain aliphatic hydrocarbon group having 18 to 30 carbon atoms. )
[0013]
[Chemical 5]

[0014]
(In formula (2) above, R 3 represents an organic residue having an ethylenically unsaturated double bond group, R 4 represents a monovalent hydrocarbon group having 7 to 30 carbon atoms, and R 5 represents a divalent hydrocarbon group having 1 to 5 carbon atoms.)
The present invention [4] includes the water repellent composition according to [3] above, wherein the non-fluorine water repellent compound is a polymer containing a structural unit derived from a reactive emulsifier.
[0015]
The present invention [5] includes the water repellent composition according to [4] above, wherein the reactive emulsifier is represented by the following formula (3).
[0016]
[Chemical 6]

[0017]
(In the above formula (3), R 10 represents an organic residue having an ethylenically unsaturated double bond group having 12 to 20 carbon atoms, and R 11 represents an oxyalkylene group having 2 to 10 carbon atoms. show.)
[0018]
The present invention [6] includes the water repellent composition according to the above [1] or [2], wherein the non-fluorine water repellent compound is a dendrimer water repellent.
[0019]
The present invention [7] is the water repellent composition according to any one of [1] to [6] above, which contains at least one selected from the group consisting of a blocked isocyanate compound, a silicone polymer and a wax. contains things.
[0020]
The present invention [8] provides the water repellent composition according to any one of [1] to [7] above, wherein the first aliphatic polyisocyanate derivative comprises an isocyanurate derivative of an aliphatic polyisocyanate. contains.
[0021]
The present invention [9] is the cationic active hydrogen compound of the first polyurethane resin compound, wherein the cationic group is a tertiary amino group, the active hydrogen group is a hydroxyl group, and the cationic active hydrogen is The compound includes the water repellent composition according to any one of [1] to [8] above, which has two or more hydroxyl groups per molecule.
[0022]
The present invention [10] is the method for producing the water repellent composition according to [3] above, wherein the monomer component is polymerized in the presence of the polyurethane resin compound, the surfactant, and the liquid medium. to produce the non-fluorine water repellent compound.
[0023]
The present invention [11] includes a textile product that is water repellent treated with the water repellent composition according to any one of [1] to [8] above.
Effect of the invention
[0024]
The water repellent composition of the present invention comprises a polyurethane resin compound containing at least one selected from the group consisting of a first polyurethane resin compound, a second polyurethane resin compound, and a third polyurethane resin compound; Aqueous compounds.
[0025]
Therefore, it is possible to improve the water repellency of the water repellent treated object treated with this water repellent composition.
[0026]
In the method for producing a water repellent composition of the present invention, a non-fluorine water repellent compound is produced by polymerizing a monomer component in the presence of a polyurethane resin compound, a surfactant and a liquid medium.
[0027]
Therefore, a water repellent composition with excellent water repellency can be produced.
[0028]
The textile product of the present invention is a water repellent product treated with the water repellent composition of the present invention.
[0029]
Therefore, this textile product has excellent water repellency.
MODE FOR CARRYING OUT THE INVENTION
[0030]
The water repellent composition of the present invention contains a polyurethane resin compound, a non-fluorine water repellent compound, a surfactant, and a liquid medium.
[0031]
Below, each component will be described in detail.
1. Polyurethane resin compound
The polyurethane resin compound contains at least one selected from the group consisting of a first polyurethane resin compound, a second polyurethane resin compound, and a third polyurethane resin compound.
1-1. First polyurethane resin compound
The first polyurethane resin compound is a reaction product of the first aliphatic polyisocyanate derivative, the first long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound.
[0032]
A first aliphatic polyisocyanate derivative is a derivative of an aliphatic polyisocyanate.
[0033]
Aliphatic polyisocyanates include, for example, hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1 ,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate.
[0034]
In addition, aliphatic polyisocyanates include alicyclic polyisocyanates.
[0035]
Alicyclic polyisocyanates include, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-, 2,4′- or 2,2′-methylenebis (cyclohexyl isocyanate) or mixtures thereof (H 12MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof (H 6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3 -cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate and methyl-2,6-cyclohexane diisocyanate.
[0036]
Preferred aliphatic polyisocyanates include hexamethylene diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter simply referred to as bis(isocyanatomethyl)cyclohexane), more preferably hexamethylene diisocyanate. be done.
[0037]
Examples of the first aliphatic polyisocyanate derivative include oligomers of the above aliphatic polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamer, etc.), allophanate derivatives (e.g., the above-described aliphatic polyisocyanate and allophanate derivatives produced by reaction with a monohydric alcohol or dihydric alcohol), polyol derivatives (e.g., the above-described aliphatic polyisocyanate and 3 polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts, etc.) produced by reaction with a hydric alcohol (e.g., trimethylolpropane, etc.), biuret derivatives (e.g., the above-mentioned aliphatic polyisocyanates, water or biuret derivatives produced by reaction with amines), urea derivatives (for example, urea derivatives produced by reaction of the above-mentioned aliphatic polyisocyanate and diamine), oxadiazinetrione derivatives (for example, the above-mentioned aliphatic poly oxadiazinetrione produced by the reaction of isocyanate and carbon dioxide), carbodiimide derivatives (such as carbodiimide derivatives produced by decarboxylation condensation reaction of the above aliphatic polyisocyanate), uretdione derivatives, uretonimine derivatives and the like.
[0038]
The first aliphatic polyisocyanate derivative preferably includes an isocyanurate derivative.
[0039]
When the first aliphatic polyisocyanate derivative contains an isocyanurate derivative, the texture is improved.
[0040]
And, as the first aliphatic polyisocyanate derivative, an isocyanurate derivative of hexamethylene diisocyanate is more preferable.
[0041]
The first aliphatic polyisocyanate derivative can be used alone or in combination of two or more.
[0042]
Also, the first aliphatic polyisocyanate derivative can be produced by a known method.
[0043]
The average number of isocyanate groups of the first aliphatic polyisocyanate derivative is 2 or more, preferably 2.5, more preferably 2.9, and is, for example, 3.8 or less.
[0044]
If the average number of isocyanate groups is equal to or greater than the lower limit, the water repellency of the water-repellent treated material treated with the water repellent composition can be improved.
[0045]
　In addition, the average isocyanate group A method for measuring the number will be described in detail in Examples described later.
[0046]
In addition, when two or more types of the first aliphatic polyisocyanate derivative are used in combination, the average number of isocyanate groups is calculated from the weight ratio of the first aliphatic polyisocyanate derivative and the average number of isocyanate functional groups.
[0047]
The first long-chain active hydrogen compound has both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group that reacts with the first aliphatic polyisocyanate derivative.
[0048]
Examples of hydrocarbon groups having 12 to 30 carbon atoms include linear or branched saturated hydrocarbon groups having 12 to 30 carbon atoms (e.g., alkyl groups), for example, 12 to 30 carbon atoms. linear or branched unsaturated hydrocarbon groups (eg, alkenyl groups, etc.).
[0049]
Examples of active hydrogen groups include hydroxyl groups.
[0050]
Examples of the first long-chain active hydrogen compound having both a hydrocarbon group and an active hydrogen group include a linear saturated hydrocarbon group-containing active hydrogen compound, a branched saturated hydrocarbon group-containing active hydrogen compound, and a straight-chain saturated hydrocarbon group-containing active hydrogen compound. Chain unsaturated hydrocarbon group-containing active hydrogen compounds, branched chain unsaturated hydrocarbon group-containing active hydrogen compounds, and the like are included.
[0051]
The linear saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear saturated hydrocarbon group having from 12 to 30 carbon atoms, such as n-tridecanol, n-tetradecanol, n - linear saturated hydrocarbon group-containing alcohols such as pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, eicosanol, for example, sorbitan tristearate linear saturated hydrocarbon group-containing sorbitan esters such as
[0052]
The branched-chain saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain saturated hydrocarbon group having 12 to 30 carbon atoms, such as isomyristyl alcohol, isocetyl alcohol, isostearyl branched chain saturated hydrocarbon group-containing alcohols such as alcohols and isoicosyl alcohol;
[0053]
The linear unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear unsaturated hydrocarbon group having from 12 to 30 carbon atoms, such as tetradecenyl alcohol, hexadecenyl alcohol, Linear unsaturated hydrocarbon group-containing alcohols such as nyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacocenyl alcohol and octacocenyl alcohol.
[0054]
A branched-chain unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain unsaturated hydrocarbon group having 12 or more and 30 or less carbon atoms, and includes, for example, phytol.
[0055]
The first long-chain active hydrogen compound preferably includes a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound.
[0056]
The first long-chain active hydrogen compound can be used alone or in combination of two or more. Preferably, a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound are used in combination. More preferably, a combination of linear saturated hydrocarbon group-containing alcohol and linear unsaturated hydrocarbon group-containing alcohol, more preferably combined use of stearyl alcohol and oleyl alcohol.
[0057]
When a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used together, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is and the total amount of 100 parts by mass of the linear unsaturated hydrocarbon group-containing alcohol, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less. Further, the blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass with respect to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. parts or more, preferably 20 parts by mass or more, and for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less.
[0058]
If the blending ratio of the linear saturated hydrocarbon group-containing alcohol is at least the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the repellency of the water repellent treated object treated with this water repellent composition is improved. Hydrophilicity can be improved.
[0059]
A cationic active hydrogen compound has both an active hydrogen group and a cationic group.
[0060]
The active hydrogen group is, as described above, an active hydrogen group that reacts with the first aliphatic polyisocyanate derivative, and includes, for example, a hydroxyl group.
[0061]
In addition, the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule.
[0062]
Examples of cationic groups include tertiary amino groups.
[0063]
That is, the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.
[0064]
According to such a cationic active hydrogen compound, it is possible to impart good dispersibility in water to the first polyurethane resin compound, and to introduce a cationic group having an affinity for textile products (described later) into the resin. Therefore, washing durability (described later) can be improved.
[0065]
More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group.
[0066]
Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine. N-methyldiethanolamine is preferred.
[0067]
The cationic active hydrogen compound can be used alone or in combination of two or more.
[0068]
An acid compound is a compound that forms a salt with a cationic group.
[0069]
Examples of acid compounds include organic acids and inorganic acids.
[0070]
Examples of organic acids include acetic acid, lactic acid, tartaric acid, and malic acid, preferably acetic acid, lactic acid, and more preferably acetic acid.
[0071]
Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid, preferably hydrochloric acid.
[0072]
The acid compound preferably includes an organic acid.
[0073]
If the acid compound contains an organic acid, the ionicity is lowered and the water resistance is improved due to volatilization of the acid by the heat treatment. From this viewpoint, the water repellency of the water repellent material treated with this water repellent composition is improved. can be made In addition, the volatilization of the acid by the heat treatment makes it easier for the cationic groups to be adsorbed on the textile product, so that the washing durability of the textile product (described later) can be improved.
[0074]
The acid compound can be used alone or in combination of two or more.
[0075]
Then, to obtain the first polyurethane resin compound, the first aliphatic polyisocyanate derivative, the first long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound are reacted.
[0076]
In order to react the first aliphatic polyisocyanate derivative, the first long-chain active hydrogen compound, the cationic active hydrogen compound and the acid compound, first, the first aliphatic polyisocyanate derivative is added with the first long-chain active hydrogen compound. A hydrogen compound is blended, and the first aliphatic polyisocyanate derivative and the first long-chain active hydrogen compound are reacted.
[0077]
At this time, for example, when the average number of isocyanate groups of the isocyanurate derivative of the aliphatic polyisocyanate is 3, the first long-chain active hydrogen compound is preferably two isocyanate derivatives of the isocyanurate derivative of the aliphatic polyisocyanate. The group is modified by the first long-chain active hydrogen compound into a hydrocarbon group having 12 to 30 carbon atoms, and one isocyanate group remains in the isocyanurate derivative of the aliphatic polyisocyanate, and It is formulated so that no isocyanurate derivative of the reactive aliphatic polyisocyanate remains.
[0078]
Specifically, the equivalent ratio of the isocyanate group to the active hydrogen group (isocyanate group/active hydrogen group) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less. Second, the first long-chain active hydrogen compound is blended with the first aliphatic polyisocyanate derivative.
[0079]
Thereby, the molecular terminal of the reaction product (hereinafter referred to as the first intermediate reaction product) of the first aliphatic polyisocyanate derivative and the first long-chain active hydrogen compound is a hydrocarbon group having 12 to 30 carbon atoms. and isocyanate groups.
[0080]
In addition, the above reaction is carried out under a nitrogen atmosphere. As for the reaction conditions, the reaction temperature is, for example, 70° C. or higher and 120° C. or lower, and the reaction time is 1 hour or longer and 6 hours or shorter.
[0081]
Also, the above reaction is carried out until the isocyanate concentration of the first intermediate reaction product reaches a predetermined calculated value.
[0082]
The isocyanate concentration can be measured by the n-dibutylamine method according to JIS K-1556 using a potentiometric titrator.
[0083]
Also, in the above reaction, a known solvent (solvent) such as methyl ethyl ketone can be blended in an appropriate proportion.
[0084]
Next, a cationic active hydrogen compound is added to the reaction solution containing the first intermediate reaction product, and the first intermediate reaction product and the cationic active hydrogen compound are allowed to react.
[0085]
At this time, the cationic active hydrogen compound has an equivalent ratio of the isocyanate group to the active hydrogen group of the cationic active hydrogen compound (isocyanate group/active hydrogen group) of, for example, 0.95 or more and, for example, 1.05 or less. It is mixed with the first intermediate reaction product so that
[0086]
In addition, the above reaction is carried out under a nitrogen atmosphere. As for the reaction conditions, the reaction temperature is, for example, 70° C. or higher and 120° C. or lower, and the reaction time is 0.5 hours or longer and 4 hours or shorter.
[0087]
Also, the above reaction is carried out until the reaction between the first intermediate reaction product and the cationic active hydrogen compound is completed.
[0088]
In addition, in the above reaction, a known solvent such as methyl ethyl ketone can be blended in an appropriate proportion.
[0089]
As a result, a reaction product (hereinafter referred to as a second intermediate reaction product) between the first intermediate reaction product and the cationic active hydrogen compound is obtained.
[0090]
The second intermediate reaction product has a hydrocarbon group with 12 to 30 carbon atoms and a cationic group.
[0091]
Next, an acid compound is added to the second intermediate reaction product.
[0092]
The mixing ratio of the acid compound is, for example, 0.5 mol or more, preferably 3 mol or more, and for example, 10 mol or less, preferably, per 1 mol of the cationic group of the cationic active hydrogen compound. It is 4 mol or less.
[0093]
Thereby, the acid compound forms a salt with the cationic group of the second intermediate reaction product, and the first aliphatic polyisocyanate derivative, the first long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound A reaction liquid containing a reaction product with is obtained.
[0094]
The above reaction product has a hydrocarbon group with 12 to 30 carbon atoms and a cationic group.
[0095]
In addition, since the above reaction product has a hydrocarbon group with 12 to 30 carbon atoms, it can self-disperse (self-emulsify) in water regardless of the dispersant (emulsifier).can be In other words, the above reaction products can be internally emulsified.
[0096]
Then, water is added to the reaction liquid to emulsify while maintaining the temperature of the reaction liquid at, for example, 50°C or higher and 100°C or lower.
[0097]
After that, the solvent is removed from this reaction solution.
[0098]
As a result, an aqueous dispersion (aqueous dispersion of the first polyurethane resin compound) containing the above reaction product is obtained.
[0099]
The solid content concentration of the aqueous dispersion is, for example, 10% by mass or more and, for example, 30% by mass or less.
[0100]
Also, in such a polyurethane resin compound, the concentration of hydrocarbon groups is 30% or more and 85% or less, preferably 50%.
[0101]
If the concentration of the hydrocarbon group is equal to or higher than the above lower limit, the water repellency of the water repellent material treated with this water repellent composition can be improved.
[0102]
On the other hand, if the concentration of the hydrocarbon group is less than the above lower limit, the water repellency of the water repellent treated object treated with this water repellent composition is lowered.
[0103]
Also, if the concentration of the hydrocarbon group is equal to or less than the above upper limit, the stability of the polyurethane resin can be improved.
[0104]
On the other hand, if the concentration of hydrocarbon groups exceeds the above upper limit, the stability of the polyurethane resin is reduced.
[0105]
It should be noted that the concentration of the above hydrocarbon group can be calculated from the charged amount of each component described above.
[0106]
In the above description, first, the first aliphatic polyisocyanate derivative and the first long-chain active hydrogen compound are reacted to obtain a reaction liquid containing the first intermediate reaction product, and then the first intermediate reaction product is obtained. and a cationic active hydrogen compound to obtain a reaction solution containing a second intermediate reaction product, and then reacting the second intermediate reaction product with an acid compound, the order of reaction being particularly For example, the first aliphatic polyisocyanate derivative and the cationic active hydrogen compound may be reacted, and then the first long-chain active hydrogen compound and the acid compound may be reacted. Alternatively, the first aliphatic polyisocyanate derivative, the first long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound may be blended together and reacted.
1-2. Second polyurethane resin compound
The second polyurethane resin compound has an isocyanate compound, an alkyl sorbitan having an alkyl group having 12 to 30 carbon atoms (hereinafter sometimes simply referred to as alkyl sorbitan), and an alkyl group having 12 to 30 carbon atoms. Alkyl citrate (hereinafter sometimes simply referred to as alkyl citrate) and a pentaerythritol ester having an alkyl group having 12 to 30 carbon atoms (hereinafter sometimes simply referred to as pentaerythritol ester) including a reaction product with at least one selected from the group;
1-2-1. isocyanate compound
Examples of isocyanate compounds include polyisocyanates such as aromatic polyisocyanates, araliphatic polyisocyanates, and aliphatic polyisocyanates.
[0107]
Aromatic polyisocyanates include, for example, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or mixtures thereof aromatic diisocyanates such as (TDI), o-tolidine diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or mixtures thereof, 4,4'-diphenyl diisocyanate, 4,4'-diphenyl ether diisocyanate is mentioned.
[0108]
Examples of araliphatic polyisocyanates include 1,3- or 1,4-bis(isocyanatomethyl)benzene (also known as 1,3- or 1,4-xylylene diisocyanate) or mixtures thereof (XDI), 1 ,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and other araliphatic diisocyanates.
[0109]
Examples of the aliphatic polyisocyanate include the aliphatic polyisocyanate of the first polyurethane resin compound described above.
[0110]
The polyisocyanate preferably includes aliphatic polyisocyanate, more preferably hexamethylene diisocyanate.
[0111]
The polyisocyanate also includes polyisocyanate derivatives. Such polyisocyanate derivatives include, for example, polyisocyanate derivatives of the first polyurethane resin compound described above, preferably biuret derivatives.
[0112]
More preferably, the isocyanate compound includes a biuret derivative of hexamethylene diisocyanate.
[0113]
The isocyanate compound can be used alone or in combination of two or more.
1-2-2. Alkylsorbitan
Alkylsorbitan is a reaction product (sorbitan ester) between sorbitan and a carboxylic acid having an alkyl group having 12 to 30 carbon atoms.
[0114]
Sorbitan includes, for example, 1,4-sorbitan, 2,5-sorbitan and 3,6-sorbitan, preferably 1,4-sorbitan.
[0115]
Sorbitan can be used alone or in combination of two or more.
[0116]
Examples of carboxylic acids having an alkyl group having 12 to 30 carbon atoms include lauric acid (dodecanoic acid), myristic acid (detradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), behenic acid (docosane linear saturated carboxylic acid having an alkyl group having 12 to 30 carbon atoms such as acid), for example, branched having an alkyl group having 12 to 30 carbon atoms such as isostearic acid (2-heptylundecanoic acid) Examples include saturated carboxylic acids, preferably linear saturated carboxylic acids having an alkyl group having 12 to 30 carbon atoms, more preferably stearic acid.
[0117]
Carboxylic acids having an alkyl group with 12 to 30 carbon atoms can be used alone or in combination of two or more.
[0118]
Alkylsorbitan is obtained by subjecting sorbitan and a carboxylic acid having an alkyl group having 12 to 30 carbon atoms to an esterification reaction.
[0119]
Specifically, in the above reaction, the hydroxyl groups of sorbitan are reacted with the carboxyl groups of the carboxylic acid having 12 to 30 alkyl groups so that 1 to 3 hydroxyl groups out of the 4 hydroxyl groups of sorbitan react with each other. and the equivalent ratio of the carboxyl group of the carboxylic acid is adjusted.
Therefore, the obtained alkylsorbitan has at least one hydroxyl group.
[0120]
Such alkyl sorbitan preferably includes sorbitan monostearate (preferably 1,4-sorbitan monostearate) and sorbitan tristearate (preferably 1,4-sorbitan tristearate). .
[0121]
Alkyl sorbitan can be used alone or in combination of two or more, preferably sorbitan monostearate and sorbitan tristearate are used in combination.
[0122]
When sorbitan monostearate and sorbitan tristearate are used together, the mixing ratio of sorbitan monostearate is, for example, 10 parts by mass or more with respect to the total amount of 100 parts by mass of sorbitan monostearate and sorbitan tristearate. Yes, and for example, 50 parts by mass or less. Moreover, the mixing ratio of sorbitan tristearate is, for example, 10 parts by mass or more and, for example, 50 parts by mass or less with respect to 100 parts by mass of the total amount of sorbitan monostearate and sorbitan tristearate.
1-2-2. Alkyl citrate
Alkyl citrate is a reaction product (citric acid ester) between citric acid and an alcohol having an alkyl group with 12 to 30 carbon atoms.
[0123]
Examples of alcohols having an alkyl group having 12 to 30 carbon atoms include linear monovalent alcohols having an alkyl group having 12 to 30 carbon atoms, such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and lanolin alcohol. Examples of alcohols include branched monohydric alcohols having an alkyl group having 12 to 30 carbon atoms, such as isostearyl alcohol, 2-octyldodecanol, and 2-decyltetradecanol.
[0124]
Alkyl citrate is obtained by subjecting citric acid and an alcohol having an alkyl group having 12 to 30 carbon atoms to an esterification reaction by a known method.
1-2-3. pentaerythritol ester
A pentaerythritol ester is a reaction product of pentaerythritol and a carboxylic acid having an alkyl group having 12 to 30 carbon atoms.
[0125]
The above-mentioned carboxylic acid having an alkyl group having 12 to 30 carbon atoms is the same as the carboxylic acid having an alkyl group having 12 to 30 carbon atoms mentioned for alkylsorbitan.
[0126]
The pentaerythritol ester is obtained by subjecting pentaerythritol and a carboxylic acid having an alkyl group having 12 to 30 carbon atoms to an esterification reaction by a known method.
[0127]
Specifically, in the above reaction, penta The equivalent ratio between the hydroxyl group of the erythritol ester and the carboxyl group of the carboxylic acid having 12 to 30 alkyl groups is adjusted.
. Therefore, the obtained pentaerythritol ester has at least one hydroxyl group.
1-2-4. Reaction of an isocyanate compound with at least one selected from the group consisting of alkylsorbitan, alkylcitrate and pentaerythritol ester
In order to react an isocyanate compound with at least one selected from the group consisting of alkylsorbitan, alkylcitrate and pentaerythritol ester, the equivalent ratio of the isocyanate group to the active hydrogen group (hydroxyl group) (isocyanate group/active hydrogen group An isocyanate compound is blended with at least one selected from the group consisting of alkylsorbitan, alkylcitrate and pentaerythritol ester such that (hydroxyl group)) is, for example, 0.9 or more and 1.2 or less.
[0128]
As a result, a reaction product between the isocyanate compound and at least one selected from the group consisting of alkylsorbitan, alkylcitrate and pentaerythritol ester is obtained.
[0129]
In the above reaction, if necessary, a known catalyst (preferably a tin catalyst such as dibutyltin dilaurate) can be blended in an appropriate proportion.
[0130]
In addition, in the above reaction, a known organic solvent (preferably 4-methyl-2-pentanone) can be blended in an appropriate proportion, if necessary. In such a case, a reaction liquid containing a reaction product of an isocyanate compound and at least one selected from the group consisting of alkylsorbitan, alkylcitrate and pentaerythritol ester is obtained.
[0131]
In the above reaction, as reaction conditions, the reaction temperature is, for example, 40° C. or higher and, for example, 90° C. or lower, and the reaction time is, for example, 1 hour or longer. , 6 hours or less.
[0132]
Next, water is added to the reaction liquid while maintaining the temperature of the reaction liquid at, for example, 50°C or higher and 100°C or lower. and an emulsifier (preferably a cationic emulsifier) ​​is added to emulsify.
[0133]
After that, the solvent is removed from this reaction solution.
[0134]
As a result, an aqueous dispersion containing a reaction product of the isocyanate compound and at least one selected from the group consisting of alkylsorbitan, alkylcitrate and pentaerythritol ester is obtained.
[0135]
The solid content concentration of the above dispersion liquid is, for example, 10% by mass or more and, for example, 40% by mass or less.
[0136]
Among such reaction products, a reaction product between an isocyanate compound and an alkylsorbitan is preferred.
1-3. Third polyurethane resin compound
The third polyurethane resin compound contains a reaction product of the second aliphatic polyisocyanate derivative and the second long-chain active hydrogen compound.
[0137]
The second aliphatic polyisocyanate derivative includes the same aliphatic polyisocyanate derivative as the first aliphatic polyisocyanate derivative of the first polyurethane resin compound described above, preferably a biuret derivative of hexamethylene diisocyanate.
[0138]
The second aliphatic polyisocyanate derivative can be used alone or in combination of two or more.
[0139]
The average number of isocyanate groups of the second aliphatic polyisocyanate derivative is 2 or more, preferably 2.5, more preferably 2.9, and is, for example, 3.8 or less.
[0140]
If the average number of isocyanate groups is equal to or greater than the lower limit, the water repellency of the water-repellent treated material treated with the water repellent composition can be improved.
[0141]
The second long-chain active hydrogen compound has both a hydrocarbon group with 12 to 30 carbon atoms and an active hydrogen group that reacts with the second aliphatic polyisocyanate derivative.
[0142]
Examples of the hydrocarbon group having 12 or more and 30 or less carbon atoms include the same hydrocarbon group as the hydrocarbon group having 12 or more and 30 or less carbon atoms of the first polyurethane resin compound described above.
[0143]
Examples of active hydrogen groups include hydroxyl groups.
[0144]
As the second long-chain active hydrogen compound, for example, the same long-chain active hydrogen compound as the first long-chain active hydrogen compound of the first polyurethane resin compound described above can be mentioned. Hydrogen compounds, more preferably stearyl alcohol.
[0145]
In order to react the second aliphatic polyisocyanate derivative with the second long-chain active hydrogen compound, the equivalent ratio of the isocyanate group to the active hydrogen group (hydroxyl group) (isocyanate group/active hydrogen group (hydroxyl group)) is For example, the second long-chain active hydrogen compound is blended with the second aliphatic polyisocyanate derivative such that the ratio is 0.9 or more and 1.2 or less.
[0146]
As a result, a reaction product between the second aliphatic polyisocyanate derivative and the second long-chain active hydrogen compound is obtained.
[0147]
In addition, in the above reaction, if necessary, a known organic solvent (methyl ethyl ketone) can be blended in an appropriate proportion. In such a case, a reaction liquid containing a reaction product of the second aliphatic polyisocyanate derivative and the second long-chain active hydrogen compound is obtained.
[0148]
In the above reaction, as reaction conditions, the reaction temperature is, for example, 40° C. or higher and, for example, 90° C. or lower, and the reaction time is, for example, 1 hour or longer. , 6 hours or less.
[0149]
Next, water and an emulsifier (preferably a cationic emulsifier) ​​are added to the reaction liquid to emulsify while maintaining the temperature of the reaction liquid at, for example, 50°C or higher and 100°C or lower.
[0150]
After that, the solvent is removed from this reaction solution.
[0151]
As a result, an aqueous dispersion containing the reaction product of the second aliphatic polyisocyanate derivative and the second long-chain active hydrogen compound is obtained.
[0152]
The solid content concentration of the above dispersion liquid is, for example, 10% by mass or more and, for example, 40% by mass or less.
[0153]
Further, as described above, the polyurethane resin compound includes at least one selected from the group consisting of the first polyurethane resin compound, the second polyurethane resin compound and the third polyurethane resin compound, and preferably the second polyurethane resin compound. 1 polyurethane resin compound, the second polyurethane resin compound, and the third polyurethane resin compound, and more preferably treated with this water repellent composition. From the viewpoint of improving the water repellency of the polyurethane resin compound, the polyurethane resin compound contains the first polyurethane resin compound.
[0154]
In particular, when the polyurethane resin compound contains the first polyurethane resin compound, the non-fluorine water-repellent compound is an acrylic polymer (specifically, a long-chain aliphatic hydrocarbon group-containing (meth)acrylate (described later). polymer containing the derived structural unit), the water repellency to urethane/polyester blend fabrics and the like is improved.
[0155]
The mixing ratio of the polyurethane resin compound is, for example, 0.1 parts by mass or more, preferably 2 parts by mass or more, and more preferably 4 parts by mass with respect to 100 parts by mass as the total amount of the polyurethane resin compound and the non-fluorine water-repellent compound. and, for example, 99.9 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or less. be.
2. Non-fluorine water-repellent compound
The non-fluorine water-repellent compound is a compound having water repellency that does not contain a fluorine atom, and is, for example, a polymer containing a structural unit derived from a long-chain aliphatic hydrocarbon group-containing (meth)acrylate and/or an amide group-containing monomer. It is a coalescence.
[0156]
Such non-fluorine water-repellent compounds are obtained by polymerizing monomer components containing long-chain aliphatic hydrocarbon group-containing (meth)acrylate and/or amide group-containing monomers.
[0157]
The long-chain aliphatic hydrocarbon group-containing (meth)acrylate is a long-chain aliphatic hydrocarbon group-containing methacrylate and/or a long-chain aliphatic hydrocarbon group-containing acrylate, and is represented by the following formula (1).
[0158]
[Chemical 7]

[0159]
In formula (1) above, R 1 represents a hydrogen atom or a methyl group.
[0160]
In the above formula (1), R 2 is a linear or branched long-chain aliphatic hydrocarbon group having 18 or more and 30 or less carbon atoms, preferably a linear hydrocarbon group having 18 or more and 30 or less carbon atoms. Indicates a chain alkyl group.
[0161]
Specific examples of such long-chain aliphatic hydrocarbon group-containing (meth)acrylates include stearyl (meth)acrylate, behenyl (meth)acrylate and the like, preferably stearyl (meth)acrylate, more preferably , stearyl acrylate.
[0162]
The long-chain aliphatic hydrocarbon group-containing (meth)acrylates can be used alone or in combination of two or more.
[0163]
The amide group-containing monomer is represented by the following formula (2).
[0164]
[Chemical 8]

[0165]
In the above formula (2), R 3 is an organic residue having an ethylenically unsaturated double bond group, and is not particularly limited as long as it has a double bond between carbon atoms.
[0166]
Examples of R 3 include -C(=O)CR 21=CH 2, -CHR 21=CH 2, -CH 2CHR 21=CH 2 and the like, where R 21 is a hydrogen atom or a The following alkyl groups are included.
[0167]
That is, when R 21 is a hydrogen atom, -C(=O)CR 21=CH 2 is an acryloyl group, -CHR 21=CH 2 is a vinyl group, and -CH 2CHR 21=CH 2 is an allyl group.
[0168]
In addition, although R 3 contains at least an ethylenically unsaturated double bond group, it may also contain various other organic groups. Containing organic groups such as hydrogen groups, cyclic hydrocarbon groups, polyoxyalkylene groups, and polysiloxane groups (including those substituted with various substituents, but excluding those containing fluorine atoms) may
[0169]
In the above formula (2), R 4 is a monovalent monovalent having 7 to 30 carbon atoms (preferably 11 or more, more preferably 15 or more, and preferably 27 or less, more preferably 23 or less). It is a hydrocarbon group, preferably a chain hydrocarbon group or a cyclic hydrocarbon group, more preferably a chain hydrocarbon group, and still more preferably a linear saturated hydrocarbon group.
[0170]
In the above formula (2), R 5 is a divalent hydrocarbon group having 1 to 5 carbon atoms, preferably a chain hydrocarbon group, more preferably a linear hydrocarbon group (saturated hydrocarbon group). hydrogen group or unsaturated hydrocarbon group), branched hydrocarbon groups (saturated hydrocarbon group or unsaturated hydrocarbon group), and the like.
[0171]
Examples of such amide group-containing monomers include palmitic acid amide ethyl (meth) acrylate, stearic acid amide ethyl (meth) acrylate, behenic acid amide ethyl (meth) acrylate, myristate amide ethyl (meth) acrylate, and lauric acid amide ethyl (meth) acrylate. , isostearic acid ethyl amide (meth) acrylate, oleic acid ethyl amide (meth) acrylate, t-butylcyclohexylcaproic acid amide ethyl (meth) acrylate, adamantane carboxylic acid ethyl amide (meth) acrylate, naphthalene carboxylic acid amide ethyl (meth) acrylate, anthracene carboxylic acid Amido group-containing (meth)acrylates such as amidoethyl (meth)acrylate, palmitamide propyl (meth)acrylate, and stearamide propyl (meth)acrylate, for example, amide groups such as palmitate amidoethyl vinyl ether and stearamide ethyl vinyl ether containing vinyl ethers, for example, amide group-containing allyl ethers such as palmitic acid amide ethyl allyl ether and stearic acid amide ethyl allyl ether, preferably amide group-containing (meth)acrylates, more preferably amide group-containing (meth)acrylates, more preferably amide ethyl (meth) palmitate Acrylate, stearamidoethyl (meth)acrylate, or a combination thereof.
[0172]
When palmitic acid amide ethyl (meth) acrylate and stearic acid amide ethyl (meth) acrylate are used together, the stearic acid amide ethyl (meth) acrylate is, for example, 55% by mass or more, preferably 60 % by mass or more, more preferably 65% ​​by mass or more, and for example, 99% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less.
[0173]
The amide group-containing monomer can be used alone or in combination of two or more.
[0174]
In addition, the above monomer component can also contain a short-chain aliphatic hydrocarbon group-containing (meth)acrylate, if necessary.
[0175]
The short-chain aliphatic hydrocarbon group-containing (meth)acrylate is represented by the following formula (3).
[0176]
[Chemical 9]

[0177]
In the above formula (3), R6 represents a hydrogen atom or a methyl group.
[0178]
In the above formula (1), R 7 is a linear or branched short-chain aliphatic hydrocarbon group having 17 or less carbon atoms (for example, a linear alkyl group having 17 or less carbon atoms, the following branched alkyl groups).
[0179]
Specific examples of such short-chain aliphatic hydrocarbon group-containing (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, lauryl ( meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate and the like.
[0180]
　Short-chain aliphatic carbonization Hydrogen group-containing (meth)acrylates can be used alone or in combination of two or more.
[0181]
In addition, the monomer component can also contain a cyclic hydrocarbon group-containing (meth)acrylate, if necessary.
[0182]
The cyclic hydrocarbon group-containing (meth)acrylate is represented by the following formula (4).
[0183]
[Chemical 10]

[0184]
In formula (4) above, R 8 represents a hydrogen atom or a methyl group.
[0185]
In addition, in the above formula (4), R 9 represents a cyclic hydrocarbon group having 4 or more and 30 or less carbon atoms (eg, an alicyclic group, an aromatic group, etc.).
[0186]
Examples of such cyclic hydrocarbon group-containing (meth)acrylates include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl ( meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl ( Examples thereof include alicyclic group-containing (meth)acrylates such as meth)acrylates, and aromatic group-containing (meth)acrylates such as benzyl (meth)acrylate.
[0187]
The cyclic hydrocarbon group-containing (meth)acrylates can be used alone or in combination of two or more.
[0188]
In addition, if necessary, the monomer component may be the above monomer component (long-chain aliphatic hydrocarbon group-containing (meth) acrylate, amide group-containing monomer, short-chain aliphatic hydrocarbon group-containing (meth) acrylate and cyclic hydrocarbon group-containing (Meth)acrylates) and non-fluorine copolymerizable monomers can also be included.
[0189]
Examples of non-fluorine copolymerizable monomers include carboxyl group-containing monomers such as (meth)acrylic acid, vinyl ester monomers such as vinyl acetate, aromatic vinyl monomers such as styrene and vinyltoluene, and acrylic acid. hydroxyl group-containing monomers such as 2-hydroxyethyl and 4-hydroxybutyl acrylate; halogenated vinyl monomers such as vinyl chloride, vinyl bromide and vinyl iodide (excluding those containing a fluorine atom); , preferably halogenated vinyl monomers (excluding those containing a fluorine atom), more preferably vinyl chloride.
[0190]
The non-fluorine copolymerizable monomers can be used alone or in combination of two or more.
[0191]
The monomer component preferably contains long-chain aliphatic hydrocarbon group-containing (meth)acrylates and/or amide group-containing monomers, and more preferably contains only long-chain aliphatic hydrocarbon group-containing (meth)acrylates.
[0192]
Further, the monomer component preferably contains a long-chain aliphatic hydrocarbon group-containing (meth)acrylate and/or amide group-containing monomer and a non-fluorinated copolymerizable monomer, more preferably a long-chain aliphatic hydrocarbon containing only a group-containing (meth)acrylate and a non-fluorinated copolymerizable monomer, or containing a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, an amide group-containing monomer, and a non-fluorinated copolymerizable monomer, More preferably, it contains only long-chain aliphatic hydrocarbon group-containing (meth)acrylates, amide group-containing monomers and non-fluorine copolymerizable monomers.
[0193]
Then, the non-fluorine water-repellent compound is obtained by polymerizing the above monomer components.
[0194]
Specifically, the non-fluorine water-repellent compound comprises a long-chain aliphatic hydrocarbon group-containing (meth)acrylate and/or an amide group-containing monomer, and a short-chain aliphatic hydrocarbon group-containing (meth)acrylate blended as necessary, It is obtained by polymerizing a cyclic hydrocarbon group-containing (meth)acrylate blended as necessary and a non-fluorinated copolymerizable monomer blended as necessary under the conditions described later.
[0195]
As a result, a non-fluorine water-repellent compound is obtained.
[0196]
Such non-fluorine water-repellent compounds are polymers containing structural units derived from long-chain aliphatic hydrocarbon group-containing (meth)acrylate and/or amide group-containing monomers.
[0197]
If the non-fluorine water repellent compound is a polymer containing a structural unit derived from a long-chain aliphatic hydrocarbon group-containing (meth)acrylate and/or an amide group-containing monomer, the water repellent composition can be treated with the water repellent composition. It is possible to improve the water repellency of the water-treated material.
[0198]
Also, although the details will be described later, the polymerization of the monomer component is preferably carried out when the water repellent composition is prepared.
[0199]
A dendrimer-based water repellent can also be employed as the non-fluorine water repellent compound.
[0200]
Examples of dendrimer-based water repellents include chain polymer compounds that have a structure that is radial and regularly branched from the center.
[0201]
Examples of chain polymer compounds include Ecoplus (manufactured by Rudolph).
[0202]
The blending ratio of the non-fluorine water-repellent compound is, for example, 0.1 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass, with respect to 100 parts by mass as the total amount of the polyurethane resin compound and the non-fluorine water-repellent compound. Part by mass or more, more preferably 70 parts by mass or more, particularly preferably 85 parts by mass or more, and, for example, 99 parts by mass or less, preferably 96 parts by mass or less, more preferably 90 parts by mass or less be.
[0203]
The blending ratio of the non-fluorine water-repellent compound is, for example, 15% by mass or more and, for example, 30% by mass or less with respect to the water-repellent composition.
[0204]
If the blending ratio of the non-fluorine water-repellent compound is within the above range, the water repellency of the water-repellent treated material treated with this water repellent composition can be improved.
3. surfactant
A surfactant is added to the water repellent composition from the viewpoint of dispersing the polyurethane resin compound and the non-fluorine water repellent compound.
[0205]
Examples of surfactants include nonionic surfactants, anionic surfactants, and amphoteric surfactants.
[0206]
Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and glycerin fatty acid esters. , polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, Examples thereof include polyethylene glycol polypropylene glycol block copolymers, preferably glycerin fatty acid esters.
[0207]
Cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydro polyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride and the like.
[0208]
Examples of amphoteric surfactants include fatty acid betaine compounds such as alanine compounds, imidazolinium betaine compounds, amidobetaine compounds, laurylbetaine, and betaine acetate.
[0209]
The surfactant preferably includes a nonionic surfactant.
[0210]
The surfactant can be used alone or in combination of two or more.
[0211]
The mixing ratio of the surfactant is, for example, 10 parts by mass or more and, for example, 40 parts by mass or less with respect to 100 parts by mass as the total amount of the polyurethane resin compound and the non-fluorine water-repellent compound.
[0212]
The mixing ratio of the surfactant is, for example, 0.01% by mass or more and, for example, 1% by mass or less with respect to the water repellent composition.
4. liquid medium
The liquid medium contains water as an essential ingredient.
[0213]
In addition, the liquid medium further contains a solvent, if necessary.
[0214]
Examples of solvents include ketones such as acetone, methyl ethyl ketone and cyclohexanone; nitriles such as acetonitrile; alkyl esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; - Aliphatic hydrocarbons such as heptane, octane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, ethanol, propylene glycol, etc. Alcohols, for example, glycol ethers such as dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol, and the like, preferably glycol ethers.
[0215]
The blending ratio of the solvent is, for example, 5% by mass or more, preferably 15% by mass or more, and, for example, 30% by mass or less, relative to the liquid medium.
[0216]
The solvent can be used alone or in combination of two or more.
[0217]
The mixing ratio of the liquid medium is, for example, 150 parts by mass or more and, for example, 400 parts by mass or less with respect to 100 parts by mass as the total amount of the polyurethane resin compound and the non-fluorine water-repellent compound.
[0218]
The mixing ratio of the liquid medium is, for example, 50% by mass or more and, for example, 80% by mass or less with respect to the water repellent composition.
5. Other ingredients
The water repellent composition optionally contains at least one selected from the group consisting of blocked isocyanate compounds, silicone polymers and waxes.
[0219]
A blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is blocked with a blocking agent.
[0220]
If the water repellent composition contains a blocked isocyanate compound, the washing durability described below can be improved.
[0221]
Specific examples of blocked isocyanate compounds include hydrophobic compounds listed in JP-A-2017-222827, and preferably urethane compounds having 3,5-dimethylpyrazole as a blocking agent.
[0222]
The blocked isocyanate compound can also be used, for example, as an aqueous dispersion that is emulsified by mixing with an emulsifier (described later).
[0223]
In such a case, the solid content concentration of the aqueous dispersion is, for example, 10% by mass or more and, for example, 40% by mass or less.
[0224]
The blocked isocyanate compound can be used alone or in combination of two or more.
[0225]
A silicone polymer is a reaction product (hydrosilylation reaction product) of a silicone having SiH groups and an aromatic compound having a vinyl group and/or an α-olefin.
[0226]
If the water repellent composition contains a silicone polymer, it is possible to improve the water repellency of the water repellent treated object treated with this water repellent composition.
[0227]
Examples of silicones having SiH groups include methylhydrogensilicone (degree of polymerization: 10 to 200), copolymers of dimethylsiloxane and methylhydrogensiloxane, and preferably methylhydrogensilicone. .
[0228]
Si Silicones having an H group can be used alone or in combination of two or more.
[0229]
Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allylphenyl ether, allylnaphthylether, allyl-p-cumylphenylether, allyl-o-phenylphenylether, allyl-tri (Phenylethyl)-phenyl ether, allyl-tri(2-phenylpropyl)phenyl ether and the like.
[0230]
The aromatic compound having a vinyl group can be used alone or in combination of two or more.
[0231]
Examples of α-olefins include ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- - α-olefins having 2 to 30 carbon atoms such as tetradecene, 1-hexadecene, 1-octadecene and 1-hexacosene, preferably ethene and 1-hexacosene, more preferably this water repellent composition From the viewpoint of improving the water repellency of the water repellent treated material treated with, 1-hexacosene can be mentioned.
[0232]
The α-olefin can be used alone or in combination of two or more.
[0233]
In order to hydrosilylate a silicone having a SiH group with an aromatic compound having a vinyl group and/or an α-olefin, the aromatic compound having a vinyl group and/or α- Blend olefin.
[0234]
The blending ratio of the silicone having a SiH group, the aromatic compound having a vinyl group, and the α-olefin is appropriately selected according to the SiH group equivalent or the number average molecular weight of the silicone having a SiH group.
[0235]
The aromatic compound having a vinyl group and/or the α-olefin can be mixed as a whole or divided.
[0236]
In the above hydrosilylation reaction, if necessary, a hydrosilylation catalyst can be blended in an appropriate proportion.
[0237]
Examples of hydrosilylation catalysts include platinum and palladium, preferably platinum.
[0238]
The hydrosilylation catalyst can be used alone or in combination of two or more.
[0239]
In addition, in the above hydrosilylation reaction, if necessary, a known organic solvent can be blended in an appropriate proportion.
[0240]
In the above hydrosilylation reaction, as reaction conditions, the reaction temperature is, for example, 50° C. or higher and, for example, 90° C. or lower, and the reaction time is, for example, 1 hour or longer. , 6 hours or less.
[0241]
The above hydrosilylation reaction is carried out until the SiH group peak of the silicone having SiH groups disappears according to infrared spectroscopy.
[0242]
As a result, a silicone polymer is obtained.
[0243]
Among such silicone polymers, preferably a reaction product of a silicone having a SiH group and an α-olefin, more preferably a reaction product of a methylhydrogensilicone and ethene (dimethylpolysiloxane), methyl A reaction product of hydrogensilicone and 1-hexacosene, more preferably a mixture of methylhydrogensilicone and 1-hexacosene from the viewpoint of improving the water repellency of a water repellent treated object treated with this water repellent composition. reaction products.
[0244]
The silicone polymer is a water dispersion obtained by mixing and emulsifying the above-described surfactant (preferably sorbitan fatty acid ester), water, the above-described solvent, and emulsifier (preferably polyoxyethylene alkyl ether) (described later). It can also be used as a liquid.
[0245]
In such a case, the solid content concentration of the aqueous dispersion is, for example, 10% by mass or more and, for example, 40% by mass or less.
[0246]
The silicone polymer can be used alone or in combination of two or more.
[0247]
Examples of waxes include natural waxes and synthetic waxes.
[0248]
Examples of natural waxes include petroleum waxes such as paraffin wax and microcrystalline wax, and natural waxes such as plant waxes such as carnauba wax and candelilla wax.
[0249]
Examples of synthetic wax include polyethylene wax.
[0250]
The wax is preferably natural wax, more preferably paraffin wax.
[0251]
The wax can also be used as an aqueous dispersion obtained by mixing and emulsifying the above surfactant (preferably sorbitan fatty acid ester), water, and an emulsifier (preferably polyoxyethylene alkyl ether) (described later). .
[0252]
In such a case, the solid content concentration of the aqueous dispersion is, for example, 10% by mass or more and, for example, 40% by mass or less.
[0253]
If the water repellent composition contains wax, the water repellency of the water repellent treated object treated with this water repellent composition can be improved.
[0254]
The wax can be used alone or in combination of two or more.
[0255]
The blending ratio of at least one selected from the group consisting of a blocked isocyanate compound, a silicone polymer and a wax is, for example, 5 parts by mass or more with respect to 100 parts by mass of the total amount of the polyurethane resin compound and the non-fluorine water-repellent compound. , or, for example, 20 parts by mass or less.
[0256]
Also, the blending ratio of at least one selected from the group consisting of a blocked isocyanate compound, a silicone polymer and a wax is 1% by mass or more and, for example, 10% by mass or less, relative to the water repellent composition. is.
[0257]
When the water repellent composition contains a blocked isocyanate compound, the blending ratio of the blocked isocyanate compound is, for example, 5% by mass with respect to the total amount of the polyurethane composition, the non-fluorine water repellent compound and the blocked isocyanate compound. or more and, for example, 20% by mass or less.
[0258]
Further, when the water repellent composition contains a silicone polymer, the proportion of the silicone polymer is, for example, 5% by mass with respect to the total amount of the polyurethane composition, the non-fluorine water repellent compound and the silicone polymer. or more and, for example, 20% by mass or less.
[0259]
Further, when the water repellent composition contains wax, the blending ratio of the wax is, for example, 5% by mass or more with respect to the total amount of the polyurethane composition, the non-fluorine water repellent compound and the wax, and For example, it is 20% by mass or less.
6. Method for producing water repellent composition
A water repellent composition is obtained by mixing a polyurethane resin compound, a non-fluorine water repellent compound, a surfactant, and a liquid medium.
[0260]
Specifically, the water repellent composition is preferably produced by polymerizing the monomer components constituting the non-fluorine water repellent compound in the presence of a polyurethane resin compound, a surfactant, and a liquid medium. It is obtained by a method of producing a fluorine water-repellent compound (hereinafter referred to as the first method).
[0261]
Examples of the polymerization method include suspension polymerization and emulsion polymerization, preferably emulsion polymerization from the viewpoint of obtaining an emulsion of a non-fluorine water-repellent compound.
[0262]
When emulsion polymerization is employed, first, the above monomer components (specifically, long-chain aliphatic hydrocarbon group-containing (meth)acrylate and / or amide group-containing monomers, and optionally blended short-chain aliphatic hydrocarbons group-containing (meth)acrylate, optionally blended cyclic hydrocarbon group-containing (meth)acrylate, and optionally blended non-fluorinated copolymerizable monomer), all or part of it, a polyurethane resin compound, and a surfactant and a liquid medium to prepare a mixture.
[0263]
The mixing ratio of the surfactant is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass, with respect to 100 parts by mass of the total amount of the monomer components. It is below the department.
[0264]
The mixing ratio of the liquid medium is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, and for example, 400 parts by mass or less, preferably 300 parts by mass, with respect to 100 parts by mass of the total amount of the monomer components. It is below.
[0265]
Then, add an emulsifier to this mixture.
[0266]
Emulsifiers include known emulsifiers, such as cationic emulsifiers and anionic emulsifiers.
[0267]
In addition, the above surfactants can also be used as emulsifiers.
[0268]
In addition, the emulsifier preferably contains a reactive emulsifier. When the emulsifier contains a reactive emulsifier, the non-fluorine water-repellent compound (the polymer of the above monomer components) is a polymer containing structural units derived from the reactive emulsifier.
[0269]
If the non-fluorine water-repellent compound is a polymer containing a structural unit derived from a reactive emulsifier, the product stability of the water dispersion (repellent agent composition) is improved without lowering the water repellency. .
[0270]
A reactive emulsifier is an emulsifying dispersant having radical reactivity, that is, an emulsifier having one or more polymerizable unsaturated groups in the molecule, and an emulsifier that can be copolymerized with the above monomer components.
[0271]
Examples of reactive emulsifiers include reactive emulsifiers disclosed in JP-A-2017-25440, and preferably reactive emulsifiers represented by the following formula (5).
[0272]
[Chemical 11]

[0273]
In the above formula (5), R 10 represents an organic residue having an ethylenically unsaturated double bond group with 12 to 20 carbon atoms.
[0274]
R 11 represents an oxyalkylene group having 2 to 10 carbon atoms, preferably an oxyethylene group
If the reactive emulsifier is the reactive emulsifier represented by the above formula (5), the product stability of the aqueous dispersion (repellent agent composition) is improved without lowering the water repellency.
[0275]
Preferred examples of the reactive emulsifier represented by the above formula (5) include polyoxyethylene alkylphenol and the like.
[0276]
The emulsifier can be used alone or in combination of two or more.
[0277]
The mixing ratio of the emulsifier is, for example, 5 parts by mass or more and, for example, 18 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer components.
[0278]
Also, the mixing ratio of the emulsifier is, for example, 8 parts by mass or more and, for example, 20 parts by mass or less with respect to 100 parts by mass as the total amount of the polyurethane resin compound and the non-fluorine water-repellent compound.
[0279]
Also, the mixing ratio of the emulsifier is, for example, 0.5% by mass or more and, for example, 5% by mass or less with respect to the water repellent composition.
[0280]
Then, after mixing the above components, the mixed liquid is stirred and ultrasonic waves are applied to the mixed liquid to emulsify the mixed liquid.
[0281]
As a method of stirring, for example, a homomixer (homomixer), an ultrasonic homogenizer, a pressurized homogenizer, a milder, a porous membrane press-fitting disperser, and the like are used, and a homomixer is preferably used.
[0282]
The stirring conditions are appropriately set, and when a homomixer is used, the rotation speed is set to, for example, 500 rpm or more and, for example, 10000 rpm or less. The stirring time is, for example, 0.5 minutes or more, and is, for example, 10 minutes or less, preferably 5 minutes or less. The stirring temperature is, for example, 50° C. or higher and, for example, 90° C. or lower.
[0283]
Next, in this mixture, if a part of the monomer component was blended when the above mixture was prepared, the rest of the above monomer component is blended.
[0284]
Next, a polymerization initiator is blended into this mixture.
[0285]
Polymerization Examples of initiators include azo compounds such as azobisisobutylamidine dihydrochloride and azobisisobutyronitrile; water-soluble polymerization initiators such as persulfates such as potassium persulfate and ammonium persulfate; Oil-soluble polymerization initiators such as organic peroxides such as peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, etc., preferably includes azo compounds, more preferably azobisisobutyronitrile.
[0286]
The mixing ratio of the polymerization initiator is, for example, 0.01 parts by mass or more and, for example, 10 parts by mass or less with respect to 100 parts by mass of the monomer component.
[0287]
In addition, a chain transfer agent can be added to this mixed solution, if necessary.
[0288]
Chain transfer agents include, for example, mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (eg, having 1 to 30 carbon atoms)), sodium hypophosphite, sodium hydrogen sulfite, and the like. Examples thereof include inorganic salts, preferably lauryl mercaptan.
[0289]
The blending ratio of the chain transfer agent is, for example, 0.01 parts by mass or more and, for example, 10 parts by mass or less with respect to 100 parts by mass of the monomer component.
[0290]
Then, this mixed solution is heated to polymerize the monomer components.
[0291]
As for the heating conditions, the heating temperature is, for example, 40° C. or higher and, for example, 80° C. or lower, and the heating time is, for example, 1 hour or longer and, for example, 6 hours or shorter.
[0292]
As a result, an emulsion of the non-fluorine water-repellent compound is obtained, and a dispersion of the water-repellent composition containing the polyurethane resin compound, the non-fluorine water-repellent compound (emulsion), the surfactant, and the liquid medium is obtained. .
[0293]
In the first method, the monomer components constituting the fluorine-free water-repellent compound are polymerized in the presence of a polyurethane resin compound, a surfactant, and a liquid medium. A polyurethane resin compound can also be added after polymerizing the monomer components (second method).
[0294]
Alternatively, the monomer component may be polymerized first to prepare a non-fluorine water-repellent compound, and then the obtained non-fluorine water-repellent compound, a polyurethane resin compound, a surfactant and a liquid medium may be blended (third Method).
[0295]
In the third method, examples of polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.
[0296]
When solution polymerization is employed, the monomer components are dissolved in an organic solvent in the presence of the polymerization initiator described above, and after purging with nitrogen, the mixture is heated while stirring.
[0297]
The mixing ratio of the polymerization initiator is, for example, 0.01 parts by mass or more, and is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, with respect to 100 parts by mass of the monomer component.
[0298]
Examples of the organic solvent include the solvents listed for the liquid medium above.
[0299]
The mixing ratio of the organic solvent is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, and for example, 2000 parts by mass or less, preferably 1000 parts by mass or less, relative to 100 parts by mass of the monomer component. be.
[0300]
As the heating conditions, the heating temperature is, for example, 30° C. or higher and, for example, 120° C. or lower, and the heating time is, for example, 1 hour or longer and, for example, 10 hours or shorter.
[0301]
As a result, a non-fluorine water-repellent compound is obtained.
[0302]
Then, after the non-fluorine water-repellent compound is produced by solution polymerization, the organic solvent is removed, and the non-fluorine water-repellent compound is added to the surfactant and the liquid medium together with the polyurethane resin compound to obtain the non-fluorine water-repellent compound. can be prepared.
[0303]
Among the methods for producing the water repellent composition described above, the first method is preferably adopted from the viewpoint of improving the water repellency of the water repellent treated object treated with this water repellent composition.
[0304]
The water repellent composition comprises a polyurethane resin compound containing at least one selected from the group consisting of a first polyurethane resin compound, a second polyurethane resin compound, and a third polyurethane resin compound, and a non-fluorine repellent Aqueous compounds.
[0305]
Therefore, it is possible to improve the water repellency of the water repellent treated object treated with this water repellent composition.
[0306]
The water repellent composition can be used, for example, as a water repellent treatment liquid diluted with water (ion-exchanged water).
[0307]
By impregnating a textile product (textile product) with such a water repellent treatment liquid, it is possible to impart water repellency to the textile product.
[0308]
In other words, the textile product is a water repellent product treated with the water repellent composition.
[0309]
Examples of fibers include natural fibers such as cotton or wool, chemical fibers such as viscose rayon and Rheocell, and synthetic fibers such as polyester, polyamide, acrylic, and polyurethane fibers. Textile products are products made from the fibers described above, and include, for example, fabrics (woven fabrics, knitted fabrics and non-woven fabrics).
[0310]
This textile product is water-repellent treated with the above-mentioned water-repellent agent composition, and is therefore excellent in water-repellency.
[0311]
In the above description, textile products are treated with water repellency, but the water repellent treated material to be water repellent treated with this water repellent composition is not particularly limited, and examples thereof include paper, stone, glass, metal, and cement. etc.
Example
[0312]
Specific numerical values ​​such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are described in the above "Mode for Carrying Out the Invention", the corresponding mixing ratio (content ratio ), physical properties, parameters, etc. can. In the description below, "parts" and "%" are based on mass unless otherwise specified.
1. Preparation of primary aliphatic polyisocyanate derivatives
Synthesis example 1 (isocyanurate derivative of hexamethylene diisocyanate)
In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, Inc., trade name: Takenate 700), 2 , 6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenolic antioxidant) 0.25 parts by mass, tetraphenyl dipropylene glycol diphosphite (organic phosphorous acid After mixing 0.25 parts by weight of ester, co-catalyst), 10.7 parts by weight of 1,3-butanediol were added to the mixture and nitrogen was introduced into the liquid phase for 1 hour. Thereafter, the mixture was heated to 80°C, reacted for 3 hours, and then cooled to 60°C. After that, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanurate catalyst and reacted for 1.5 hours. After that, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. After that, this reaction mixture is passed through a thin film distillation apparatus (temperature 150° C., degree of vacuum 93.3 Pa) and distilled until the amount of residual HDI monomer becomes 0.5% or less, and the first aliphatic polyisocyanate is obtained. A derivative (isocyanurate derivative of hexamethylene diisocyanate) was obtained. The obtained first aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functional group number of 3.0.
2. Preparation of polyurethane resin compound
　　Production example 1 (first polyurethane resin compound)
100.20 g of the first aliphatic polyisocyanate derivative of Synthesis Example 1 as the first aliphatic polyisocyanate derivative and the first long-chain active hydrogen compound were placed in a reactor equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas inlet tube. As a solution, 67.60 g of Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) and 22.30 g of olein alcohol were mixed and reacted at 110 ° C. in a nitrogen atmosphere for 4 hours until the concentration of isocyanate groups reached 3.67%. .
[0313]
Then, the reaction solution was cooled to 80°C, 9.90 g of N-methyldiethanolamine was added as a cationic active hydrogen compound, and reacted at 80°C for 1 hour.
[0314]
Then, 50.00 g of methyl ethyl ketone was added as a solvent and reacted at 80°C until the disappearance of the isocyanate group could be confirmed by infrared absorption spectrum.
[0315]
Then, 57.69 g of methyl el ketone was added to the reaction liquid, the temperature was raised to 80°C, and the mixture was mixed until the reaction liquid was completely dissolved, and then cooled to 75°C.
[0316]
After that, 18.96 g of acetic acid was added as an acid compound to neutralize it.
[0317]
Then, while maintaining the reaction solution at 75°C, 800.0 g of deionized water heated to 70°C was gradually added to emulsify (internal emulsify).
[0318]
Next, in an evaporator, the solvent was removed at a water bath temperature of 60°C under reduced pressure until the solid content concentration reached 20% by mass or more.
[0319]
Then, an aqueous dispersion containing the first polyurethane resin compound was obtained by adjusting with ion-exchanged water so that the solid content concentration excluding the acid compound (acetic acid) was 20% by mass.
[0320]
　　Production example 2 (second polyurethane resin compound)
116 g of sorbitan tristearate and 150 g of 4-methyl-2-pentanone (MIBK) were charged into a 500 mL four-necked flask equipped with a stirrer, thermometer, and reflux tube. Then, in order to remove excess water vapor from the mixture, the mixture was stirred while maintaining the temperature of the mixture at 70°C, the mixture was refluxed for 1 hour, and then allowed to cool to 50°C. Then, while maintaining stirring, 30 g of Desmodur N-100 (a biuret derivative of hexamethylene diisocyanate, Covestro) was added dropwise from a dropping funnel to the mixture. After completion of dropping, one drop of dibutyltin dilaurate was added as a catalyst and reacted at 80° C. for 1 hour. Then, 25 g of sorbitan monostearate was added and further reacted at 80° C. for 4 hours.
[0321]
Then, after cooling to 60°C, the reaction solution was recovered, and the reaction solution was slowly mixed with water at 60°C containing arbitrary amounts of cationic emulsifier and polyoxyethylene alkyl ether. The mixture was stirred at 6000 rpm for 1 minute using a homomixer, and then emulsified and dispersed with ultrasonic waves for 15 minutes. Then, after removing the solvent (MIBK) by depressurization, the concentration was adjusted by adding pure water to obtain an aqueous dispersion containing the second polyurethane resin compound with a solid concentration of 20%.
[0322]
　　Production example 3 (third polyurethane resin compound)
150 g of methyl ethyl ketone (MEK) and 51 g of stearyl alcohol were charged into a 500 mL four-necked flask equipped with a stirrer, thermometer, and reflux tube. Then, in order to remove excess water vapor from the mixture, the mixture was stirred while maintaining the temperature of the mixture at 70°C, the mixture was refluxed for 1 hour, and then allowed to cool to 50°C. Then, 30 g of Desmodur N3200A (a biuret derivative of hexamethylene diisocyanate, manufactured by Covestro) was added to the mixed solution, and the mixture was further reacted at 80° C. for 4 hours.
[0323]
Then, after cooling to 60°C, the reaction liquid was recovered, and the reaction liquid was slowly mixed with water at 60°C containing an arbitrary amount of polyoxyethylene alkyl ether. This mixed liquid was stirred with a homomixer at 6000 rpm for 1 minute, and then emulsified and dispersed with ultrasonic waves for 15 minutes.
[0324]
Then, after the solvent (MEK) was removed by depressurization, pure water was added to adjust the concentration to obtain an aqueous dispersion containing the third polyurethane resin compound with a solid content concentration of 20%.
3. Non-fluorine repellent Preparation of dispersion containing aqueous compound, surfactant and liquid medium
　　Production example 4
In a 500 ml plastic container, 30 g of a water-soluble glycol-based solvent and 120 g of pure water as liquid medium, 40 g of stearyl acrylate as long-chain aliphatic hydrocarbon group-containing (meth)acrylate, 2 g of sorbitan fatty acid ester as surfactant, As emulsifiers, 2 g of a cationic emulsifier and 6 g of polyoxyethylene alkyl ether were charged, heated to 80° C., stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasonic waves for 15 minutes.
[0325]
Next, this mixture was transferred to a 500 ml autoclave, and after purging with nitrogen, 0.2 g of lauryl mercaptan as a chain transfer agent and 20 g of vinyl chloride as a non-fluorine copolymerizable monomer were charged. Furthermore, 1 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, the temperature was raised to 60° C., and reaction was performed for 4 hours to obtain an aqueous dispersion of a polymer (non-fluorine water-repellent compound). This dispersion is further diluted with pure water to obtain an aqueous dispersion of a non-fluorine water-repellent compound having a solid concentration of 30% (specifically, a dispersion containing a non-fluorine water-repellent compound, a surfactant and a liquid medium). was prepared.
[0326]
Manufacturing example 5 to manufacturing example 7
According to Table 1, a dispersion containing a non-fluorine water-repellent compound, a surfactant, and a liquid medium was prepared in the same manner as in Production Example 4, except that the formulation was changed.
4. Preparation of silicone polymer
Manufacturing example 8
A 200 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube was charged with 12 g of methyl hydrogen silicone oil (SiH:SiCH3 molar ratio measured by 1H NMR = 50:50) and 0.02 g of a platinum catalyst. is. Then, 36 g of 1-hexacosene was charged into the dropping funnel, and 1-hexacosene was dropped from the dropping funnel while maintaining the temperature at 70°C. After completion of the dropwise addition, the mixture was further reacted at 70° C. for 3 hours. It was confirmed by infrared spectroscopy (IR) that the SiH peak had disappeared, and 47 g of a solid silicone polymer was obtained.
[0327]
Next, 28 g of silicone polymer, 5.6 g of water-soluble glycol-based solvent, 60 g of pure water, 1.7 g of sorbitan fatty acid ester, 0.7 g of polyoxyethylene alkyl ether, and 0.6 g of cationic emulsifier were charged into a 250 ml glass container, After heating to 75° C. and stirring with a homomixer at 2000 rpm for 1 minute, the mixture was emulsified and dispersed with ultrasonic waves for 10 minutes to obtain an aqueous dispersion of a silicone polymer. After that, pure water was added to prepare an aqueous dispersion of a silicone polymer having a solid content concentration of 30% by mass.
5. Wax preparation
　　Production example 9
150 g of paraffin wax (melting point: 75°C), 350 g of pure water, 4.5 g of polyoxyethylene alkyl ether, and 3 g of sorbitan fatty acid ester are placed in a pressure reaction vessel and sealed. Aqueous dispersions of waxes were prepared by high pressure emulsification for 30 minutes under low pressure. Thereafter, pure water was added to prepare an aqueous dispersion of wax having a solid content of 30%.
6. Water repellent composition

Example 1
Dispersion containing 2.5 g of the polyurethane composition of Production Example 1 (solid content concentration 20% by mass) and the non-fluorine water-repellent compound of Production Example 4, a surfactant, and a liquid medium (solid content concentration 30% by mass) 31 .7 g was mixed to prepare a water repellent composition.
[0328]
Examples 2 to 30, 35 and 36
A water repellent composition was prepared according to Tables 2 to 5 in the same manner as in Example 1, except that the formulation was changed.
[0329]
In Tables 2 to 5, each component (polyurethane composition, non-fluorine water-repellent compound, silicone polymer, wax , block isocyanate compound) is shown as a blending ratio (% by mass) of an effective amount.
[0330]
In addition, in Tables 2 to 5, the stearyl group-containing amide acrylate is stearamide ethyl acrylate.
[0331]
In addition, in Tables 2 to 5, polyoxyethylene alkylphenol is Ramtel PD-420 manufactured by Kao Corporation.
[0332]
In addition, in Tables 2 to 5, the dendrimer-based water repellent is specifically Ecoplus (manufactured by Rudolph).
[0333]
Further, in Tables 2 to 5, the blocked isocyanate composition is specifically a urethane compound having 3,5-dimethylpyrazole as a blocking agent.

Example 31
In a 500 ml plastic container, 25.5 g of a water-soluble glycol-based solvent, 113 g of pure water, 34 g of stearyl acrylate as a long-chain aliphatic hydrocarbon group-containing (meth)acrylate, and sorbitan fatty acid ester as a surfactant are placed in a 500 ml plastic container. 1.7 g of cationic emulsifier and 5.1 g of polyoxyethylene alkyl ether as emulsifiers; 11 g of silicone polymer of Production Example 8 as silicone polymer; 28 g of an aqueous dispersion of a polyurethane composition (solid concentration: 20% by mass) was charged, heated to 80° C., stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed with ultrasonic waves for 15 minutes. This dispersion liquid was transferred to a 500 ml autoclave, and after purging with nitrogen, 0.17 g of lauryl mercaptan as a chain transfer agent and 17 g of vinyl chloride as a non-fluorine copolymerizable monomer were charged. Further, 0.85 g of an azo group-containing water-soluble initiator was added as a polymerization initiator, heated to 60° C., and allowed to react for 4 hours to prepare an aqueous dispersion of the water repellent composition. After that, pure water was added to prepare an aqueous dispersion of a liquid drug composition with a solid content of 30%.
[0334]
Table 4 shows the blending ratio of effective amounts of each component (polyurethane composition, non-fluorine water-repellent compound and silicone polymer) to the polyurethane composition, non-fluorine water-repellent compound and silicone polymer in Example 31 ( mass %).
[0335]
Example 32 to Example 34
A water repellent composition was prepared according to Table 6 in the same manner as in Example 31, except that the formulation was changed.
[0336]
Table 4 shows the effective amount of each component (polyurethane composition, non-fluorine water-repellent compound and silicone polymer) for the polyurethane composition, non-fluorine water-repellent compound and silicone polymer in Examples 32 to 34. The compounding ratio (% by mass) is shown.

Comparative Examples 1 to 17
A water repellent composition was prepared in the same manner as in Example 1 according to Tables 4 and 5, except that the formulation was changed.
7. evaluation
(Average number of isocyanate functional groups)
The average isocyanate functional group number of the aliphatic polyisocyanate derivative of each synthesis example is the isocyanate group concentration A of the aliphatic polyisocyanate derivative, the solid content concentration B, and the gel permeation chromatography measured under the following equipment and conditions. It was calculated from the number average molecular weight C by the following formula (6).
[0337]
Average number of isocyanate functional groups = A/B x C/42.02 (6)
(Wherein, A represents the isocyanate group concentration of the aliphatic polyisocyanate derivative, B represents the solid content concentration, and C represents the number average molecular weight.)
(Measurement conditions for number average molecular weight)
Apparatus: HLC-8220GPC (manufactured by Tosoh)
Column: TSKgelG1000HXL, TSKgelG2000HXL, and TSKgelG3000HXL (manufactured by Tosoh) connected in series
Detector: Differential refractometer
Injection volume: 100 μL
Eluent: Tetrahydrofuran
Flow rate: 0.8mL/min
Temperature: 40°C
Calibration curve: standard polyethylene oxide in the range of 106 to 22450 (manufactured by Tosoh, trade name: TSK standard polyethylene oxide)
(Water repellency evaluation)

　The water repellent composition of each example and each comparative example was diluted with tap water to prepare 1000 g of a test liquid having a solid content concentration of 1.0% by mass.
[0338]
Next, after impregnating a test cloth (urethane/polyester mixed fabric, urethane/nylon mixed fabric, polyester fabric, and nylon fabric) with this test liquid 1, it is passed through a mangle, and the test cloth is placed at 160 ° C. for 1 minute with a pin tenter. dried and cured.

The water repellency of each of the test cloths described above was evaluated according to the spray method of JIS-L-1092 (AATCC-22).
[0339]
The water repellency was evaluated according to the criteria shown below. In addition, it means that water repellency is so favorable that a score is large. The results are shown in Tables 2-5.
100 No wetting or adhesion of water droplets was observed on the surface.
90　The surface was not wetted, but small water droplets were observed.
80 Wetness on small individual water droplets was observed on the surface.
70 Wetness was observed on half of the surface, and a state in which small individual wettings permeated the fabric was observed.
50 Wetness was observed on the entire surface.
0 Wetness was observed on the entire surface and back surface.

For each of the test cloths described above, according to the Bundesmann test described in JIS-L-1092 (C) method, the rainfall amount is 80 cc / min, the rainwater temperature is 20 ° C., and the rainfall time is 1 minute. The amount of water leakage (mL) was measured. The amount of water leakage indicates the amount of water (ml) that passed through the surface of the fabric during the Bundesmann test. The results are shown in Tables 2-5.

For each of the test cloths described above, the water repellency of the test cloth was evaluated according to JIS L-0217 103 after being washed 20 times and then dried in a tumbler (60°C for 30 minutes). The results are shown in Tables 2-5.
[0340]
[table 1]

[0341]
[Table 2]

[0342]
[Table 3]

[0343]
[Table 4]

[0344]
[Table 5]

[0345]
[Table 6]

[0346]
Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an illustration and should not be construed as limiting. Variations of the invention that are obvious to those skilled in the art are intended to be included in the following claims.
Industrial applicability
[0347]
The water repellent composition and the method for producing the water repellent composition of the present invention can be used for various industrial products, and can be suitably used for surface treatment agents, for example. The textile product of the present invention is suitably used for manufacturing various industrial products.
The scope of the claims
[Claim 1]
　Containing a polyurethane resin compound, a non-fluorine water-repellent compound, a surfactant, and a liquid medium,
The polyurethane resin compound is
The following (A) first polyurethane resin compound,
The following (B) second polyurethane resin compound,
A water repellent composition comprising at least one selected from the group consisting of (C) the third polyurethane resin compound below.
(A) a first aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more;
a first long-chain active hydrogen compound having both a hydrocarbon group with 12 to 30 carbon atoms and an active hydrogen group;
a cationic active hydrogen compound having both an active hydrogen group and a cationic group,
　It is a reaction product between a cationic group and an acid compound that forms a salt,
A first polyurethane resin compound having a hydrocarbon group concentration of 30% or more and 85% or less.
(B) an isocyanate compound;
selected from the group consisting of alkylsorbitan having an alkyl group having 12 to 30 carbon atoms, alkyl citrate having an alkyl group having 12 to 30 carbon atoms and pentaerythritol ester having an alkyl group having 12 to 30 carbon atoms A second polyurethane resin compound comprising a reaction product with at least one.
(C) a second aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more and a second long-chain active hydrogen compound having both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group; 3 Polyurethane resin compounds.
[Claim 2]
The ratio of the non-fluorine water-repellent compound to the total amount of 100 parts by mass of the polyurethane resin compound and the non-fluorine water-repellent compound is2. The water repellent composition according to claim 1, which is 0.1 parts by mass or more and 99 parts by mass or less.
[Claim 3]
The non-fluorine water-repellent compound is a polymer containing structural units derived from a long-chain aliphatic hydrocarbon group-containing (meth)acrylate represented by the following formula (1) and/or an amide group-containing monomer represented by the following formula (2) The water repellent composition according to claim 1, characterized in that
[Chemical 1]

(In formula (1) above, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a linear or branched long-chain aliphatic hydrocarbon group having 18 to 30 carbon atoms. )
[Chemical 2]

(In formula (2) above, R 3 represents an organic residue having an ethylenically unsaturated double bond group, R 4 represents a monovalent hydrocarbon group having 7 to 30 carbon atoms, and R 5 represents a divalent hydrocarbon group having 1 to 5 carbon atoms.)
[Claim 4]
The water repellent composition according to claim 3, wherein the non-fluorine water repellent compound is a polymer containing a structural unit derived from a reactive emulsifier.
[Claim 5]
The water repellent composition according to claim 4, wherein the reactive emulsifier is represented by the following formula (3).
[Chemical 3]

(In the above formula (3), R 10 represents an organic residue having an ethylenically unsaturated double bond group having 12 to 20 carbon atoms, and R 11 represents an oxyalkylene group having 2 to 10 carbon atoms. show.)
[Claim 6]
The water repellent composition according to claim 1, wherein the non-fluorine water repellent compound is a dendrimer water repellent.
[Claim 7]
The water repellent composition according to claim 1, comprising at least one selected from the group consisting of a blocked isocyanate compound, a silicone polymer and a wax.
[Claim 8]
The water repellent composition according to claim 1, wherein the first aliphatic polyisocyanate derivative contains an isocyanurate derivative of an aliphatic polyisocyanate.
[Claim 9]
In the cationic active hydrogen compound of the first polyurethane resin compound,
the cationic group is a tertiary amino group,
the active hydrogen group is a hydroxyl group,
The water repellent composition according to claim 1, wherein the cationic active hydrogen compound has two or more hydroxyl groups per molecule.
[Claim 10]
A method for producing the water repellent composition according to claim 3,
Production of a water repellent composition, characterized in that the non-fluorine water repellent compound is produced by polymerizing the monomer component in the presence of the polyurethane resin compound, the surfactant, and the liquid medium. Method.
[Claim 11]
A textile product characterized by being a water-repellent product treated with the water-repellent composition according to claim 1.