Invention name: Polyurethane resin composition, repellent agent, textile water repellent agent and antifouling coating agent
Technical field
[0001]
TECHNICAL FIELD The present invention relates to a polyurethane resin composition, a repellent agent, a water repellent agent for fibers, and an antifouling coating agent. It relates to a liquid agent and an antifouling coating agent containing the polyurethane resin composition.
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 fluorine-free water repellent, for example, a compound that is a reaction product of a polyisocyanate compound and an alkylsorbitan has been proposed (see Patent Document 1, for example).
prior art documents
patent literature
[0005]
Patent Document 1: Japanese Patent Publication No. 2016-524628
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0006]
In recent years, non-fluorine-based water repellents are required to have improved water repellency.
[0007]
Non-fluorine-based water repellents are also required to have washing durability against textiles.
[0008]
The present invention provides a polyurethane resin composition that is excellent in water repellency and washing durability to fibers, a repellent agent containing the polyurethane resin composition, a fiber water repellent agent containing the polyurethane resin composition, and a polyurethane resin composition thereof. To provide an antifouling coating agent containing
Means to solve problems
[0009]
The present invention [1] comprises an aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more, a long-chain active hydrogen compound having both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group, a cationic group and an active hydrogen A polyurethane resin composition containing a reaction product of a cationic active hydrogen compound having both a group and an acid compound that forms a salt with the cationic group, wherein the concentration of the hydrocarbon group is 30% or more and 85% or less. is.
[0010]
The present invention [2] includes the polyurethane resin composition according to [1] above, wherein the aliphatic polyisocyanate derivative includes an isocyanurate derivative of an aliphatic polyisocyanate.
[0011]
The present invention [3] is the cationic active hydrogen compound, wherein the cationic group is a tertiary amino group, the active hydrogen group is a hydroxyl group, and the cationic active hydrogen compound contains 2 It contains the polyurethane resin composition described in [1] or [2] above, which has one or more hydroxyl groups.
[0012]
The present invention [4] includes the polyurethane resin composition according to any one of [1] to [3] above, wherein the acid compound contains an organic acid.
[0013]
The present invention [5] includes a repellent agent containing the polyurethane resin composition according to any one of [1] to [4] above.
[0014]
The present invention [6] contains a fiber water repellent agent containing the polyurethane resin composition according to any one of [1] to [4] above.
[0015]
The present invention [7] contains an antifouling coating agent containing the polyurethane resin composition according to any one of [1] to [4] above.
Effect of the invention
[0016]
The polyurethane resin composition of the present invention contains a reaction product obtained using a long-chain active hydrogen compound, and has a predetermined concentration of hydrocarbon groups. Therefore, this polyurethane resin composition is excellent in water repellency.
[0017]
In addition, this polyurethane resin composition contains a reaction product obtained using a cationic active hydrogen compound.
[0018]
Therefore, this polyurethane resin composition has improved affinity with fibers, and as a result, has excellent washing durability to fibers.
[0019]
The repellent agent of the present invention contains the polyurethane resin composition of the present invention.
[0020]
Therefore, this repellent has excellent water repellency, oil repellency, and oil resistance, and also has excellent washing durability for textiles.
[0021]
The textile water repellent agent of the present invention contains the polyurethane resin composition of the present invention.
[0022]
Therefore, this textile water repellent has excellent water repellency and excellent washing durability for textiles.
[0023]
The antifouling coating agent of the present invention contains the polyurethane resin composition of the present invention.
[0024]
Therefore, this antifouling coating agent has excellent antifouling properties.
MODE FOR CARRYING OUT THE INVENTION
[0025]
The polyurethane resin composition of the present invention contains a reaction product of an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound.
[0026]
An aliphatic polyisocyanate derivative is a derivative of an aliphatic polyisocyanate.
[0027]
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.
[0028]
In addition, aliphatic polyisocyanates include alicyclic polyisocyanates.
[0029]
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.
[0030]
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.
[0031]
Aliphatic polyisocyanate derivatives include, for example, oligomers (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, and heptamers of the above-described aliphatic polyisocyanates. body, 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 trihydric alcohol (e.g., trimethylolpropane, etc.) and polyol derivatives (alcohol adducts, preferably trimethylolpropane adducts) produced by reaction), biuret derivatives (e.g., the above-described aliphatic polyisocyanate, water or amines biuret derivatives produced by the reaction with), urea derivatives (for example, urea derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanate and diamine), oxadiazinetrione derivatives (for example, the above-mentioned aliphatic polyisocyanate and oxadiazinetrione produced by reaction with carbon dioxide), carbodiimide derivatives (such as carbodiimide derivatives produced by decarboxylation condensation reaction of the above-mentioned aliphatic polyisocyanate), uretdione derivatives, uretonimine derivatives and the like.
[0032]
The aliphatic polyisocyanate derivatives preferably include isocyanurate derivatives, trimethylolpropane adducts, allophanate derivatives and biuret derivatives, and more preferably isocyanurate derivatives.
[0033]
When the aliphatic polyisocyanate derivative contains an isocyanurate derivative, the texture is improved.
[0034]
As the aliphatic polyisocyanate derivative, more preferably, an isocyanurate derivative of hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, a biuret derivative of hexamethylene diisocyanate, bis(isocyanatomethyl ) isocyanurate derivatives of cyclohexane, more preferably isocyanurate derivatives of hexamethylene diisocyanate.
[0035]
Aliphatic polyisocyanate derivatives can be used alone or in combination of two or more. Preferably, isocyanurate derivatives of hexamethylene diisocyanate are used alone, isocyanurate derivatives of hexamethylene diisocyanate, and bis(isocyanatomethyl)cyclohexane. Combination with at least one selected from the group consisting of isocyanurate derivatives, trimethylolpropane adducts of hexamethylene diisocyanate, allophanate derivatives of hexamethylene diisocyanate, and biuret derivatives of hexamethylene diisocyanate.
[0036]
In that case, the mixing ratio of the isocyanurate derivative of hexamethylene diisocyanate is as follows: the isocyanurate derivative of hexamethylene diisocyanate, the isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, the trimethylolpropane adduct of hexamethylene diisocyanate, and hexamethylene. For example, 60 parts by mass or more, preferably 70 parts by mass or more, and For example, 85 parts by mass or less, and from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate The blending ratio of at least one selected is, for example, 15 parts by mass or more, and is, for example, 40 parts by mass or less, preferably 30 parts by mass or less.
[0037]
In addition, aliphatic polyisocyanate derivatives can be produced by known methods.
[0038]
The average number of isocyanate groups of the aliphatic polyisocyanate derivative is 2 or more, preferably 2.5, more preferably 2.9, and is, for example, 3.8 or less.
[0039]
If the average number of isocyanate groups is equal to or higher than the lower limit, water repellency can be improved.
[0040]
The method for measuring the average number of isocyanate groups will be described in detail in Examples described later.
[0041]
In addition, when two or more types of aliphatic polyisocyanate derivatives are used in combination, the average number of isocyanate groups is calculated from the weight ratio of the aliphatic polyisocyanate derivatives and the average number of isocyanate functional groups.
[0042]
The long-chain active hydrogen compound has both a hydrocarbon group with 12 to 30 carbon atoms and an active hydrogen group that reacts with an aliphatic polyisocyanate derivative.
[0043]
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.).
[0044]
For example, as an active hydrogen group, A hydroxyl group is mentioned.
[0045]
Such long-chain active hydrogen compounds having both a hydrocarbon group and an active hydrogen group include, for example, linear saturated hydrocarbon group-containing active hydrogen compounds, branched saturated hydrocarbon group-containing active hydrogen compounds, linear Examples include unsaturated hydrocarbon group-containing active hydrogen compounds and branched unsaturated hydrocarbon group-containing active hydrogen compounds.
[0046]
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
[0047]
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;
[0048]
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.
[0049]
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.
[0050]
The 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.
[0051]
The long-chain active hydrogen compounds can be used singly or in combination of two or more.
[0052]
When a long-chain active hydrogen compound is used alone, preferably a linear saturated hydrocarbon group-containing active hydrogen compound is used alone, more preferably a linear saturated hydrocarbon group-containing alcohol is used alone, and more preferably. includes the use of stearyl alcohol alone.
[0053]
When two or more long-chain active hydrogen compounds are used in combination, preferably a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound are used in combination. Combined use of an alcohol containing a saturated chain hydrocarbon group and an alcohol containing a linear unsaturated hydrocarbon group, an alcohol containing a linear saturated hydrocarbon group, a sorbitan ester containing a linear saturated hydrocarbon group, and a linear unsaturated hydrocarbon A combined use with a group-containing alcohol is mentioned.
[0054]
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 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, relative to 100 parts by mass of the total amount of the linear unsaturated hydrocarbon group-containing alcohol. In addition, the blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 60 mass parts per 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 less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less.
[0055]
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 water repellency can be improved.
[0056]
When a linear saturated hydrocarbon group-containing alcohol, a linear saturated hydrocarbon group-containing sorbitan ester and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the linear saturated hydrocarbon group-containing alcohol is, for example, 30 parts by mass with respect to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. It is above and, for example, it is 60 mass parts or less. The blending ratio of the linear saturated hydrocarbon group-containing sorbitan ester is the ratio of the linear saturated hydrocarbon group-containing sorbitan ester, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. For example, it is 20 parts by mass or more and, for example, 50 parts by mass or less with respect to the total amount of 100 parts by mass. In addition, the mixing ratio of the linear unsaturated hydrocarbon group-containing alcohol is the ratio of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. For example, it is 10 parts by mass or more and, for example, 20 parts by mass or less with respect to the total amount of 100 parts by mass.
[0057]
When two or more long-chain active hydrogen compounds are used in combination, more preferably, a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, and stearyl alcohol and oleyl are particularly preferred. Use with alcohol.
[0058]
A cationic active hydrogen compound has both an active hydrogen group and a cationic group.
[0059]
The active hydrogen group is, as described above, an active hydrogen group that reacts with the aliphatic polyisocyanate derivative, and includes, for example, a hydroxyl group.
[0060]
In addition, the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule.
[0061]
Examples of cationic groups include tertiary amino groups.
[0062]
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.
[0063]
With such a cationic active hydrogen compound, the polyurethane resin composition can be imparted with good dispersibility in water, and a cationic group having an affinity for fibers (described later) can be introduced into the resin. Washing durability can be improved.
[0064]
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.
[0065]
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.
[0066]
The cationic active hydrogen compound can be used alone or in combination of two or more.
[0067]
An acid compound is a compound that forms a salt with a cationic group.
[0068]
Examples of acid compounds include organic acids and inorganic acids.
[0069]
Examples of organic acids include acetic acid, lactic acid, tartaric acid, and malic acid, preferably acetic acid, lactic acid, and more preferably acetic acid.
[0070]
Examples of inorganic acids include hydrochloric acid, sulfuric acid, and phosphoric acid, preferably hydrochloric acid.
[0071]
The acid compound preferably includes an organic acid.
[0072]
If the acid compound contains an organic acid, the heat treatment causes the acid to volatilize, which reduces the ionicity and improves the water resistance, and thus the water repellency can be improved. In addition, the volatilization of the acid by the heat treatment makes it easier for the cationic groups to be adsorbed on the fibers, and thus the washing durability of the fibers (described later) can be improved.
[0073]
The acid compound can be used alone or in combination of two or more.
[0074]
Then, to obtain a polyurethane resin composition, an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound are reacted.
[0075]
In order to react an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound, first, an aliphatic polyisocyanate derivative is blended with a long-chain active hydrogen compound, and an aliphatic A polyisocyanate derivative is reacted with a long-chain active hydrogen compound.
[0076]
At this time, for example, when the average number of isocyanate groups of the isocyanurate derivative of the aliphatic polyisocyanate is 3, the long-chain active hydrogen compound preferably has two isocyanate groups among the isocyanurate derivatives of the aliphatic polyisocyanate. , modified with a long-chain active hydrogen compound into a hydrocarbon group having 12 to 30 carbon atoms, and among the isocyanurate derivatives of the aliphatic polyisocyanate, one isocyanate group remains, and an unreacted aliphatic It is formulated so that no isocyanurate derivative of polyisocyanate remains.
[0077]
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, a long-chain active hydrogen compound is blended with the aliphatic polyisocyanate derivative.
[0078]
As a result, the molecular end of the reaction product (hereinafter referred to as the first intermediate reaction product) of the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound is combined with a hydrocarbon group having 12 to 30 carbon atoms and an isocyanate group. Become.
[0079]
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.
[0080]
Also, the above reaction is carried out until the isocyanate concentration of the first intermediate reaction product reaches a predetermined calculated value.
[0081]
The isocyanate concentration can be measured by the n-dibutylamine method according to JIS K-1556 using a potentiometric titrator.
[0082]
Also, in the above reaction, a known solvent (solvent) such as methyl ethyl ketone can be blended in an appropriate proportion.
[0083]
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.
[0084]
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
[0085]
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.
[0086]
Also, the above reaction is carried out until the reaction between the first intermediate reaction product and the cationic active hydrogen compound is completed.
[0087]
In addition, in the above reaction, a known solvent such as methyl ethyl ketone can be blended in an appropriate proportion.
[0088]
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.
[0089]
The second intermediate reaction product has a hydrocarbon group with 12 to 30 carbon atoms and a cationic group.
[0090]
Next, an acid compound is added to the second intermediate reaction product.
[0091]
The mixing ratio of the acid compound is, for example, 0.5 mol or more, preferably 3 mol or more, relative to 1 mol of the cationic group of the cationic active hydrogen compound.It is 0 mol or less, preferably 4 mol or less.
[0092]
As a result, the acid compound forms a salt with the cationic group of the second intermediate reaction product, and the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound react to form A reaction solution containing the substance is obtained.
[0093]
The above reaction product has a hydrocarbon group with 12 to 30 carbon atoms and a cationic group.
[0094]
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). In other words, the above reaction products can be internally emulsified.
[0095]
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.
[0096]
After that, the solvent is removed from this reaction solution.
[0097]
As a result, an aqueous dispersion (aqueous dispersion of the polyurethane resin composition) containing the above reaction product is obtained.
[0098]
The solid content concentration of the aqueous dispersion is, for example, 10% by mass or more and, for example, 30% by mass or less.
[0099]
Because such a polyurethane resin composition contains a reaction product obtained using a long-chain active hydrogen compound, it has excellent water repellency, oil repellency, oil resistance, and antifouling properties.
[0100]
In addition, since the polyurethane resin composition contains a reaction product obtained using a cationic active hydrogen compound, the affinity with fibers (described later) is improved, and as a result, the washing durability of fibers (described later) is excellent. .
[0101]
Also, in such a polyurethane resin composition, the concentration of hydrocarbon groups is 30% or more and 85% or less, preferably 50%.
[0102]
If the concentration of the hydrocarbon group is equal to or higher than the above lower limit, the water repellency can be improved.
[0103]
On the other hand, if the concentration of the hydrocarbon group is less than the above lower limit, the water repellency is lowered.
[0104]
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.
[0105]
On the other hand, if the concentration of hydrocarbon groups exceeds the above upper limit, the stability of the polyurethane resin is reduced.
[0106]
It should be noted that the concentration of the above hydrocarbon group can be calculated from the charged amount of each component described above.
[0107]
In the above description, first, an aliphatic polyisocyanate derivative and a long-chain active hydrogen compound are reacted to obtain a reaction liquid containing a first intermediate reaction product, then the first intermediate reaction product and a cation A reaction solution containing a second intermediate reaction product was obtained by reacting with an active hydrogen compound, and then the second intermediate reaction product was reacted with an acid compound, but the order of reaction is not particularly limited, For example, an aliphatic polyisocyanate derivative may be reacted with a cationic active hydrogen compound, and then a long-chain active hydrogen compound and an acid compound may be reacted. Alternatively, the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound may be blended together and reacted.
[0108]
The polyurethane resin composition can be used, for example, as a water-repellent treatment liquid diluted with water (ion-exchanged water).
[0109]
By impregnating fibers (textile products), which will be described later, with such a water-repellent treatment liquid, it is possible to impart oil repellency, oil resistance, and antifouling properties to the fibers (textile products).
[0110]
A blocked isocyanate composition can also be added to the water-repellent treatment liquid.
[0111]
The blocked isocyanate composition contains a blocked isocyanate obtained by blocking the isocyanate group of the reaction product of a polyisocyanate and a hydrophilic group-containing active hydrogen compound with a blocking agent.
[0112]
Polyisocyanates preferably include aliphatic polyisocyanate derivatives, more preferably isocyanurate derivatives of hexamethylene diisocyanate.
[0113]
The hydrophilic group-containing active hydrogen compound is a compound having both a hydrophilic group such as a nonionic group such as a polyoxyethylene group and an ionic group such as an anionic group or a cationic group, and an active hydrogen group. , for example, anionic active hydrogen compounds such as 2,2-dimethylolpropionic acid, cationic active hydrogen compounds described above, nonionic active hydrogen compounds such as methoxypolyoxyethylene glycol, etc., preferably , cationic active hydrogen compounds, more preferably N-methyldiethanolamine.
[0114]
Preferably, the blocked isocyanate composition contains a blocked isocyanate in which the isocyanate group of the reaction product of an aliphatic polyisocyanate and a cationic active hydrogen compound is blocked with a blocking agent.
[0115]
The blocking agent is not particularly limited, and known blocking agents are employed, and examples thereof include pyrazole compounds such as 3,5-dimethylpyrazole.
[0116]
In order to obtain such a blocked isocyanate composition, first, an aliphatic polyisocyanate derivative and a cationic active hydrogen compound are reacted.
[0117]
After that, a blocking agent is added to the reaction liquid containing the reaction product of the aliphatic polyisocyanate derivative and the cationic active hydrogen compound to block the isocyanate groups of this reaction product.
[0118]
After that, the cationic groups of this reaction product are neutralized with an acid compound to obtain a blocked isocyanate composition.
[0119]
The blending ratio of the blocked isocyanate composition is, for example, 20% by mass or more and, for example, 40% by mass or less with respect to the water-repellent treatment liquid.
[0120]
Also, the blending ratio of the blocked isocyanate composition is, for example, 20 parts by mass or more and, for example, 40 parts by mass or less with respect to the total amount of 100 parts by mass of the polyurethane resin composition and the blocked isocyanate composition.
[0121]
As described above, the polyurethane resin composition has excellent water repellency, oil repellency, and oil resistance, so it can be suitably used for repellent agents (as a component of repellent agents).
[0122]
The repellent agent of the present invention is specifically a water repellent agent, an oil repellent agent, and an oil resistant agent, and includes the polyurethane resin composition described above.
[0123]
Since the repellent contains the above polyurethane resin composition, it has excellent water repellency, oil repellency, and oil resistance, and also has excellent washing durability to fibers (described later).
[0124]
The object to be treated with such a repellent agent is not particularly limited, and examples thereof include fibers (textile products) (described later), paper, stone, glass, metal, cement, and resin film.
[0125]
In addition, as described above, the above polyurethane resin composition is excellent in washing durability to fibers, and therefore is more preferably used as a component of a water repellent agent (textile water repellent agent) for use in fibers (textile products). be able to.
[0126]
The textile water repellent agent of the present invention is for treating fibers (textile products) with water repellency, and includes the polyurethane resin composition described above.
[0127]
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).
[0128]
Since the textile water repellent contains the above polyurethane resin composition, it has excellent water repellency and excellent washing durability to textiles.
[0129]
In addition, as described above, the above polyurethane resin composition is excellent in antifouling properties, so it can be suitably used as a component of an antifouling coating agent.
[0130]
The antifouling coating agent of the present invention contains the polyurethane resin composition described above.
[0131]
The antifouling coating agent contains the polyurethane resin composition described above, so it has excellent antifouling properties.
[0132]
The object to be treated with such an antifouling coating agent is not particularly limited, and examples thereof include those exemplified as the object to be treated with the repellent agent.
Example
[0133]
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 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. Thereafter, 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 is 0.5% or less, and the aliphatic polyisocyanate derivative ( isocyanurate derivative of hexamethylene diisocyanate). The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functional group number of 3.0.
[0134]
Synthesis Example 2 (isocyanurate derivative of bis(isocyanatomethyl)cyclohexane) Bis(isocyanatomethyl)cyclohexane (H 6XDI , Mitsui Chemicals, Inc., trade name: Takenate 600) and 14.8 g of isobutyl alcohol were charged, heated to 90°C, and held for 2 hours. Thereafter, 0.2 g of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as a reaction catalyst, and the reaction was allowed to proceed for 2 hours while adjusting the reaction temperature to 90±5°C. Thereafter, 0.02 g of o-toluenesulfonic acid amide was added as a catalyst deactivator to deactivate the reaction catalyst and terminate the reaction. Thereafter, this reaction mixture was passed through a thin film distillation apparatus (temperature 150° C., degree of vacuum 93.3 Pa) and distilled until the amount of residual H 6XDI monomer became 0.5% or less. The isocyanate group content of the obtained reaction liquid was 20.2%. Furthermore, ethyl acetate was added to this reaction solution to obtain a reaction solution containing an aliphatic polyisocyanate derivative (isocyanurate derivative of bis(isocyanatomethyl)cyclohexane) at a concentration of 75%. The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 15.2% and an average isocyanate functional group number of 3.0.
[0135]
Synthesis example 3 (trimethylolpropane adduct of hexamethylene diisocyanate)
　In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a cooling tube, 1,6-hexamethylene 500 parts by mass of diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700) and 45.8 parts by mass of trimethylolpropane (abbreviation: TMP) were charged. Under a nitrogen atmosphere, the temperature was raised to 75°C, and after confirming that the trimethylolpropane was dissolved, the isocyanate group concentration reached the calculated value (theoretical amount of unreacted isocyanate groups) of 37.9%. reacted. Thereafter, the reaction solution is cooled to 55° C., 350 parts by mass of a mixed extraction solvent (n-hexane/ethyl acetate=90/10 (mass ratio)) is added, stirred for 10 minutes, left to stand for 10 minutes, and then extracted. The solvent layer was removed. The same extraction operation was repeated four times. After that, the obtained reaction solution was heated to 80° C. under reduced pressure to remove the extraction solvent remaining in the reaction solution. The isocyanate group concentration of this reaction liquid was 17.1% by mass. Furthermore, ethyl acetate was added to obtain a reaction liquid containing an aliphatic polyisocyanate derivative (hexamethylene diisocyanate-trimethylolpropane adduct) at a concentration of 75%. The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 12.8% and an average isocyanate functional group number of 3.3.
[0136]
Synthesis Example 4 (Allophanate 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), isobutyl Alcohol 24 parts by weight, 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenolic antioxidant) 0.3 parts by weight, tris (tridecyl) phosphite 0 . 30 parts by mass was added and urethanized at 85° C. for 3 hours. Thereafter, 0.02 part by mass of tris(2-ethylhexanoic acid) bismuth was added as an allophanate catalyst, and the reaction was allowed to proceed until the isocyanate group concentration reached the calculated value (46.7%). 02 parts by mass were added. Thereafter, this reaction mixture was 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 became 0.5% or less. Thereafter, 0.02 part by mass of o-toluenesulfonamide was added to 100 parts by mass of the reaction solution to obtain an aliphatic polyisocyanate derivative (an allophanate derivative of hexamethylene diisocyanate). The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 19.3% and an average isocyanate functional group number of 2.1.
[0137]
Synthesis example 5 (biuret 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), Tris 0.3 parts by mass of (tridecyl)phosphite, 8 parts by mass of trimethylphosphoric acid, and 3.57 parts by mass of water were charged, heated to 130° C., and reacted until the isocyanate group content reached 44.6%. rice field. Thereafter, 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 is 0.5% or less, and the aliphatic polyisocyanate derivative ( A biuret derivative of hexamethylene diisocyanate) was obtained. The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 22.6% and an average isocyanate functional group number of 2.8.
2. Preparation of polyurethane resin composition and water-repellent treatment liquid
Example 1
A reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas inlet tube was charged with 100.08 g of the aliphatic polyisocyanate derivative of Synthesis Example 1 as the aliphatic polyisocyanate derivative, and Calcol 8098 (stearyl 90.03 g of alcohol (manufactured by Kao Corporation) was mixed and reacted at 110° C. in a nitrogen atmosphere for 4 hours until the isocyanate group concentration reached 3.67%.
[0138]
Then, the reaction solution was cooled to 80°C, 9.89 g of N-methyldiethanolamine was added as a cationic active hydrogen compound, and reacted at 80°C for 1 hour.
[0139]
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.
[0140]
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.
[0141]
After that, 18.93 g of acetic acid was added as an acid compound to neutralize it.
[0142]
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).
[0143]
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.
[0144]
Then, the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound and the acid compound are adjusted with ion-exchanged water so that the solid content concentration excluding the acid compound (acetic acid) is 20% by mass. An aqueous dispersion containing a reaction product (aqueous dispersion containing a polyurethane resin composition) was obtained.
[0145]
Further, 95 g of ion-exchanged water was added to 5 g of the aqueous dispersion containing the obtained polyurethane resin composition for dilution, and a water-repellent treatment liquid was prepared so that the solid concentration excluding the acid compound was 1%. .
[0146]
Examples 2 and 3, Example 5, Examples 8-11, and Comparative Example 1
According to Table 1, an aqueous dispersion containing a polyurethane resin composition and a water-repellent treatment liquid were prepared in the same manner as in Example 1, except that the formulation was changed.
[0147]
Example 4
According to Table 1, an aqueous dispersion containing a polyurethane resin composition was produced in the same manner as in Example 1, except that the formulation was changed.
[0148]
Then, the polyurethane resin composition and the blocked isocyanate composition of Reference Example 1 described later were mixed at a ratio of 7:3. Then, 95 g of ion-exchanged water was added to 5 g of this mixture to dilute it, and a water-repellent treatment liquid was prepared so that the solid concentration excluding the acid compound was 1%.
[0149]
Example 6
In a reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introduction tube, 79.88 g of the aliphatic polyisocyanate derivative of Synthesis Example 1 and the aliphatic polyisocyanate derivative of Synthesis Example 2 were added as aliphatic polyisocyanate derivatives. 27.55 g, 67.37 g of Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound, and 22.22 g of oleyl alcohol were mixed, and the concentration of isocyanate groups per solid content was measured at 80°C under a nitrogen atmosphere. was allowed to react until it reached 3.66%.
[0150]
Then, 9.86 g of N-methyldiethanolamine was added as a cationic active hydrogen compound and reacted at 80°C for 1 hour.
[0151]
Then, 78.83 g of methyl ethyl ketone was added to the reaction solution, and the mixture was allowed to react at 80°C until the disappearance of the isocyanate group could be confirmed by the infrared absorption spectrum.
[0152]
Then, 77.92 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.
[0153]
Then, 18.89 g of acetic acid was added as an acid compound for neutralization.
[0154]
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).
[0155]
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.
[0156]
Then, the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound and the acid compound are adjusted with ion-exchanged water so that the solid content concentration excluding the acid compound (acetic acid) is 20% by mass. An aqueous dispersion containing a reaction product (aqueous dispersion containing a polyurethane resin composition) was obtained.
[0157]
Further, 95 g of ion-exchanged water was added to 5 g of the aqueous dispersion containing the obtained polyurethane resin composition for dilution, and a water-repellent treatment liquid was prepared so that the solid concentration excluding the acid compound was 1%. .
[0158]
Example 7
According to Table 1, an aqueous dispersion containing a polyurethane resin composition and a water-repellent treatment liquid were prepared in the same manner as in Example 6, except that the formulation was changed.
[0159]
　　Comparative example 2
A reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas inlet tube was charged with 99.46 g of the aliphatic polyisocyanate derivative of Synthesis Example 1 and Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound. 89.48 g were mixed and reacted at 110° C. for 4 hours under a nitrogen atmosphere until the isocyanate group concentration per solid content reached 3.67%.
[0160]
Then, the reaction solution was cooled to 80°C, 11.06 g of dimethylolpropionic acid was added, and the reaction was allowed to proceed at 80°C for 1 hour.
[0161]
Then, 85.71 g of methyl ethyl ketone was added to the reaction solution, and the mixture was allowed to react at 80°C until the disappearance of the isocyanate group could be confirmed by the infrared absorption spectrum.
[0162]
Next, 98.90 g of methyl el ketone was added to the reaction liquid, heated to 80°C, mixed until the reaction liquid was completely dissolved, and then cooled to 75°C.
[0163]
Then, as a neutralizing agent, 25.03 g of triethylamine was added for neutralization.
[0164]
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).
[0165]
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.
[0166]
Then, an aqueous dispersion containing a polyurethane resin composition was obtained by adjusting with ion-exchanged water such that the solid content concentration excluding the neutralizing agent (triethylamine) was 20% by mass.
[0167]
Further, 95 g of ion-exchanged water was added to 5 g of the aqueous dispersion containing the obtained polyurethane resin composition for dilution, and a water-repellent treatment liquid was prepared so that the solid concentration excluding the neutralizing agent was 1%. did.
[0168]
　　Comparative example 3
In a 250 ml four-necked round bottom flask equipped with an overhead stirrer, thermocouple, Dean Stark/condenser, 116.0 g of Rhedol SP-S30V (sorbitan tristearate, manufactured by Kao Corporation) and 4-methyl-2 - 150 g of pentanone (MIBK) were added. The resulting reaction was refluxed for 1 hour to remove any residual moisture. After 1 hour, the reaction was cooled to 50°C and 30 g of DESMODUR N-100 (a biuret derivative of hexamethylene diisocyanate, manufactured by Bayer) was added, followed by the catalyst to bring the solution to 80°C. Heated for 1 hour. This prepared a sorbitan urethane/MIBK solution.
[0169]
Separately, 300 g of water, ARMEEN DM-18D (manufactured by Akzo-Nobel, N,N-dimethyl-n-octadecylamine) 5.6 g, TERGITOL TMN-10 (manufactured by Sigma-Aldrich, polyethylene glycol trimethyl 2.8 g of nonyl ether) and 3.4 g of acetic acid were added to a beaker and stirred to prepare a surfactant solution, which was heated to 60°C. The above sorbitan urethane/MIBK solution was then cooled to 60° C. and the surfactant solution was slowly added to the sorbitan urethane/MIBK solution to obtain a mixture. This produced a milky emulsion (external emulsification). The mixture was then homogenized at 41 MPa (6000 psi) and the resulting emulsion was distilled under reduced pressure to remove the solvent to obtain an aqueous dispersion containing 25% by weight of the polyurethane resin composition.[0170]
Further, 95 g of ion-exchanged water was added to 5 g of the aqueous dispersion containing the obtained polyurethane resin composition for dilution, and a water-repellent treatment liquid was prepared so that the solid concentration excluding the acid compound was 1%. .
[0171]
　　Reference example 1
A reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas inlet tube was charged with 141.09 g of the aliphatic polyisocyanate derivative of Synthesis Example 1, 13.94 g of N-methyldiethanolamine as a cationic active hydrogen compound, and 13.94 g of N-methyldiethanolamine as a solvent. 85.71 g of methyl ethyl ketone was mixed and reacted in a nitrogen atmosphere at 60°C for 2 hours, after which the temperature was raised to 70°C until the isocyanate group concentration per solid content reached 12.7%.
[0172]
Next, this reaction solution was cooled to 22°C, and 44.97 g of 3,5-dimethylpyrazole as a blocking agent was added in several portions so that the temperature of the reaction solution did not exceed 50°C. It was confirmed by the infrared absorption spectrum that the isocyanate group was blocked after reacting for a period of time.
[0173]
Then, the reaction solution was cooled to 25°C and neutralized by adding 7.02 g of acetic acid as an acid compound.
[0174]
Next, 800.0 g of ion-exchanged water was gradually added to the reaction solution to emulsify.
[0175]
Next, in an evaporator, the solvent was removed at a water bath temperature of 40°C under reduced pressure until the solid content concentration reached 20% by mass or more.
[0176]
Next, a blocked isocyanate composition was obtained by adjusting with ion-exchanged water so that the solid content concentration excluding the acid compound (acetic acid) was 20% by mass.
[0177]
Further, 95 g of ion-exchanged water was added to 5 g of the aqueous dispersion containing the obtained polyurethane resin composition for dilution, and a water-repellent treatment liquid was prepared so that the solid concentration excluding the acid compound was 1%. .
3. evaluation
a) average isocyanate functionality
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 (1).
[0178]
Average number of isocyanate functional groups = A/B x C/42.02 (1)
(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.)
In addition, the average number of isocyanate functional groups in Examples 6 to 9, in which two types of aliphatic polyisocyanate derivatives were used in combination, was calculated from the weight ratio of the aliphatic polyisocyanate derivatives and the average number of isocyanate functional groups. Table 1 shows the results.
(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)
b) water repellency and wash durability
(Preparation of treatment cloth)
After impregnating the test cotton cloth (Kanakin No. 3) once with the water repellent treatment liquid of each example and each comparative example, squeeze the test cotton cloth once (pick up 100%), then at 110 ° C. for 2 minutes. Dried.
[0179]
After that, it was heated at 170°C for 2 minutes to obtain a treated cloth (170°C for 2 minutes), and separately heated at 170°C for 10 minutes to obtain a treated cloth (170°C for 10 minutes).
(water repellency before washing)
10 drops of water were dropped on the treated cloth (170 ° C. 2 minutes) and the treated cloth (170 ° C. 10 minutes) of each example and each comparative example with a dropper, and the water droplets were left without soaking into the treated cloth. number was counted.
[0180]
In addition, the measurement was performed after 15 minutes and 30 minutes had passed since 10 drops of water had been dropped with a dropper. Table 2 shows the results.
(water repellency after washing)
After washing the treated cloth (170°C for 2 minutes) and the treated cloth (170°C for 10 minutes) of each example and each comparative example (after washing 5 or 10 times) under the following conditions, 10 drops of water were applied with a dropper. The number of water droplets that remained without soaking into the treated cloth was counted. The measurement was performed after 15 minutes, 30 minutes, or 90 minutes had passed since 10 water droplets had been dropped with the dropper. Table 2 shows the results.
[0181]

Washing: Toshiba AW-F42S (pulsator type washing machine) standard mode
Detergent: Synthetic laundry detergent Bold Fresh Pure Clean (manufactured by Procter & Gamble Japan Co., Ltd.) Concentration described (approximately 43 g of detergent per 45 L of water)
Drying: Toshiba ED-50 (tumbler dryer) standard mode
(Evaluation of water repellency and washing durability)
For each example and each comparative example, the water repellency was evaluated based on the following criteria. Table 2 shows the results.
◯: Regarding the treated cloth (10 minutes at 170° C.), the number of water droplets is 10 in both the water repellency evaluation before washing (after 15 minutes) and the water repellency evaluation before washing (after 30 minutes).
△: Regarding the treated cloth (170 ° C. 10 minutes), the number of water droplets in at least one of the water repellency evaluation before washing (after 15 minutes) and the water repellency evaluation before washing (after 30 minutes) is 1 or more and less than 10 is.
x: Regarding the treated cloth (10 minutes at 170°C), the number of water droplets in at least one of the water repellency evaluation before washing (after 15 minutes) and the water repellency evaluation before washing (after 30 minutes) is 0.
[0182]
In addition, washing durability was evaluated for each example and each comparative example based on the following criteria. Table 2 shows the results.
○: Regarding the treated cloth (10 minutes at 170 ° C), the number of water droplets in the water repellency evaluation after washing (after washing 10 times, after 15 minutes) and the water repellency evaluation after washing (after washing 10 times, after 30 minutes) , are both 10.
△: Regarding the treated cloth (170 ° C. 10 minutes), at least among the water repellency evaluation after washing (after 10 washings, after 15 minutes) and after washing water repellency evaluation (after 10 washings, after 30 minutes)) The number of water droplets on one side is 1 or more and less than 10.
×: Regarding the treated fabric (170 ° C. 10 minutes), at least among the water repellency evaluation after washing (after 10 washings, after 15 minutes) and after washing water repellency evaluation (after 10 washings, after 30 minutes)) The number of water droplets on one side is zero.
(Anti-fouling)
The water-repellent treatment liquid of Example 2 was applied to each substrate (glass, bonder steel plate, acrylic (white), and PET film) under the following conditions to create a coating film.
[0183]
The water-repellent treatment liquid of Example 2 was applied to half of one side of the glass with a bar coater so that the thickness after drying was about 5 μm, dried at room temperature, and further heated at 110° C. for 1 hour. . As a result, a coating film was obtained, and a coated portion having a coating film formed thereon and an uncoated portion having no coating film formed thereon were formed on one surface of the glass.
[0184]
Separately, the water-repellent treatment liquid of Example 2 was applied to half of one surface of a Bonde steel plate (Testpiece Co., Ltd.) with a bar coater so that the thickness after drying was about 5 μm, and then dried at room temperature. and further heated at 110° C. for 1 hour. As a result, a coating film was obtained, and on one surface of the bonder steel plate, a coated portion having a coating film formed thereon and an uncoated portion having no coating film formed thereon were formed.
[0185]
Separately, the water-repellent treatment liquid of Example 2 was applied to half of one side of acrylic (white) (Test Piece Co., Ltd.) with a bar coater so that the thickness after drying was about 5 μm, and then at room temperature. It was dried and further heated at 110° C. for 1 hour. As a result, a coating film was obtained, and on one side of the acrylic (white), a coating portion having a coating film formed thereon and a non-coating portion having no coating film formed thereon were formed.
[0186]
Separately, the water-repellent treatment liquid of Example 2 was applied to half of one side (corona-treated side) of a PET film (manufactured by Toyobo Co., Ltd., trade name E5102, thickness 12 μm) so that the thickness after drying was about 2 μm. It was applied with a coater and heated at 110° C. for 2 minutes. As a result, a coating film was obtained, and a coated portion having a coating film formed thereon and an uncoated portion having no coating film formed thereon were formed on one side of the PET film.
[0187]
Water was dripped on the coated part and the non-coated part on one side of each base material.
[0188]
For all base materials, the coated part repelled water better than the non-coated part.
[0189]
From this, it was found that water repellency can be imparted to each substrate by using a polyurethane resin composition.
[0190]
In addition, by wiping the coated part of each base material with water, it was possible to easily remove traces of fingerprints attached to the coated part.
[0191]
From this, it was found that the use of a polyurethane resin composition can impart antifouling properties to each substrate.
[0192]
[table 1]

[0193]
[Table 2]

[0194]
4. consideration
Examples 1 to 11, in which the hydrocarbon group concentration is 30% or more and 85% or less, are superior in water repellency and washing durability to Comparative Example 1, in which the hydrocarbon group concentration is less than 30%. .
[0195]
From this, it was found that water repellency and durability to washing can be improved if the concentration of hydrocarbon groups is 30% or more and 85% or less.
[0196]
In addition, Examples 1 to 11 using a cationic active hydrogen compound are superior in water repellency and washing durability to Comparative Example 2 using an anionic active hydrogen compound.
[0197]
From this, it was found that using a cationic active hydrogen compound can improve water repellency and washing durability.
[0198]
Also, compared to Example 5, which was obtained by internal emulsification, and Comparative Example 3, which was obtained by external emulsification, it has excellent washing durability.
[0199]
From this, it was found that washing durability can be improved by preparing a reaction product by internal emulsification.
[0200]
In addition, Example 5, which is internally emulsified, is superior in washing durability to Comparative Example 3, which is externally emulsified.
[0201]
Even if the water repellency before washing is the same, in Example 5, which is internally emulsified, cationic groups that have an affinity for fibers are introduced into the resin, so they can interact with fibers and do not fall off after washing. Although water repellency is maintained, in Comparative Example 3, which is externally emulsified, cationic groups that have an affinity for fibers are not introduced into the resin, so the resin is likely to fall off by washing, so it is presumed that the water repellency decreased after washing. be.
[0202]
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
[0203]
The polyurethane resin composition, repellent agent, fiber water repellent agent, and antifouling coating agent of the present invention can be used for various industrial products, and can be suitably used, for example, as surface treatment agents.
The scope of the claims
[Claim 1]
an aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more,
a 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,
containing reaction products of cationic groups and acid compounds that form salts,
A polyurethane resin composition, characterized in that the concentration of the hydrocarbon group is 30% or more and 85% or less.
[Claim 2]
The polyurethane resin composition according to claim 1, wherein the aliphatic polyisocyanate derivative contains an isocyanurate derivative of an aliphatic polyisocyanate.
[Claim 3]
In the cationic active hydrogen compound,
the cationic group is a tertiary amino group,
the active hydrogen group is a hydroxyl group,
The polyurethane resin composition according to claim 1, wherein the cationic active hydrogen compound has two or more hydroxyl groups per molecule.
[Claim 4]
The polyurethane resin composition according to claim 1, wherein the acid compound contains an organic acid.
[Claim 5]A repellent agent comprising the polyurethane resin composition according to claim 1 .
[Claim 6]
A textile water repellent comprising the polyurethane resin composition according to claim 1.
[Claim 7]
An antifouling coating agent comprising the polyurethane resin composition according to claim 1.