Technical field
[0001]
　The present invention relates to aqueous dispersions and the laminated body, particularly, water dispersion, and a laminate obtained by using the aqueous dispersion.
Background technique
[0002]
　Conventionally, in the various industrial fields, plastic film, metallized film, metal foil, paper, a substrate such as a nonwoven fabric, bonded by hot-pressing (i.e., heat sealing) is known. In heat sealing, usually the adhesive layer is formed in advance on the substrate, and their base material to each other, the base and the other adherend is bonded via an adhesive layer.
[0003]
　The material used for such a heat sealing, for example, olefin polymer (A), resin particles containing acrylic-based polymer and (B) in the same particle, an emulsion is dispersed in water heat sealing adhesive composition comprising, and heat sealing material formed by coating the heat-sealing adhesive composition to a substrate has been proposed. More specifically, in the presence of 150 parts of polyolefin-based emulsion, the polymerization of methyl methacrylate 55 parts of 1-butyl acrylate, to obtain a heat-sealing adhesive composition further obtained hot sealing adhesive composition and applied to a paper, dried, and thermally sealing the coated surface with each other, has been proposed (e.g., Patent Document 1 see.).
CITATION
Patent Document
[0004]
Patent Document 1: Laid-Open Patent Publication No. 2001-179909 (Mika Example 1)
Summary of the Invention
Problems that the Invention is to Solve
[0005]
　And the type of substrate and the adherend, by such applications, there is a case where further improvement of the adhesive strength and the blocking resistance are required.
[0006]
　An object of the present invention, an aqueous dispersion having excellent adhesive strength and blocking resistance, and to provide a laminate obtained by using the aqueous dispersion.
Means for Solving the Problems
[0007]
　Composite invention [1] contains a resin component, a water dispersing the resin component, said resin component containing an ethylene-unsaturated carboxylic acid copolymer (A) and the acrylic polymer (B) It comprises particles (C), the ethylene-unsaturated carboxylic acid copolymer (a) is ethylene and containing an unsaturated carboxylic acid, co of the first monomer component content of the ethylene is not less than 75 wt% obtained by polymerization, the acrylic polymer (B) is obtained by polymerization of (meth) containing acrylic acid ester, the (meth) second monomer component content of the acrylic acid ester is not less than 50 wt% the glass transition temperature of the acrylic polymer (B) is, and at 80 ° C. or less -28 ° C. or higher, the content of the ethylene-unsaturated carboxylic acid copolymer with respect to the total amount of the resin component (a) 5 Wherein the mass% or more and 90 mass% or less, an aqueous dispersion, which comprise.
[0008]
　Further, the present invention [2], wherein the resin component is further characterized in that it comprises a resin particle comprising an olefin-based polymer (D) (E), water according to the above [1] or [2] the dispersion, which comprise.
[0009]
　Further, the present invention [3] comprises a substrate and an adhesive layer laminated on at least one side surface of the substrate, wherein the adhesive layer is to dry the aqueous dispersion according to claim 1 characterized in that it is obtained by a layered structure comprise.
[0010]
　Further, the present invention [4] is further characterized in that it comprises a adherend layer laminated on one side surface of the adhesive layer, a laminate according to [3], comprise.
[0011]
　Further, the present invention [5], the adherend layer, characterized in that it consists of polyvinyl chloride and / or polyvinylidene chloride, a laminate according to [4], which comprise.
Effect of the Invention
[0012]
　Aqueous dispersion of the present invention, and, according to the laminate obtained by using the aqueous dispersion, it is possible to obtain excellent adhesive strength and blocking resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013]
[1] Figure 1 is a schematic diagram showing an embodiment of the laminate of the present invention.
DESCRIPTION OF THE INVENTION
[0014]
　Aqueous dispersion of the present invention contains a resin component, a water dispersing the resin component.
[0015]
　Resin component comprises ethylene-unsaturated carboxylic acid copolymer (A) and the acrylic polymer composite particles comprising (B) (C).
[0016]
　Ethylene-unsaturated carboxylic acid copolymer (A) is obtained by copolymerization of the first monomer component.
[0017]
　The first monomer component contains ethylene and unsaturated carboxylic acids, preferably comprising ethylene and unsaturated carboxylic acids.
[0018]
　Unsaturated carboxylic acid, a monomer having both at least one ethylenically unsaturated bond and a carboxyl group, for example, acrylic acid, methacrylic acid, monobasic acids such as crotonic acid, e.g., maleic acid, fumaric acid, such as dibasic acids such as itaconic acid.
[0019]
　These unsaturated carboxylic acids may be used alone or in combination of two or more.
[0020]
　As the unsaturated carboxylic acid, from the viewpoint of water resistance, preferably, it includes monobasic acids, more preferably, acrylic acid, methacrylic acid.
[0021]
　Further, the unsaturated carboxylic acid may be used in combination vinyl acetate, vinyl esters such as vinyl carboxylate esters such as vinyl propionate. In such a case, the mixing ratio of the vinyl esters, depending on the purpose and application, are set appropriately.
[0022]
　In the first monomer component, the content of ethylene and unsaturated carboxylic acids, for those total, ethylene, 75 wt% or more, or preferably 78 mass% or more, e.g., 90 wt% or less, preferably is 88 wt% or less. Further, unsaturated carboxylic acids, for example, 10 mass% or more, preferably not 12 wt% or more, 25 wt% or less, preferably not more than 22 wt%.
[0023]
　If ethylene and content is within the above range of unsaturated carboxylic acids, it is possible to obtain excellent adhesive strength and blocking resistance.
[0024]
　Polymerization of the first monomer component is not particularly limited and a known polymerization method is employed. For example, a first monomer component described above, and a known polymerization initiator such as a peroxide, and a method of contacting at elevated temperature and pressure conditions.
[0025]
　The ethylene-unsaturated carboxylic acid copolymer (A) can be obtained as a dispersion of the particles dispersed in water. In such a case, for example, Kokoku 7-008933 Patent, Kokoku 5-039975 Patent, Kokoku 4-030970, JP-B-42-000275, JP-B-42-023085, JP-B-45-029909, JP by the method described in such as Sho 51-062890, it can be polymerized first monomer component.
[0026]
　In the production of ethylene-unsaturated carboxylic acid copolymer (A), from the viewpoint of improving the production stability, if necessary, it can be blended emulsifier (surfactant) which will be described later. The proportion of the emulsifier, depending on the purpose and application, are set appropriately.
[0027]
　In the production of ethylene-unsaturated carboxylic acid copolymer (A), from the viewpoint of improving the production stability, e.g., pH adjusting agents, such as ethylenediamine tetraacetic acid and sequestrant such as a salt thereof , for example, mercaptans, molecular weight modifier such as low molecular halogen compounds (chain transfer agent) such as, can be blended at an appropriate ratio known additives.
[0028]
　The ethylene-unsaturated carboxylic acid copolymer (A), the dispersion stability of the composite particles (C), from the viewpoint of improving the printability of the laminate (described below) are preferably used are neutralized .
[0029]
　In the neutralization, for example, ethylene-unsaturated carboxylic acid copolymer (A), specifically, a dispersion of ethylene-unsaturated carboxylic acid copolymer (A), a basic compound as a neutralizing agent There are added.
[0030]
　Examples of the basic compound include sodium hydroxide, inorganic basic compounds such as potassium hydroxide, for example, ammonia, triethylamine, triethanolamine, organic basic compounds such as amines such as dimethylethanolamine and the like.
[0031]
　These basic compounds may be used alone or in combination of two or more kinds.
[0032]
　As the basic compound, preferably an inorganic basic compound, and more preferably it includes, and sodium hydroxide.
[0033]
　The addition amount of the basic compound, dispersion stability of the composite particles (C), from the viewpoint of improving the printability of the laminate (described below), carboxy groups 100 moles in the ethylene-unsaturated carboxylic acid copolymer (A) against, for example, 5 moles or more, preferably 30 mol or more, more preferably 50 mol or more, for example, 200 moles or less, or preferably 150 mol or less.
[0034]
　When the addition amount of the basic compound is less than the above range may elicit reduced stability of the composite particles (C) in the aqueous dispersion, a reduction in printability. Also, when the addition amount of the basic compound exceeds the above range may elicit high viscosity of the aqueous dispersion, a reduction in workability.
[0035]
　Further, after addition of a neutralizing agent, preferably for a predetermined time at a predetermined temperature.
[0036]
　The holding condition, holding temperature, e.g., 40 ° C. or higher, preferably not 50 ° C. or higher, e.g., 90 ° C. or less, preferably 80 ° C. or less. The holding time, for example, 30 minutes or more, preferably, not less than 1 hour, for example, 12 hours or less, preferably 10 hours or less.
[0037]
　By keeping the above condition, a carboxy group is neutralized, it is possible to improve the printability of the dispersion stability, laminates of the composite particles (C) (described later).
[0038]
　If the ethylene-unsaturated carboxylic acid copolymer (A) is neutralized, the degree of neutralization, for example, 30% or more, preferably 50% or more, for example, 200% or less, preferably, 150 % or less.
[0039]
　If the degree of neutralization is in the above range, it is possible to obtain excellent adhesive strength and blocking resistance. Incidentally, the degree of neutralization is calculated in compliance with the examples described later.
[0040]
　The weight average molecular weight of the ethylene-unsaturated carboxylic acid copolymer (A), in terms of standard polystyrene by gel permeation chromatography (GPC), for example, 10,000 or more, or preferably, 30,000 or more, for example, 20 10,000 or less, preferably 150,000 or less.
[0041]
　The melting point of the ethylene-unsaturated carboxylic acid copolymer (A) is, for example, 55 ° C. or higher, preferably not 65 ° C. or higher, for example, 110 ° C. or less, preferably 100 ° C. or less. The melting point can be determined by DSC (differential scanning calorimetry).
[0042]
　The weight average particle diameter of the ethylene-unsaturated carboxylic acid copolymer (A) (Measurement method: light scattering measurements), for example, 0.01 [mu] m or more, or preferably, 0.02 [mu] m or more, for example, 10 [mu] m or less preferably is 1μm or less.
[0043]
　Moreover, the solid concentration of the ethylene-unsaturated carboxylic acid copolymer in the dispersion of the ethylene-unsaturated carboxylic acid copolymer (A) (A) is, for example, 10 mass% or more, preferably more than 20 wt% , and the example, 60 wt% or less, preferably not more than 50 wt%.
[0044]
　Further, dispersion of ethylene-unsaturated carboxylic acid copolymer (A) can also be obtained commercially. As commercially available products, for example, trade name Chemipearl S100 (ethylene content in the feed: 85 wt%, the type of the unsaturated carboxylic acid: methacrylic acid, sodium hydroxide neutralization product, 27% solids, manufactured by Mitsui Chemicals, Inc.) , trade name CHEMIPEARL S80N (ethylene content in the feed: 80 wt%, the type of the unsaturated carboxylic acids: acrylic acid, ammonium hydroxide neutralization product, solids 24%, manufactured by Mitsui Chemicals, Inc.), trade name CHEMIPEARL S650 ( the ethylene content in the feed: 80 wt%, the type of the unsaturated carboxylic acid: methacrylic acid, sodium hydroxide neutralization product, 27% solids, manufactured by Mitsui Chemicals, Inc.) and the like.
[0045]
　These ethylene-unsaturated carboxylic acid copolymer (A) may be used alone or in combination of two or more.
[0046]
　Acrylic polymer (B) is obtained by polymerization of the second monomer component.
[0047]
　The second monomer component, as essential components, contains a (meth) acrylic acid ester. Here, the (meth) acrylic acid ester, is defined as acrylic acid ester and / or methacrylic acid ester. Also, "(meth) acryl", as described below, the Like, is defined as "acrylic" and / or "methacryl".
[0048]
　The (meth) acrylic acid esters, e.g., methyl (meth) acrylate, (meth) acrylate, (meth) acrylate, propyl (meth) acrylate n- butyl (meth) an iso-butyl acrylate, (meth) butyl s- acrylate, butyl (meth) t- acrylate, (meth) hexyl acrylate, 2-ethyl, (meth) such as lauryl acrylate, having alkyl portions of 1 to 12 carbon atoms (meth ) acrylic acid ester.
[0049]
　These (meth) acrylic acid esters can be used alone or in combination of two or more.
[0050]
　(Meth) acrylic acid ester, t-preferably, (meth) acrylate, (meth) acrylate, (meth) acrylate n- butyl (meth) butyl iso- acrylate, (meth) acrylic acid butyl, (meth) hexyl can be mentioned to acrylic acid 2-ethyl, more preferably methyl (meth) acrylate, it includes n- butyl (meth) acrylate, more preferably, methyl methacrylate, n - butyl, butyl acrylate.
[0051]
　The second monomer component, as an optional component, may contain (meth) acrylic acid ester and copolymerizable copolymerizable monomers.
[0052]
　As the copolymerizable monomer, for example, functional group-containing vinyl monomers, vinyl esters, aromatic vinyl monomers, N- substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, halogenated vinylidene compounds, alpha-olefins, dienes kind and the like.
[0053]
　The functional group-containing vinyl monomers, for example, carboxyl group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, amino group-containing vinyl monomers, glycidyl group-containing vinyl monomers, cyano group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers and salts thereof, aceto acetoxy group-containing vinyl monomers, phosphoric acid group-containing compound, an amide group-containing vinyl monomer.
[0054]
　The carboxyl group-containing vinyl monomers, for example, (meth) acrylic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, and crotonic acid.
[0055]
　The hydroxyl group-containing vinyl monomers, for example, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 2-hydroxypropyl.
[0056]
　The amino group-containing vinyl monomers, for example, (meth) 2-aminoethyl acrylate, (meth) acrylic acid 2- (N-methylamino) ethyl, (meth) acrylic acid 2- (N, N- dimethylamino) ethyl and the like.
[0057]
　The glycidyl group-containing vinyl monomers include, for example, glycidyl (meth) acrylate.
[0058]
　The cyano group-containing vinyl monomers include, for example, (meth) acrylonitrile.
[0059]
　The sulfonic acid group-containing vinyl monomers, for example, allyl sulfonic acid, methallyl sulfonic acid. As the salt thereof, the sulfonic acid group-containing vinyl monomers, for example, sodium salts, alkali metal salts such as potassium salts, for example, and ammonium salts. Specifically, for example, sodium allyl sulfonate, sodium methallyl sulfonate, such as meta-ammonium Lil acid.
[0060]
　The acetoacetoxy group-containing vinyl monomers include, for example, (meth) acetoacetoxyethyl acrylate.
[0061]
　Examples of the phosphoric acid group-containing compounds, such as 2-methacryloyloxypropyl ethyl acid phosphate.
[0062]
　Examples of the amide group-containing vinyl monomers include, for example, (meth) acrylamide.
[0063]
　Examples of the vinyl esters include vinyl acetate, vinyl propionate, etc. may be mentioned.
[0064]
　Examples of the aromatic vinyl monomers, e.g., styrene, alpha-methyl styrene, and divinylbenzene.
[0065]
　The N- substituted unsaturated carboxylic acid amides, such as N- methylol (meth) acrylamide.
[0066]
　The heterocyclic vinyl compounds, for example, and vinyl pyrrolidone.
[0067]
　The halogenated vinylidene compounds, such as vinylidene chloride, vinylidene fluoride is.
[0068]
　The α- olefins such as ethylene, propylene, and the like.
[0069]
　The dienes, e.g., butadiene and the like.
[0070]
　Further, as the copolymerizable monomer, it may be mentioned crosslinkable vinyl monomer.
[0071]
　The crosslinkable vinyl monomers, for example, methylenebis (meth) acrylamide, divinylbenzene, polyethylene glycol chain-containing di (meth) acrylate, and compounds containing two or more vinyl groups.
[0072]
　These copolymerizable monomers may be used alone or in combination of two or more kinds.
[0073]
　As the copolymerizable monomer, preferably, the functional group-containing vinyl monomers, aromatic vinyl monomers or a combination thereof, and more preferably include include single use of the aromatic vinyl monomer.
[0074]
　Further, as described above (meth) acrylic, including acrylic and methacrylic, in the second monomer component, from the viewpoint of water resistance, preferably, it is mentioned methacrylic is.
[0075]
　In a second monomer component, the content of the (meth) acrylic acid ester and a copolymerizable monomer, the total amount of the second monomer component, (meth) acrylic acid ester is 50 mass% or more, preferably, 70 mass% or more, more preferably 77 mass% or more. Further, the copolymerizable monomer is preferably 50 mass% or less, preferably 30 wt% or less, and more preferably not more than 23 wt%.
[0076]
　(Meth) if the content is above the range of the copolymerizable monomer and acrylic acid esters, it is possible to obtain excellent adhesive strength and blocking resistance.
[0077]
　That is, the second monomer component without containing copolymerizable monomer, (meth) may be only the acrylic acid ester, also (meth) and a copolymerizable monomer and acrylic acid esters in a proportion of the it may be used in combination. Preferably, either alone (meth) acrylic acid ester, or (meth) and a copolymerizable monomer and acrylic acid esters is used together with the above ratio.
[0078]
　When the second monomer component is only (meth) acrylic acid ester, as a second monomer component, more preferably having an alkyl moiety having 4 carbon atoms (meth) or composed of only acrylic acid ester, or 1 carbon atoms and the alkyl moiety having the (meth) acrylic acid esters of, and a combination of (meth) acrylic acid ester having an alkyl moiety of 4 carbon atoms.
[0079]
　The second monomer component, if consisting only of (meth) acrylic acid ester having an alkyl moiety of 4 carbon atoms, especially preferably, either consist of only methacrylic acid n- butyl, also methacrylic acid n- butyl, acrylic acid combination of n- butyl.
[0080]
　Further, when the second monomer component is a combination of having alkyl portions of one carbon and (meth) acrylic acid ester having an alkyl moiety of 4 carbon atoms and (meth) acrylic acid ester, particularly preferably, methacrylic combination of methyl and methacrylic acid n- butyl, a combination of methyl methacrylate and n- butyl acrylate.
[0081]
　The second monomer component, (meth) is a combination of a copolymerizable monomer and acrylic acid esters, as the second monomer component, more preferably having an alkyl moiety having 4 carbon atoms (meth) acrylic acid ester When, the combination of the styrene and the like, especially preferably a combination of acrylic acid n- butyl and styrene, and a combination of methacrylic acid n- butyl and styrene.
[0082]
　According to the second monomer component, it is possible to adjust the glass transition temperature of the acrylic polymer (B) in the range described below.
[0083]
　Further, as the copolymerizable monomer, if the carboxy group-containing vinyl monomer is used, its content is, in terms of production stability of the composite particles (C), based on the total amount of the second monomer component, for example, 5 mass % or less, preferably 3 mass% or less. Incidentally, preferably, the second monomer component does not contain a carboxyl group-containing vinyl monomer.
[0084]
　The polymerization of the second monomer component is not particularly limited and a known polymerization method is employed. For example, water, a second monomer component and the polymerization initiator are blended, in water, the second monomer component is polymerized.
[0085]
　The polymerization initiator is not particularly limited, for example, hydrogen peroxide, for example, ammonium persulfate, potassium persulfate, persulfates such as sodium persulfate, for example, cumene hydroperoxide, t- butyl hydroperoxide, benzoyl peroxide, t- butyl peroxy-2-ethylhexanoate, t- butyl peroxybenzoate, organic peroxides such as lauroyl peroxide, for example, azo compounds such as azobisisobutyronitrile, or, with these iron ions, such as metal ions and sodium sulfoxylate, formaldehyde, pyrosulfite soda, sodium bisulfite, L- ascorbic acid, and the like redox initiators in combination with reducing agents such as Rongalit. These polymerization initiators may be used alone or in combination of two or more kinds.
[0086]
　The mixing ratio of the polymerization initiator, depending on the purpose and application, but is appropriately set, based on the total amount of the second monomer component, for example, not less than 0.1 wt%, e.g., 5 wt% or less it is.
[0087]
　In the polymerization, it can be optionally formulated molecular weight modifier.
[0088]
　The molecular weight modifier, for example, t-dodecyl mercaptan, n- mercaptans such as dodecyl mercaptan, for example, allyl sulfonic acid, methallyl sulfonic acid and allyl compounds such as these sodium salts. These molecular weight modifiers may be used alone or in combination of two or more. The mixing ratio of the molecular weight modifier, depending on the purpose and application, are set appropriately.
[0089]
　The polymerization conditions, under normal pressure, the polymerization temperature is, for example, 30 ° C. or higher, preferably not 50 ° C. or higher, e.g., 95 ° C. or less, preferably 85 ° C. or less. The polymerization time is, for example, 1 hour or more, preferably, not less than 2 hours, for example, 30 hours or less, preferably less than 20 hours.
[0090]
　Further, in the production of the acrylic polymer (B), from the viewpoint of improving the production stability, if necessary, it can be blended emulsifier (surfactant).
[0091]
　The emulsifier (surfactant), for example, anionic surfactants, nonionic surfactants, and the like cationic surface active agents.
[0092]
　Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyl diphenyl ether disulfonate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl sulfosuccinate , polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sodium dialkyl sulfosuccinate sulfate, sodium stearate, sodium oleate, tert- octylphenoxyethoxypolyethoxyethyl sodium sulfate, etc. and the like.
[0093]
　Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene-oxypropylene block copolymer, tert- octylphenoxy ethyl polyethoxy ethanol, and the like nonyl phenoxyethyl polyethoxy ethanol.
[0094]
　Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride.
[0095]
　These emulsifiers (surfactants) may be used alone or in combination of two or more kinds.
[0096]
　As an emulsifier (surfactant), preferably, include anionic surface active agent, more preferably, sodium dodecyl benzene sulfonate.
[0097]
　The mixing ratio of the emulsifier (surfactant) is not particularly limited, from the viewpoint of production stability of the composite particles (C), based on the total amount of the second monomer component, for example, 0.02 wt% or more, for example, 5 wt% or less.
[0098]
　Further, in the production of the acrylic polymer (B), from the viewpoint of improving the production stability, e.g., pH adjusting agents, such as ethylenediamine tetraacetic acid and sequestrant such as a salt, for example, mercaptans, such as molecular weight modifier such as low molecular halogen compounds (chain transfer agent) may be blended at an appropriate ratio known additives.
[0099]
　The weight average molecular weight of the acrylic polymer (B), in terms of standard polystyrene by gel permeation chromatography (GPC), for example, 05,000 or more, or preferably, 10,000 or more, for example, 1,000,000, preferably it is 500,000 or less.
[0100]
　The glass transition temperature of the acrylic polymer (B), -28 ° C. or higher, preferably not -10 ° C. or higher, 80 ° C. or less, preferably 60 ° C. or less.
[0101]
　If the glass transition temperature is above the range of the acrylic polymer (B), it is possible to obtain excellent adhesive strength and blocking resistance. The glass transition temperature can be measured in accordance with Examples described later.
[0102]
　Composite particles (C) is as long as it contains the above ethylene-unsaturated carboxylic acid copolymer (A) and the acrylic polymer (B), the form thereof is not particularly limited, for example, ethylene-unsaturated carboxylic acid structure acrylic polymer in the continuous phase (B) is dispersed in the copolymer (a), a core / shell structure, composite structure, localized structure, potbelly-shaped structure, octopus-shaped structure, raspberry-like structure, multi-particle composite structure , and the like IPN structure.
[0103]
　As composite particles (C), preferably, the acrylic polymer in the continuous phase of the ethylene-unsaturated carboxylic acid copolymer (A) (B) can be cited dispersed structure.
[0104]
　Method of manufacturing such a composite particle (C) is not particularly limited, it may be a known method.
[0105]
　For example, by the following method, it is possible to obtain ethylene-unsaturated carboxylic acid copolymer of acrylic polymer in a continuous phase of (A) (B) composite particles (C) of the dispersed structure.
[0106]
　That is, first, in the presence of manufactures ethylene-unsaturated carboxylic acid copolymer (A) in the manner described above, the resulting ethylene-unsaturated carboxylic acid copolymer (A), acrylic polymer in the manner described above (B) by producing, it is possible to obtain composite particles (C).
[0107]
　Further, for example, first, preparing an acrylic polymer (B) in the above method, the presence of the resulting acrylic polymer (B) (e.g., disk Parr Deployment), the ethylene-unsaturated carboxylic acid in the manner described above by producing the copolymer (a), it is possible to obtain composite particles (C).
[0108]
　Preferably, first, to produce ethylene-unsaturated carboxylic acid copolymer (A), ethylene-unsaturated carboxylic acid copolymer obtained the presence of (A) (e.g., disk Parr Deployment), the acrylic polymer (B) by producing obtain composite particles (C). As the ethylene-unsaturated carboxylic acid copolymer (A), as described above, a commercially available product can be used.
[0109]
　In the composite particles (C), the content of the ethylene-unsaturated carboxylic acid copolymer (A) and the acrylic polymer and (B), relative to the total amount of them, ethylene-unsaturated carboxylic acid copolymer (A ) is, for example, 1 mass% or more, preferably 5 mass% or more, more preferably, 10 mass% or more, e.g., 95 wt% or less, preferably 70 wt% or less, more preferably, less than 50 wt% it is. Also, the acrylic polymer (B), for example, 5 wt% or more, preferably 30 mass% or more, more preferably, exceed 50 mass%, for example, 99 mass% or less, preferably 95 wt% or less , more preferably 90 mass% or less.
[0110]
　If the content is above the range of the ethylene-unsaturated carboxylic acid copolymer (A) and the acrylic polymer (B), and it is possible to obtain excellent adhesive strength and blocking resistance.
[0111]
　Incidentally, the content of the ethylene-unsaturated carboxylic acid copolymer (A) and the acrylic polymer and (B) in the composite particles (C) can be calculated from the charging ratio of the raw material components.
[0112]
　The weight average particle diameter of the composite particles (C) (Measurement method: light scattering measurements) is, for example, 10nm or more, e.g., 10 [mu] m or less, preferably 1μm or less.
[0113]
　The average particle size of the composite particles observed by electron microscopy (C) are, for example, 50 nm or more, preferably, 60 nm or more, more preferably at 80nm or more, e.g., 300 nm or less, more preferably 200 nm or less , still more preferably 120nm or less.
[0114]
　If the average particle diameter within the above range, it is possible to improve the storage stability of the aqueous dispersion of the composite particles (C), also be a good transparency and water resistance of the laminate (described below) it can.
[0115]
　The water dispersion, in addition to the above-mentioned composite particles (C), as a resin component may further contain resin particles (E).
[0116]
　Resin particles (E) is a particle made of different resin from the composite particles (C), specifically, comprising an olefin-based polymer (D).
[0117]
　The olefin-based polymer (D), for example, polyolefin resins. More specifically, for example, alpha-olefins having 2 to 16 carbon atoms (e.g., ethylene, propylene, 1-butene, 3-methyl - 1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene, homopolymers and copolymers of 1-like dodecene) is and the like.
[0118]
　Further, as the olefinic polymer (D), in addition to the above, the ethylene-unsaturated carboxylic acid copolymer (A) are also included.
[0119]
　That is, the resin component of the aqueous dispersion, in addition to containing the ethylene-unsaturated carboxylic acid copolymer in the composite particles (C) (A), further, as the olefin-based polymer in the resin particles (E) (D) , it can contain an ethylene-unsaturated carboxylic acid copolymer (a). Incidentally, in such a case, the ethylene-unsaturated carboxylic acid copolymer as the olefin polymer in the resin particles (E) (D) (A) is not complexed with an acrylic polymer (B), the composite as a separate particles and particles (C), it is dispersed in water dispersion.
[0120]
　These olefinic polymer (D) may be used alone or in combination of two or more.
[0121]
　As the olefin polymer (D), preferably, ethylene-unsaturated carboxylic acid copolymer (A).
[0122]
　Further, olefinic ethylene-unsaturated carboxylic acid copolymer used as polymer (D) (A), the ethylene-unsaturated carboxylic acid copolymer different from (A) type contained in the composite particles (C) Although it may be, preferably, ethylene-unsaturated carboxylic acid copolymer of ethylene-unsaturated carboxylic acid copolymer (a) and same composition (a) is contained in the composite resin (C), olefin used as the polymer (D).
[0123]
　If the olefin polymer aqueous dispersion consisting of (D) the resin particle (E) is blended, the blending method is not particularly limited, for example, a dispersion of composite particles (C), resin particles (E ) dispersion and may be mixed in, also the dispersion of the composite particles (C), may be added resin particles (E) (solid content of dispersion of), further, the resin particles (E the dispersion of), the composite particles (C) (solid content of dispersion of) may be added.
[0124]
　Further, for example, at the time of manufacture of the dispersion of the composite particles (C), by adjusting the like amount of the first monomer component and the second monomer component, thereby forming composite particles (C), the complex separately from the particles (C), ethylene-unsaturated carboxylic acid copolymer consisting (a) alone polymer particles (i.e., resin particles made of olefin-based polymer (D) (E)) can also be formed.
[0125]
　When the resin particles made of olefin-based polymer (D) (E) is blended, the content, the total amount of the resin component (i.e., the composite particles (C) and resin particles (E) the total amount of) against the resin particles (E) are, for example, 5 wt% or more, or preferably 10 mass% or more, e.g., 80 wt% or less, preferably 70 mass% or less.
[0126]
　The content of the content of the ethylene-unsaturated carboxylic acid copolymer to the total amount of the resin component (A) (i.e., ethylene-unsaturated carboxylic acid copolymer in the composite particles (C) (A), further, when the ethylene-unsaturated carboxylic acid copolymer in the resin particles (E) (a) is contained, the content of the ethylene-unsaturated carboxylic acid copolymer in the composite particles (C) (a) , the total amount of the content of the ethylene-unsaturated carboxylic acid copolymer in the resin particles (E) (a)) is 58 mass% or more, preferably, not less than 65 wt%, 90 wt% or less, preferably is 80 wt% or less. Further, other components (such as an acrylic polymer (B)) is 10 mass% or more, preferably not less than 20 wt%, 42 wt% or less, or preferably 35 mass% or less.
[0127]
　If the content is above the range of the ethylene-unsaturated carboxylic acid copolymer to the total amount of the resin component (A), it is possible to obtain excellent adhesive strength and blocking resistance.
[0128]
　Incidentally, the content of the ethylene-unsaturated carboxylic acid copolymer in the resin component (A) can be calculated from the charging ratio of the raw material components.
[0129]
　The water dispersion, in addition to the above resin components can further contain additives.
[0130]
　As the additive, for example, emulsifiers mentioned above, other curing agents, crosslinking agents, coalescents, defoaming agents, cissing inhibitor, leveling agents, tackifiers, hardness imparting agents, preservatives, thickeners, antifreeze agents, dispersing agents, inorganic pigments, known additives such as an organic pigment. These additives may be used alone or in combination of two or more kinds. Timing of blending ratio and formulation additives, depending on the purpose and application, are appropriately set
　also solid concentration of the aqueous dispersion, for example, 10 mass% or more, or preferably 20 mass% or more, For example, 60 wt% or less, preferably not more than 50 wt%.
[0131]
　Further, pH of the aqueous dispersion, for example, 7 or more, preferably, 8 or more, e.g., 11 or less, preferably 10 or less.
[0132]
　Such aqueous dispersions, the use in the formation of the adhesive layer of the laminate (heat seal layer), it is possible to obtain a laminate with excellent bonding strength and blocking resistance.
[0133]
　Therefore, aqueous dispersions, a substrate, in the laminate comprising an adhesive layer laminated on at least one side surface of the substrate, as an adhesive composition for forming the adhesive layer, preferably used be able to.
[0134]
　More specifically, in FIG. 1, the laminate 1 comprises a substrate 2, an adhesive layer 3 laminated on one side surface of the substrate 2.
[0135]
　As the substrate 2, for example, cellophane, polyethylene, ethylene-vinyl acetate copolymer, ionomer, polypropylene, polyamides (nylons), polyesters, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate, polystyrene, plastic film made of plastic material such as polyacrylonitrile copolymers also, on these plastic films, aluminum, gold, silver, copper, nickel, zinc, titanium, cobalt, indium, a metal such as chromium, for example, aluminum oxide, deposited film with a deposit of such oxides of silicon oxide, for example, a metal foil such as aluminum foil, for example, paper, such as a nonwoven fabric and the like.
[0136]
　These substrates 2 may be used alone or in combination of two or more kinds.
[0137]
　As the substrate 2, preferably, a metal foil, more preferably, include aluminum foil.
[0138]
　The adhesive layer 3 may be obtained on one side surface of the substrate 2, by the above aqueous dispersion coating (coating) and dried.
[0139]
　The coating (coating) method of the aqueous dispersion is not particularly limited, for example, gravure coating, roll coating, dip coating, known methods such as spray coating is employed.
[0140]
　As the drying conditions, the drying temperature is, for example, a 100-200 ° C., the drying time is, for example, 10 seconds to 30 minutes.
[0141]
　Further, prior to coating and drying, in order to improve the adhesion between the substrate 2 and the adhesive layer 3, the base material 2, it is possible to coat the primer (such as titanate or polyethylene imine), It can also be subjected to pretreatment such as corona discharge treatment or chemical treatment.
[0142]
　According to such a laminate 1, since the aqueous dispersion is used for the adhesive layer 3, it is possible to obtain excellent adhesive strength and blocking resistance.
[0143]
　Therefore, the laminated body 1, in various industrial fields, used as a heat seal material.
[0144]
　In heat sealing, as shown in FIG. 1, a substrate 2, the adherend layer 4 (see FIG. 1 the dashed line), but it is adhered through an adhesive layer 3.
[0145]
　Adherend layer 4 is a material laminate 1 described above is bonded, for example, cellophane, polyethylene, ethylene-vinyl acetate copolymer, ionomer, polypropylene, polyamides (nylons), polyesters, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate, polystyrene, plastic film made of plastic material such as polyacrylonitrile copolymer, also on these plastic films, aluminum, gold, silver, copper, nickel, zinc, titanium, cobalt, indium, a metal such as chromium, for example, vapor deposition films deposited aluminum oxide, oxide of silicon oxide and the like, for example, a metal foil such as aluminum foil, for example, paper, nonwoven fabric, etc. are .
[0146]
　Further, as the adherend layer 4, the laminate 1 comprises a substrate 2 and adhesive layer 3 can be mentioned.
[0147]
　These adherend layer 4 may be used alone or in combination of two or more kinds.
[0148]
　As the adherend layer 4, from the viewpoint of adhesive strength and adhesion ease, preferably, polyvinyl chloride, plastic film made of polyvinylidene chloride.
[0149]
　The the substrate 2 and the adherend layer 4 as a method for heat sealing is not particularly limited and a known method is employed. For example, as shown in FIG. 1, the the base member 2 and the adherend layer 4, are laminated through an adhesive layer 3, then heated and pressurized. In the case where the laminate 1 is used as the adherend layer 4 is bonded is an adhesive layer 3 between them two layers via an adhesive layer 3 of the two substrates 2 are laminated, heat and pressure It is pressed.
[0150]
　The heating temperature is, for example, 80 ° C. or higher, preferably not 100 ° C. or higher, for example, 250 ° C. or less, preferably 200 ° C. or less. The pressure is, for example, more than 50 kPa, preferably not less than 100 kPa, for example, 500 kPa or less, preferably not more than 300 kPa.
[0151]
　Thus, the substrate 2 is the adherend layer 4 are heat seal (thermocompression bonding).
[0152]
　Incidentally, if this way laminate adherend layer 4 are laminated 1 (i.e. on one side surface of the adhesive layer 3, the adherend layer 4 laminated on one side surface of the adhesive layer 3 laminate 1) comprising, the heat seal condition (i.e., regardless of the front and back) of the heat seal, are included in the present invention.
[0153]
　Then, such a laminated body 1, since with excellent adhesion strength and blocking resistance, in various industrial fields, it is suitably used as a packaging material.
[0154]
　The articles to be packaged that is wrapped by the laminate 1 is not particularly limited, for example, confectionery, food products of tea leaves, such as spices, for example, tobacco, fragrance such as fragrant wood, other pharmaceuticals, a variety of paper and other industrial products, and the like.
Example
[0155]
　The following examples and comparative examples, the present invention will be described in detail, the present invention is not limited thereto. The blend ratio used in the following description (content), physical properties, the specific values ​​of such parameters are described in the "Description of the Invention" section above, the blending ratio corresponding to them ( content), physical properties, the upper limit of such appropriate according parameter ( "hereinafter" substitute defined numerical are) or the lower limit value as "less than" ( "or" numerical values ​​is defined as "excess") be able to.
[0156]
　　Example 1
　Ethylene content of CHEMIPEARL S100 (in the raw materials as ethylene-unsaturated carboxylic acid copolymer (A): 85 wt%, the type of the unsaturated carboxylic acid: methacrylic acid, sodium hydroxide neutralization product, solids 27%, manufactured by Mitsui Chemicals, Inc.) 200 parts by weight, were charged deionized water 27 parts by weight in the reaction vessel, the temperature was raised to 80 ° C. under a stream of nitrogen, was added 0.3 part by weight of potassium persulfate. The degree of neutralization at this time was measured by the following method.
[0157]
　Separately, methacrylic acid n- butyl 100 parts by mass of n- dodecyl mercaptan (molecular weight modifier) ​​and 0.2 part by weight, the sodium dodecylbenzenesulfonate (emulsifier) ​​0.4 parts by weight, of deionized water 40 parts by weight is emulsified, the resulting emulsion mixture was added dropwise to the reaction vessel for 2 hours, then, by holding at the same temperature for 2 hours to complete the polymerization. Thus, as to form an acrylic polymer (B), to obtain a dispersion of the composite resin (C).
[0158]
　Incidentally, drying a portion of the resulting aqueous dispersion, Observation of the solid particles with an electron microscope, a 80 ~ 120 nm particle size, the continuous phase of the ethylene-methacrylic acid copolymer (A) composite particles of structure methacrylate n- butyl dispersed (C) was observed at. Further, the glass transition temperature of the acrylic polymer (B), was calculated by the following method.
[0159]
　Then added 1 part by weight of polyoxyethylene lauryl ether (emulsifier), then the dispersion obtained, as the resin particles (E), Chemipearl S100 (ethylene content in the feed: 85 wt%, unsaturated carboxylic type of acid: methacrylic acid, sodium hydroxide neutralization product, 27% solids, manufactured by Mitsui Chemicals, Inc.) 911 parts by weight was added and after mixing, was adjusted to 28 wt% solids with deionized water, water to obtain a dispersion.
[0160]
　Examples 2-8 and Comparative Examples 1-8
　kind and amount of the ethylene-unsaturated carboxylic acid copolymer (A), the kind and amount of the acrylic polymer raw material monomer (second monomer component) of (B), further, the type and amount of the resin particles (E), except for changing as described in Table 1, in the same manner as in example 1 to obtain an aqueous dispersion.
[0161]
　In Comparative Example 5, the acrylic polymer (B), rather than produced in the presence of ethylene-unsaturated carboxylic acid copolymer (A), ethylene-unsaturated carboxylic acid copolymer (A) and prepared acrylic polymer and (B) were separately mixed in a ratio described in Table 1.
[0162]
　
1) neutralization degree
　measuring the infrared absorption spectrum of the sample, 1700 cm corresponds to a carboxy group -1 seeking peak height of the absorption of the (peak height and a.).
[0163]
　Further, by contacting the sample with hydrochloric acid to remove the metal ions in the resin (demetalated) ions
give the acid copolymer which are not binding (intramolecular bridge). The infrared absorption spectrum of a sample of the acid copolymer is measured, 1700 cm -1 obtains a peak height of the absorption of the (peak height and b.).
[0164]
　Peak height a corresponds to the number of carboxyl groups which are not ionic bond in the resin.
[0165]
　The peak height b corresponds to the number of all carboxyl groups in the resin.
[0166]
　Therefore, by the following equation, it obtains degree of neutralization (%).
[0167]
　　Degree of neutralization (%) = 100-100 × a /
b 2) Glass transition temperature
　The glass transition temperature, Computational Materials Science of Polymers (A.A.Askadskii , Cambridge Intl Science Pub (2005/12/30)) Chapter XII determined by the method described in. Here, calculation software CHEOPS (version4.0, Million Zillion Software Inc.) the above method is employed using the obtained glass transition temperature.
[0168]
[Table 1]

[0169]
　It should be noted that following the details of the abbreviations in the table.
S100: trade name CHEMIPEARL S100, the ethylene content in the feed: 85 wt%, the type of the unsaturated carboxylic acid: methacrylic acid, sodium hydroxide neutralization product, 27% solids, manufactured by Mitsui Chemicals, Inc.
S80N: trade name CHEMIPEARL S80N , ethylene content in the feed: 80 wt%, the type of the unsaturated carboxylic acids: acrylic acid, sodium hydroxide neutralization product, solids 24%, manufactured by Mitsui Chemicals Inc.
S650: trade name CHEMIPEARL S650, the ethylene content in the feed the amount: 80 wt%, the type of the unsaturated carboxylic acid: methacrylic acid, sodium hydroxide neutralization product, 27% solids, manufactured by Mitsui Chemicals Inc.
AN: acrylonitrile
ST: styrene
AAC: acrylic acid
MMA: methyl methacrylate
nBMA: methacrylic acid n- butyl
iBA: butyl iso- acrylate
nBA: butyl n- acrylate
　　evaluation
　1) peel strength g / 15 mm)
　coated amount into a hard aluminum foil (thickness 20 [mu] m) is 3 g / m 2 water dispersion was coated by a wire bar so as to, dried 1 minute at 120 ° C., to obtain a laminate.
[0170]
　The resulting laminate was overnight left at room temperature, cut into strips of 15mm width, superposed and coated surface, and a polyvinyl chloride sheet (thickness 200 [mu] m), at 155 ° C., the pressure 196 kPa (2 kg / cm 2 was 0.5 seconds heat sealed with). Using the obtained test pieces, the peel strength was measured at a tensile rate of 200 mm / min conditions. The evaluation results are shown in Table 1. In addition, the peel strength was evaluated according to the following criteria. The results are shown together in Table 1.
◎: is 1200g / 15mm or more.
○: less than 900g / 15mm more than 1200g / 15mm.
△: less than 500g / 15mm more than 900g / 15mm.
×: it is 500g / 15mm or less.
[0171]
　2) Blocking resistance
　The laminate obtained above was cut into a square aspect each 5 cm, overlapped with the coated surface with each other, 45 ° C., 250 g / cm 2 , the following criteria blocking resistance under conditions of 24 hours It was evaluated according to. The results are shown in Table 1.
○: between overlapping of the coated surface was is, away without resistance.
△: sticking to the part of the coating film (adhesive layer) was observed.
×: sticking to the entire surface of the coating film (adhesive layer) was observed.
[0172]
　3) polymerization stability
　by observing the state of the composite particles (C) aqueous dispersion after preparation was evaluated according to the following criteria. The results are shown in Table 1.
○: no occurrence of a large amount of aggregates, fluidity was maintained.
△: Although a large amount of aggregates is occurring, the fluidity of the liquid was maintained.
×: a large amount of aggregate occurred, the fluidity of the liquid was lost.
DESCRIPTION OF SYMBOLS
[0173]
1 stack
2 substrate
3 adhesive layer
adherend 4
　The above invention has been provided as illustrative embodiments of the present invention, this is merely illustrative and should not be construed restrictively. Modification of the present invention that will be obvious to those skilled in the art will be covered by the following claims.
Industrial Applicability
[0174]
　Aqueous dispersions and the laminated body of the present invention, for example, preferred confectionery, food products of tea leaves, such as spices, for example, tobacco, fragrance such as fragrant wood, other pharmaceuticals, as a packaging material for various industrial products such as paper used to.

The scope of the claims
[Claim 1]
　Contains a resin component, a water dispersing the resin component,
　the resin component comprises a composite particle (C) containing the ethylene-unsaturated carboxylic acid copolymer (A) and the acrylic polymer (B),
　the ethylene-unsaturated carboxylic acid copolymer (a)
　　contains ethylene and unsaturated carboxylic acids, obtained by copolymerization of the first monomer component content of the ethylene is not less than 75 wt%,
　the acrylic polymer (B) is
　　(meth) containing acrylic acid ester, the (meth) content of the acrylic acid ester is obtained by polymerization of the second monomer component is not less than 50 wt%,
　the acrylic polymer (B the glass transition temperature of) the, is at 80 ° C. or less -28 ° C. or higher,
　the content ratio of the ethylene-unsaturated carboxylic acid copolymer with respect to the total amount of the resin component (a) is 58 mass% or more 90 Or less by mass%
, wherein the water dispersion.
[Claim 2]
　Wherein the resin component is further characterized in that it comprises a resin particle (E) consisting of an olefin-based polymer (D), aqueous dispersion of claim 1.
[Claim 3]
　Comprising a substrate and an adhesive layer laminated on at least one side surface of the substrate,
　the adhesive layer, characterized in that it is obtained by drying the aqueous dispersion according to claim 1 , laminate.
[Claim 4]
　Further characterized in that it comprises a adherend layer laminated on one side surface of the adhesive layer, the laminated body according to claim 3.
[Claim 5]
　The adherend layer, characterized in that it consists of polyvinyl chloride and / or polyvinylidene chloride, laminate according to claim 4.