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
[0002]Conventionally, in the various industrial fields, plastic film, metallized film, metal foil, paper, a substrate such as a nonwoven fabric, bonded by heat and pressure (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. (E.g., see Patent Document 1 and Patent Document 2).
CITATION
Patent Document
[0004]
Patent Document 1: JP 2001-179909 Patent Publication
JP 2: WO2016 / 076130 pamphlet
Summary of the Invention
Problems that the Invention is to Solve
[0005]
　And the type of substrate and the adherend, by such applications, it may be required to heat seal a shorter time and / or at a low temperature.
[0006]
　An object of the present invention, the water dispersion with a short heat sealing time excellent adhesive strength and blocking resistance, and to provide a laminate obtained by using the aqueous dispersion.
[0007]
　Here, the blocking resistance, even superposed laminate, means that not sticking to each other.
Means for Solving the Problems
[0008]
　The present invention [1], a resin component, a water dispersion containing water, wherein the resin component is ethylene-unsaturated carboxylic acid copolymer polymer (A), as polymerized units an acrylic acid ester unit polymer having (B), and comprises an ethylene-vinyl acetate copolymer (C), the ethylene-unsaturated carboxylic acid copolymer (a), and a polymer having the acrylic acid ester units as polymerized units including composite particles having (B) and (D), the ethylene-unsaturated carboxylic acid copolymer (a), and, the composite particles having the ethylene-vinyl acetate copolymer (C) and (E) the aqueous dispersion, which comprise.
[0009]
　The present invention [2], with respect to the resin component 100 wt%, the content of the ethylene-unsaturated carboxylic acid copolymer (A) is 35 to 70%, having an acrylic acid ester units as polymerized units is from 25 to 64.5% the content of the polymer (B), the content of the ethylene-vinyl acetate copolymer (C) is from 0.5 to 20% water of the above-mentioned [1], wherein It contains a dispersion. (Provided (A) (B) (the total amount to 100% of C))
　present invention [3] is a method for producing an aqueous dispersion according to [1], in the presence of water, ethylene-unsaturated carboxylic acid copolymer (a) is emulsified, obtaining a dispersion liquid 1 containing the resin particles (I) made of the ethylene-unsaturated carboxylic acid copolymer (a), the dispersion 1 during, and a (meth) was added to acrylic acid ester monomer, polymerizing a polymer having acrylic acid ester units as polymerized units (B), the copolymer (a) and the polymer (B) obtaining a dispersion liquid 2 containing composite particles (D), in the presence of water, emulsified ethylene-unsaturated carboxylic acid copolymer (a) and ethylene-vinyl acetate copolymer and (C) simultaneously, containing composite particles (E) having said copolymer and said copolymer (a) (C) Obtaining a dispersion 3, was mixed with the dispersion liquid 3 and the dispersion liquid 2, and a step of obtaining a dispersion liquid containing the composite particles (D) and the composite particles (E), water-dispersible it includes a method for manufacturing the body.
[0010]
　The present invention [4], comprising a substrate, and an adhesive layer laminated on at least one side surface of the substrate, wherein the adhesive layer is, drying the aqueous dispersion according to the above [1] the resulting includes a laminate.
[0011]
　The present invention [5], further comprising a adherend layer laminated on one side surface of the adhesive layer comprises a laminate according to [4].
[0012]
　The present invention [6], the adherend layer comprises a polyvinyl chloride and / or polyvinylidene chloride, containing a laminate according to [5].
The invention's effect
[0013]
　Aqueous dispersion of the present invention, and, according to the laminate obtained by using the aqueous dispersion, even if the heat sealing in a short period of time and / or low temperature, it is possible to obtain excellent adhesive strength and blocking resistance .
BRIEF DESCRIPTION OF THE DRAWINGS
[0014]
[1] Figure 1 is a schematic diagram showing an embodiment of the laminate of the present invention.
DESCRIPTION OF THE INVENTION
[0015]
　In the present specification, the numerical range expressed using "to" means a range including numerical values ​​described before and after "to" as the lower and upper limits.
[0016]
　In numerical ranges are stepwise described herein, the upper or lower limit as described in one of the numerical ranges, be replaced by the upper limit value or the lower limit of the numerical range of the other graded according good.
[0017]
　Aqueous dispersion of the present invention contains a resin component, a water dispersing the resin component.
[0018]
　Resin component, ethylene-unsaturated carboxylic acid copolymer polymer (A), and (meth) polymer having an acrylic acid ester unit as polymerized units (B), and ethylene-vinyl acetate copolymer (C) which comprise.
[0019]
　The aqueous dispersion of the present invention, to form an ethylene-unsaturated carboxylic acid copolymer polymer (A), a (meth) polymer having an acrylic acid ester unit as polymerized units (B) and the composite particles (D). The ethylene-unsaturated carboxylic acid copolymer (A) and ethylene-vinyl acetate copolymer (C), but to form a composite particle (E). The aqueous dispersion comprises a (A) and composite particles having a (B) (D), and (A) and composite particles having (C) (E).
[0020]
　
　ethylene-unsaturated carboxylic acid copolymer (A) is obtained by copolymerization of the first monomer component.
[0021]
　The first monomer component containing ethylene and unsaturated carboxylic acids.
[0022]
　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.
[0023]
　These unsaturated carboxylic acids may be used alone or in combination of two or more.
[0024]
　As the unsaturated carboxylic acid, from the viewpoint of water resistance, preferably, it includes monobasic acids, more preferably, acrylic acid, methacrylic acid.
[0025]
　In the first monomer component, the content of ethylene and unsaturated carboxylic acids, for those total, ethylene, e.g., 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%.
[0026]
　If ethylene and content is within the above range of unsaturated carboxylic acids, it is possible to obtain excellent adhesive strength and blocking resistance.
[0027]
　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.
[0028]
　The ethylene-unsaturated carboxylic acid copolymer (A) can be obtained as dispersion (aqueous dispersion) of the resin particles (I) is 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. Ethylene-unsaturated carboxylic acid copolymer (A) has a self-emulsifying.
[0029]
　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.
[0030]
　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.
[0031]
　The ethylene-unsaturated carboxylic acid copolymer (A), the composite particles (D), dispersion stability of the composite particles (E) and the resin particles (I), to improve the printability of the laminate (described below) from the viewpoint, preferably used are neutralized.
[0032]
　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.
[0033]
　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.
[0034]
　These basic compounds may be used alone or in combination of two or more kinds.
[0035]
　As the basic compound, preferably an inorganic basic compound, and more preferably it includes, and sodium hydroxide.
[0036]
　The addition amount of the basic compound, the composite particles (D), dispersion stability of the composite particles (E) and the resin particles (I), from the viewpoint of improving the printability of the laminate (described below), ethylene-unsaturated carboxylic respect carboxy group 100 moles of acid copolymer (A), for example, 5 moles or more, preferably 30 mol or more, more preferably 50 mol or more, for example, 200 moles or less, preferably, 150 mole less.
[0037]
　When the addition amount of the basic compound is less than the above range, the composite particles in the aqueous dispersion (D), elicits a reduction in the stability of the drop, printing of the composite particles (E) and the resin particles (I) If there is a. 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.
[0038]
　Further, after addition of a neutralizing agent, preferably for a predetermined time at a predetermined temperature.
[0039]
　The holding condition, holding temperature, e.g., 40 ° C. or higher, preferably not 50 ° C. or higher, for example, 190 ° C. or less, preferably 180 ° 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.
[0040]
　By keeping the above condition, a carboxy group is neutralized, the composite particles (D), dispersion stability of the composite particles (E) and the resin particles (I), to improve the printability of the laminate (described below) can.
[0041]
　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.
[0042]
　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.
[0043]
　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.
[0044]
　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).
[0045]
　The weight average particle size of the resin particles made of ethylene-unsaturated carboxylic acid copolymer (A) (I) (Measurement method: light scattering measurements), for example, 0.01 [mu] m or more, preferably more than 0.02μm , and the example, 10 [mu] m or less, preferably 1μm or less.
[0046]
　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%.
[0047]
　Further, dispersion of the 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.
[0048]
　These ethylene-unsaturated carboxylic acid copolymer (A) may be used alone or in combination of two or more.
[0049]
　
　The polymer (B) is a polymer obtained by polymerization of the second monomer component, (meth) acrylic acid ester obtained from ((meth) acrylic acid ester monomers) (meth) acrylic acid ester units and have at least as polymerized units. That is, the second monomer component, (meth) which contains as an essential ingredient an acrylic acid ester, a polymer obtained by the polymerization (B) is an acrylic polymer.
[0050]
　Here, the (meth) acrylic acid ester, is defined as acrylic acid ester and / or methacrylic acid ester.
[0051]
　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.
[0052]
　These (meth) acrylic acid esters can be used alone or in combination of two or more.
[0053]
　(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.
[0054]
　Further, the polymer (B) as an optional component, may contain polymerized units derived from (meth) acrylic acid ester and copolymerizable copolymerizable monomers.
[0055]
　As the copolymerizable monomer, for example, include functional group-containing vinyl monomers, aromatic vinyl monomers, N- substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, halogenated vinylidene compounds, alpha-olefins, such as dienes It is.
[0056]
　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.
[0057]
　The carboxyl group-containing vinyl monomers, for example, (meth) acrylic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, and crotonic acid.
[0058]
　The hydroxyl group-containing vinyl monomers, for example, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 2-hydroxypropyl.
[0059]
　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.
[0060]
　The glycidyl group-containing vinyl monomers include, for example, glycidyl (meth) acrylate.
[0061]
　The cyano group-containing vinyl monomers include, for example, (meth) acrylonitrile.
[0062]
　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.
[0063]
　The acetoacetoxy group-containing vinyl monomers include, for example, (meth) acetoacetoxyethyl acrylate.
[0064]
　Examples of the phosphoric acid group-containing compounds, such as 2-methacryloyloxypropyl ethyl acid phosphate.
[0065]
　Examples of the amide group-containing vinyl monomers include, for example, (meth) acrylamide.
[0066]
　Examples of the vinyl esters include vinyl propionate, etc. may be mentioned (except vinyl acetate).
[0067]
　Examples of the aromatic vinyl monomers, e.g., styrene, alpha-methyl styrene, and divinylbenzene.
[0068]
　The N- substituted unsaturated carboxylic acid amides, such as N- methylol (meth) acrylamide.
[0069]
　The heterocyclic vinyl compounds, for example, and vinyl pyrrolidone.
[0070]
　The halogenated vinylidene compounds, such as vinylidene chloride, vinylidene fluoride is.
[0071]
　The α- olefins such as ethylene, propylene, and the like.
[0072]
　The dienes, e.g., butadiene and the like.
[0073]
　Further, as the copolymerizable monomer, it may be mentioned crosslinkable vinyl monomer.
[0074]
　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.
[0075]
　These copolymerizable monomers may be used alone or in combination of two or more kinds.
[0076]
　As the copolymerizable monomer, preferably, a functional group-containing vinyl monomer.
[0077]
　Further, as described above with (meth) acrylic acid ester, which comprises an acrylic acid ester and methacrylic acid ester, from the viewpoint of water resistance, preferably, methacrylic acid esters.
[0078]
　In the polymer (B), the content of the (meth) acrylic acid ester and a copolymerizable monomer, the total amount of the monomer components, (meth) acrylic acid ester, for example, 50 mass% or more, 70 wt% 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%.
[0079]
　(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.
[0080]
　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.
[0081]
　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.
[0082]
　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.
[0083]
　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.
[0084]
　According to the second monomer component, a glass transition temperature of the polymer (B) can be adjusted to the range described later.
[0085]
　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 (D), 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.
[0086]
　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.
[0087]
　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.
[0088]
　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.
[0089]
　In the polymerization, it can be optionally formulated molecular weight modifier.
[0090]
　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.
[0091]
　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.
[0092]
　In the production of the polymer (B), from the viewpoint of improving the production stability, if necessary, it can be blended emulsifier (surfactant).
[0093]
　The emulsifier (surfactant), for example, anionic surfactants, nonionic surfactants, and the like cationic surface active agents.
[0094]
　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, t-octyl phenoxy ethoxy polyethoxy ethyl sulfate sodium salt, etc. and the like.
[0095]
　Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene-oxypropylene block copolymer, t-octylphenoxy ethyl polyethoxy ethanol, and the like nonyl phenoxyethyl polyethoxy ethanol.
[0096]
　Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride.
[0097]
　These emulsifiers (surfactants) may be used alone or in combination of two or more kinds.
[0098]
　As an emulsifier (surfactant), preferably, include anionic surface active agent, more preferably, sodium dodecyl benzene sulfonate.
[0099]
　The mixing ratio of the emulsifier (surfactant) is not particularly limited, from the viewpoint of production stability of the composite particles (D), the total amount of the second monomer component, for example, 0.02 wt% or more, for example, 5 wt% or less.
[0100]
　In the production of the polymer (B), from the viewpoint of improving the production stability, e.g., pH adjusting agents, for example, sequestering such as ethylenediaminetetraacetic acid and its salts, for example, mercaptans, low such as molecular weight regulator such as molecular halogen compounds (chain transfer agent) may be blended at an appropriate ratio known additives.
[0101]
　The weight average molecular weight of the polymer (B), in terms of standard polystyrene by gel permeation chromatography (GPC), for example, 05,000 or more, preferably is 10,000 or more, for example, 1,000,000, preferably it is 500,000 or less.
[0102]
　The glass transition temperature of the polymer (B), -28 ° C. or higher, preferably not -10 ° C. or higher, 80 ° C. or less, preferably 60 ° C. or less.
[0103]
　If the glass transition temperature of the polymer (B) is within the above range, it is possible to obtain excellent adhesive strength and blocking resistance.
[0104]
　Especially, from the viewpoint of improving the adhesion strength, the glass transition temperature of the polymer (B), preferably 20 ° C. or less, further preferably 10 ° C. or less.
[0105]
　From the viewpoint of improving the blocking resistance, the glass transition temperature of the polymer (B), preferably, exceed 0 ° C., further preferably 10 ° C. or more
　
　ethylene-vinyl acetate copolymer (C), ethylene and vinyl acetate is copolymerized. During the ethylene-vinyl acetate copolymer (C), copolymerization ratio of ethylene and vinyl acetate, ethylene is preferably 50 to 95 mass%, vinyl acetate is preferably from 5 to 50 mass%.
[0106]
　During copolymer (C), ethylene is preferably 52 wt% or more, more preferably at 54 mass% or more, preferably 90 wt% or less, more preferably 85 wt% or less, the adhesion strength from the viewpoint of improving, more preferably 80 mass% or less. Further, vinyl acetate is preferably 10 mass% or more, more preferably, 15 mass% or more, from the viewpoint of improving the adhesion strength, more preferably not less than 20 wt%, preferably more than 48 wt% , more preferably not more than 46 wt%.
[0107]
　When ethylene and vinyl acetate copolymer ratio is in the above range, the heat seal material having excellent low-temperature heat-sealing property can be obtained.
[0108]
　Ethylene-vinyl acetate copolymer (C) of the invention may contain carbon monoxide as polymerized units. Carbon monoxide units 2 to 40% by weight of the copolymer, more preferably 5 to 30 wt%.
[0109]
　Ethylene-vinyl acetate copolymer (C) MFR (Melt flow rate) is preferably 2 ~ 1000 g / 10min, more preferably 5 ~ 500g / 10min.
[0110]
　
　to 100% by weight resin component of the present invention, the content of the ethylene-unsaturated carboxylic acid copolymer (A) is preferably preferably 35 to 70 mass%, further 40 to 68 wt%, 45 to 67% by weight it is particularly preferred.
[0111]
　If the content of the ethylene-unsaturated carboxylic acid copolymer to the total amount of the resin component (A) is within the above range, it is possible to obtain excellent adhesive strength.
[0112]
　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.
[0113]
　The content of the polymer having an acrylic acid ester unit as polymerized units (B) is preferably from 25 to 64.5 wt%, preferably more 27 to 55% by weight, particularly preferably 28 to 50 mass%.
[0114]
　The content of the ethylene-vinyl acetate copolymer (C) is preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%, and particularly preferably 2 to 10% by weight.
(Provided (A) (B) (a to 100% the total amount of C))
　
　The ethylene-unsaturated carboxylic acid copolymer (A) and the polymer (B), the composite particles (D) can be formed. Composite particles (D) is as long as it contains the above ethylene-unsaturated carboxylic acid copolymer (A) and polymer (B), the form thereof is not particularly limited, for example, a core / shell structure, composite structure , localized structure, potbelly-shaped structure, octopus-shaped structure, raspberry-like structure, multi-particle composite structure, such as IPN structure.
[0115]
　Especially continuous phase in the polymer of the ethylene-unsaturated carboxylic acid copolymer (A) (B) is dispersed structure is preferred.
[0116]
　Method of manufacturing such a composite particle (D) is not particularly limited, it may be a known method.
[0117]
　For example, it is possible to obtain ethylene-unsaturated carboxylic acid copolymer continuous phase in the polymer of (A) (B) composite particles of the dispersed structure (D) by the following method.
[0118]
　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), the polymer in the manner described above (B) by manufacturing, it is possible to obtain composite particles (D). Or, in the presence of water, emulsified ethylene-unsaturated carboxylic acid copolymer (A), after obtaining the ethylene-unsaturated carboxylic acid copolymer (A) the dispersion containing the resin particles (I) consisting of , that the in the dispersion was added to (meth) acrylic acid ester monomer, polymerizing the polymer (B), to produce composite particles having a copolymer (a) and the polymer (B) (D) can.
[0119]
　Further, for example, firstly, prepared polymers by the above method (B), the presence of the polymer obtained (B) (e.g., disk Parr John), the ethylene-unsaturated carboxylic acid copolymer in the manner described above the heavy by manufacturing coalescing (a), it is possible to obtain composite particles (D).
[0120]
　Preferably, in the presence of water, emulsified ethylene-unsaturated carboxylic acid copolymer (A), to obtain a dispersion containing an ethylene-unsaturated carboxylic acid copolymer (A) resin particles (I) from the addition of (meth) acrylic acid ester monomer in the dispersion, and polymerizing the polymer (B), to obtain composite particles having a copolymer (a) and the polymer (B) (D). Ethylene-unsaturated carboxylic acid copolymer (A) is to have a self-emulsifying, it is possible to reduce the amount of emulsifying agent (surfactant). When many amount of the emulsifier, which may affect the adhesion. As the ethylene-unsaturated carboxylic acid copolymer (A), as described above, a commercially available product can be used.
[0121]
　In the composite particles (D), ethylene-unsaturated carboxylic acid copolymer (A) and the polymer content of the (B), relative to the total amount of them, ethylene-unsaturated carboxylic acid copolymer (A) but, 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% is there. Further, the polymer (B) is, 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.
[0122]
　If the content of the ethylene-unsaturated carboxylic acid copolymer (A) and polymer (B) and is within the above range, it is possible to obtain excellent adhesive strength.
[0123]
　The content ratio of the ethylene-unsaturated carboxylic acid copolymer in the composite particles (D) (A) and the polymer (B) can be calculated from the charging ratio of the raw material components.
[0124]
　The weight average particle diameter of the composite particles (D) (Measurement method: light scattering measurements) is, for example, 10nm or more, e.g., 10 [mu] m or less, preferably 1μm or less.
[0125]
　The average particle size of the composite particles observed by electron microscopy (D) 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.
[0126]
　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 (D), also be a good transparency and water resistance of the laminate (described below) it can.
[0127]
　
　The ethylene-unsaturated carboxylic acid copolymer (A) and ethylene-vinyl acetate copolymer (C) can form a composite particle (E). Composite particles (E) is as long as it contains the above ethylene-unsaturated carboxylic acid copolymer (A) and ethylene-vinyl acetate copolymer (C), the form thereof is not particularly limited, for example, the core / shell structure, composite structure, localized structure, potbelly-shaped structure, octopus-shaped structure, raspberry-like structure, multi-particle composite structure, such as IPN structure.
[0128]
　In particular, ethylene-vinyl acetate copolymer continuous phase in the ethylene-unsaturated carboxylic acid copolymer (C) (A) is dispersed structure is preferred. The weight average particle diameter of the composite particles (E) is usually about 50 ~ 300 nm, preferably 60 ~ 200 nm, especially 80 ~ 120 nm is preferred.
[0129]
　Method of manufacturing such a composite particle (E) is not particularly limited, it may be a known method.
[0130]
　For example, it is possible to obtain the ethylene-unsaturated carboxylic acid copolymer in the continuous phase of the ethylene-vinyl acetate copolymer (C) (A) a composite particle of the dispersed structure (E) by the following method.
[0131]
　First, the ethylene-unsaturated carboxylic acid copolymer by the above method (A) and, to produce ethylene-vinyl acetate copolymer (C), respectively, the ethylene-unsaturated carboxylic acid copolymer (A) and ethylene - vinyl acetate copolymer and by emulsion simultaneously combined (C), it is possible to obtain composite particles (E). Ethylene-unsaturated carboxylic acid copolymer (A) is to have a self-emulsifying, it is possible to reduce the amount of emulsifying agent (surfactant). When many amount of the emulsifier, which may affect the adhesion. As the ethylene-vinyl acetate copolymer (C), as described above, a commercially available product can be used.
[0132]
　In the composite particles (E), the content of the ethylene-unsaturated carboxylic acid copolymer (A) and ethylene-vinyl acetate copolymer (C), relative to the total amount of them, ethylene-vinyl acetate copolymer polymer (C) 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%. The ethylene-unsaturated carboxylic acid copolymer (A) is, for example, 5 wt% or more, preferably 30 mass% or more, more preferably, exceed 50 mass%, for example, 99 mass% or less, preferably is 95 wt% or less, more preferably 90 mass% or less.
[0133]
　If the content of the ethylene-unsaturated carboxylic acid copolymer (A) and ethylene-vinyl acetate copolymer (C) is within the above range, it is possible to obtain excellent adhesive strength.
[0134]
　Incidentally, the content of the ethylene-unsaturated carboxylic acid copolymer in the composite particles (E) and (A) an ethylene-vinyl acetate copolymer (C) can be calculated from the charging ratio of the raw material components.
[0135]
　The weight average particle diameter of the composite particles (E) (Measurement method: light scattering measurements) is, for example, 10nm or more, e.g., 10 [mu] m or less, preferably 1μm or less.
[0136]
　If the weight average particle diameter of the above range, it is possible to improve the storage stability of the aqueous dispersion of the composite particles (E), also be a good transparency and water resistance of the laminate (described below) can.
[0137]
　The water dispersion, in addition to the above resin components can further contain additives.
[0138]
　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 set appropriately.
[0139]
　Moreover, the solid concentration of the aqueous dispersion, for example, 10 mass% or more, preferably not less than 20 wt%, e.g., 60 wt% or less, preferably not more than 50 wt%.
[0140]
　Further, pH of the aqueous dispersion, for example, 7 or more, preferably, 8 or more, e.g., 11 or less, preferably 10 or less.
[0141]
　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.
[0142]
　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.
[0143]
　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.
[0144]
　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.
[0145]
　These substrates 2 may be used alone or in combination of two or more kinds.
[0146]
　As the substrate 2, preferably, a metal foil, more preferably, include aluminum foil.
[0147]
　The adhesive layer 3 may be obtained on one side surface of the substrate 2, by the above aqueous dispersion coating (coating) and dried.
[0148]
　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.
[0149]
　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.
[0150]
　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.
[0151]
　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. Further, an aqueous dispersion, ethyl acetate, since the particles in an organic solvent such as toluene is not a dispersion are dispersed, residual organic solvent content of the adhesive layer 3 is preferably 100ppm or less, more preferably 10ppm following to be able to.
[0152]
　Therefore, the laminated body 1, in various industrial fields, used as a heat seal material.
[0153]
　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.
[0154]
　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 .
[0155]
　Further, as the adherend layer 4, the laminate 1 comprises a substrate 2 and adhesive layer 3 can be mentioned.
[0156]
　These adherend layer 4 may be used alone or in combination of two or more kinds.
[0157]
　As the adherend layer 4, from the viewpoint of adhesive strength and adhesion ease, preferably, polyvinyl chloride, plastic film made of polyvinylidene chloride.
[0158]
　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.
[0159]
　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.
[0160]
　Thus, the substrate 2 is the adherend layer 4 are heat seal (thermocompression bonding).
[0161]
　Adhesion strength between the substrate 2 and the adherend layer 4 can be measured by the peel strength between the substrate 2 and the adherend layer 4. Preferably at a temperature 110 ° C., a pressure 2 kg / cm 2 after crimping 0.5 seconds heat in is the peel strength of 180 degrees peeling 900 g / 15 mm or more.
[0162]
　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.
[0163]
　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.
[0164]
　The articles to be packaged that is wrapped by the laminate 1 is not particularly limited, for example, confectionery, food products, daily necessities, pharmaceuticals, and various industrial products, such as paper.
[0165]
　In particular, in the pharmaceutical and food packaging field, prevents the packaging material and the packaged articles when heat sealing is deteriorated effect, reducing power consumption and improving the productivity by speeding up the filling speed, the effect of such expected . Further, since the adhesive composition for forming the adhesive layer 3 is water dispersion has a feature that the load on the environment is small.
Example
[0166]
　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.
[0167]
　　Example 1
　Ethylene content: 85 wt%, methacrylic acid content: 15 wt%, solid content: 27% 200 parts by weight of sodium hydroxide neutralization product of ethylene-unsaturated carboxylic acid copolymer (A), de g of 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.
[0168]
　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 for 2 hours at 80 ° C., to complete the polymerization. Thus, as to form an acrylic polymer (B), the solid content concentration to obtain a water dispersion of 38% of the composite particles (D).
[0169]
　Then, the ethylene content of the above: 85% by weight, methacrylic acid content: 15 wt% of the ethylene-unsaturated carboxylic acid copolymer (A), and ethylene content: 67 wt%, vinyl acetate content: 33 mass % of ethylene-vinyl acetate copolymer (C), using a single-screw extruder, 100 parts by weight of the resin obtained by melt-kneading at 0.99 ° C., 5 parts by weight of 48% potassium hydroxide, deionized water 239 were charged parts by weight in the reaction vessel, the temperature was raised to 0.99 ° C. under a stream of nitrogen and kept at the same temperature for 4 hours. The degree of neutralization at this time was measured by the following method. Accordingly, ethylene-unsaturated carboxylic acid copolymer (A) and ethylene-vinyl acetate copolymer containing (C), the solid content concentration to obtain a water dispersion of 42% of the composite particles (E).
[0170]
　Thereafter, the aqueous dispersion 100 parts by weight of the composite particles (D), an aqueous dispersion of the composite particles (E) were added 31 parts by mass, were mixed to adjust the solid content concentration to 40% with deionized water, to obtain an aqueous dispersion.
[0171]
　The amount of each component of the resulting aqueous dispersion are shown in Table 1 (A) + (B) + (C) as 100%. Incidentally, the component (A) amount of the component (A) content derived from the composite particles (D), the sum of the composite particles (E) derived from the component (A) amount.
[0172]
　Examples 2-4
　ethylene-unsaturated carboxylic acid copolymer (A), except that the polymer (B) and ethylene-vinyl acetate copolymer (C), were changed as described in Table 1, exemplary in the same manner as in example 1 to obtain an aqueous dispersion.
[0173]
　Example 5
　except for changing in Example 2 (meth) acrylic acid ester monomer 80 parts by mass of 20 mass parts of acrylic acid n- butyl methacrylate n- butyl, in the same manner as in Example 2, an aqueous dispersion Obtained.
[0174]
　Example 6
　except for changing the (meth) 90 parts by mass of methacrylic acid n- butyl and 10 parts of acrylic acid n- butyl acrylate monomer of Example 2, in the same manner as in Example 2, an aqueous dispersion Obtained.
[0175]
　Example 7
　Ethylene-vinyl acetate copolymer of Example 2 (C) Ethylene content: 72 wt%, vinyl acetate content: was changed to 28 wt% of ethylene-vinyl acetate copolymer (C) Otherwise, in the same manner as in example 2, to obtain an aqueous dispersion.
[0176]
　EXAMPLE 8
　Ethylene-vinyl acetate copolymer of Example 2 (C) Ethylene content: 81 wt%, vinyl acetate content: was changed to 19 wt% of ethylene-vinyl acetate copolymer (C) Otherwise, in the same manner as in example 2, to obtain an aqueous dispersion.
[0177]
　Comparative Example 1
Ethylene content: 85 wt%, methacrylic acid content: 15 wt% of the ethylene-unsaturated carboxylic acid copolymer (A) 100 parts by mass of, 6 parts by weight of 48% potassium hydroxide, deionized water 241 parts by mass charged part in the reaction vessel, the temperature was raised to 0.99 ° C. under a stream of nitrogen, was prepared by keeping 4 hours at the same temperature, solid concentration of 42% ethylene-unsaturated carboxylic acid copolymer (a) the aqueous dispersion was used in place of the aqueous dispersion of the composite particles (E), the same procedure as in example 1 to obtain an aqueous dispersion.
[0178]
　Comparative Examples 2 and 3
　ethylene-unsaturated carboxylic acid copolymer (A), a polymer (B), except for changing as described in Table 1, in the same manner as in Comparative Example 1, to obtain an aqueous dispersion It was.
[0179]
　Comparative Example 4
　except that the comparative example 2 (meth) acrylic acid ester monomer was changed to 80 parts by mass of n- butyl 20 parts of acrylic acid methacrylic acid n- butyl, in the same manner as in Comparative Example 2, an aqueous dispersion Obtained.
[0180]
　Comparative Example 5
　except that in Comparative Example 2 (meth) acrylic acid ester monomer was changed to 59 parts by weight methacrylic acid n- butyl 41 parts by mass of n- butyl acrylate, in the same manner as in Comparative Example 2, an aqueous dispersion Obtained.
[0181]
　Comparative Example 6
　Ethylene content: 81 wt%, vinyl acetate content: 19 wt% of water in the aqueous dispersion of the ethylene-vinyl acetate copolymer (C) (solid content concentration: 40%) of the composite particle (E) except that was used instead of the dispersion, ethylene-unsaturated carboxylic acid copolymer (a), the polymer (B) and ethylene-vinyl acetate copolymer (C), were changed as described in Table 1 , the same procedure as in example 1 to obtain an aqueous dispersion.
[0182]
　
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.).
[0183]
　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.).
[0184]
　Peak height a corresponds to the number of carboxyl groups which are not ionic bond in the resin.
[0185]
　The peak height b corresponds to the number of all carboxyl groups in the resin.
[0186]
　Therefore, by the following equation, it obtains degree of neutralization (%).
[0187]
　　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.
3) Peel strength (g / 15 mm)
　coated amount into a hard aluminum foil (20 [mu] m) is 3 g / m 2 of aqueous dispersion by a wire bar so that coating and dried for 1 minute at 120 ° C., to obtain a laminate It was.
[0188]
　The resulting laminate was overnight left at room temperature, cut into strips of 15mm width, overlay coating surface and PVC sheet (200 [mu] m) between, at 110 ° C. or 155 ° C., a pressure 2 kg / cm 2 at 0.5 the second heat seal. Using the obtained test piece was measured 90 degree peel strength and 180 ° peel strength under the conditions of tensile speed 200 mm / sec min. The evaluation results are shown in Table 1. Further, in 180-degree peel strength in the heat sealing temperature 110 ° C., and evaluated according to the following criteria adhesion. The results are shown together in Table 1.
◎: 1300 g / 15 mm or higher
○: 1000 g / 15 mm or more 1300 g / below 15 mm
△: 500 g / 15 mm or more 1000 g / 15 mm less
×: 500 g / 15 mm less than
4) Blocking resistance
　The laminate obtained above aspect each 5cm cut into squares, superimposing the coated surface with each other, 45 ° C., 250 g / cm 2 was evaluated according to the criteria below blocking resistance under conditions of 24 hours. 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.
[0189]
[Table 1]

[0190]
　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
[0191]
　Aqueous dispersions and the laminated body of the present invention, for example, confectionery, food products, daily necessities, medicines, is suitably used as a packaging material for various industrial products such as paper.

WE CLAIM

A resin component, a water dispersion containing water,
　wherein the resin component is ethylene-unsaturated carboxylic acid copolymer polymer (A), a polymer having an acrylic acid ester unit as polymerized units and (B) comprises ethylene-vinyl acetate copolymer (C),
　the ethylene-unsaturated carboxylic acid copolymer (a), and, the composite particles having a polymer with the acrylic acid ester units as polymerized units (B) (D) and,
　the ethylene-unsaturated carboxylic acid copolymer (a), and the ethylene-vinyl acetate copolymer and the composite particles (E) having a (C)
including, aqueous dispersion.
[Requested item 2]
　The resin component 100 wt% with respect to,
　　the content of the ethylene-unsaturated carboxylic acid copolymer (A) is 35 to 70%,
　　containing polymer having the acrylic acid ester units as polymerized units (B) the amount is 25 to 64.5%,
　　the content of the ethylene-vinyl acetate copolymer (C) is from 0.5 to 20% claim 1 aqueous dispersion according. (Provided (A) (B) (a to 100% the total amount of C))
[Requested item 3]
　A method for producing an aqueous dispersion according to claim 1,
　in the presence of water, ethylene-unsaturated carboxylic acid copolymer (A) is emulsified, the ethylene-unsaturated carboxylic acid copolymer (A ) obtaining a dispersion liquid 1 containing resin particles (I) made of,
　during said dispersion 1, (meth) was added to acrylic acid ester monomer, a polymer having an acrylic acid ester unit as polymerized units (B ) was polymerized, obtaining a dispersion liquid 2 containing the composite particles (D) having said copolymer (a) and the polymer (B),
　in the presence of water, ethylene-unsaturated carboxylic acid copolymerization coalesced emulsion (a) and ethylene-vinyl acetate copolymer and (C) at the same time, the dispersion liquid 3 containing composite particles (E) having said copolymer and said copolymer (a) (C) obtaining a,
　and mixing the dispersion liquid 3 and the dispersion liquid 2, the double Obtaining a dispersion liquid containing particles (D) and the composite particles (E),
including method of aqueous dispersion.
[Requested item 4]
　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.
[Requested item 5]
　Further characterized in that it comprises a adherend layer laminated on one side surface of the adhesive layer, The laminate of claim 4.
[Requested item 6]
　The adherend layer, characterized in that it comprises a polyvinyl chloride and / or polyvinylidene chloride, laminate according to claim 5.
[Requested item 7]
　A substrate, and an adhesive layer laminated on at least one side surface of the substrate,
　wherein the adhesive layer is
　　polymerized ethylene-unsaturated carboxylic acid copolymer (A), and the acrylic acid ester unit a polymer having as a unit composite particles having (B) and (D),
　　ethylene-unsaturated carboxylic acid copolymer (a), and, the composite particles having a ethylene-vinyl acetate copolymer (C) (E) DOO
characterized in that it comprises a laminate.