JP2017036342A - Aqueous emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous emulsion for providing an aqueous adhesive capable of adhering an adherend with sufficient strength.SOLUTION: There is provided an aqueous emulsion containing a polymer component containing at least one polymer (1) selected from a group consisting of a polymer (A) and a polymer (B) and at least one kind selected from a group consisting of a photoinitiator and aromatic polyisocyanate. Polymer (A): a polymer having at least one kind selected from a hydroxy group and a carboxyl group, where all binding hydroxyl group and carboxyl group directly bind to a carbon atom constituting a main chain and percentage of the carbon atom in atoms constituting the main chain is 95% or more. Polymer (B): a polymer having at least one kind selected from a carboxyl group and a carboxylic acid anhydride structure and a chlorine atom with percentage of the carbon atom in atoms constituting the main chain of 95% or more.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous emulsion.

  Patent Document 1 discloses an aqueous emulsion containing a carboxy-modified resin of a saponified ethylene-vinyl acetate copolymer, an ethylenically unsaturated monomer, and a photopolymerization initiator. Patent Document 2 discloses an aqueous emulsion containing an olefin resin and an aliphatic polyisocyanate.

JP 2001-220474 A JP 2003-155379 A

  The aqueous emulsions described in Patent Document 1 and Patent Document 2 have not been sufficient in adhesion to the adherend.

（式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して、アルキル基又はアリール基を表す。ｎは１又は２を表す。ｍは２又は３を表す。ｒは１又は２を表す。ｓは０〜２の整数を表す。ｐは０〜１００の整数を表す。）
[１０] 芳香族ポリイソシアナートが、式（５）で表される化合物、式（６）で表される化合物及びトリス(ｐ−イソシアナートフェニル)チオホスフェートからなる群から選ばれる少なくとも１種である[９]に記載の水性エマルション。
[１１] ｐが１〜１００である前記式（６）で表される化合物を含む[９]又は[１０]に記載の水性エマルション。
[１２] 芳香族ポリイソシアナートを含む[１]〜[１１]のいずれかに記載の水性エマルション。
[１３] 芳香族ポリイソシアナート１質量部に対する重合体（１）の含有量が０．１〜１０質量部である[１２]に記載の水性エマルション。
[１４] さらに、エチレン性不飽和モノマーを含む[１]〜[１３]のいずれかに記載の水性エマルション。
[１５] さらに、ポリマー成分がポリウレタンを含む[１]〜[１４]のいずれかに記載の水性エマルション。
[１６] さらに、式（Ｂ）で表される界面活性剤を含む[１]〜[１５]のいずれかに記載の水性エマルション。

（式中、ｎは１〜３の整数を表す。ｍは１〜１００の整数を表す。）
[１７] [１]〜[１６]のいずれかに記載の水性エマルションを含む水系接着剤。
[１８] [１７]に記載の水系接着剤から得られる接着層を、被着体の間に挟持した積層体。
[１９] 紫外線を照射された、[１７]に記載の水系接着剤から得られる接着層を、被着体の間に挟持した積層体。
[２０] 被着体が、セルロース系材料又はプラスチック材料である[１８]又は[１９]に記載の積層体。
[２１] 被着体が、エチレン−酢酸ビニル共重合体である[１８]又は[１９]に記載の積層体。 The present invention includes the following inventions.
[1] A polymer component comprising at least one polymer (1) selected from the group consisting of the following polymer (A) and polymer (B), and a group consisting of a photopolymerization initiator and an aromatic polyisocyanate. An aqueous emulsion containing at least one selected.
Polymer (A): having at least one kind selected from a hydroxyl group and a carboxy group, all the hydroxyl groups and carboxy groups to be bonded are directly bonded to the carbon atoms constituting the main chain, and the carbon atoms in the atoms constituting the main chain The polymer whose ratio is 95% or more Polymer (B): The ratio of the carbon atom in the atom which has at least 1 sort (s) chosen from a carboxy group and a carboxylic anhydride structure, and a chlorine atom, and comprises a principal chain Whose polymer is 95% or more
[2] The aqueous emulsion according to [1], wherein the content of the polymer (1) is 0.1 to 10% by mass.
[3] The aqueous emulsion according to [1] or [2] containing a photopolymerization initiator.
[4] The aqueous emulsion according to [3], wherein the content of the polymer (1) with respect to 1 part by mass of the photopolymerization initiator is 3 to 1000 parts by mass.
[5] The aqueous emulsion according to any one of [1] to [4], comprising two or more types of polymers (A) having different structural units.
[6] The polymer (A) is a polymer having at least one selected from a hydroxyl group and a carboxy group at each of at least two carbon atoms constituting the end of the main chain [1] to [5]. The water-based emulsion in any one of.
[7] The aqueous emulsion according to any one of [1] to [6], wherein the polymer (A) has a carboxy group.
[8] The aqueous emulsion according to any one of [1] to [7], which contains the polymer (B).
[9] The aromatic polyisocyanate is a compound represented by the formula (5), a compound represented by the formula (6), a tris (p-isocyanatophenyl) thiophosphate, a compound represented by the formula (5) Or isocyanurate obtained from the compound represented by formula (6), biuret obtained from the compound represented by formula (5) or the compound represented by formula (6), and represented by formula (5) The aqueous emulsion according to any one of [1] to [8], which is at least one selected from the group consisting of a compound or an adduct of trimethylolpropane obtained from the compound represented by formula (6).

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group. N represents 1 or 2. m represents 2 or 3. r represents 1 or 2. S represents an integer of 0 to 2. p represents an integer of 0 to 100.)
[10] The aromatic polyisocyanate is at least one selected from the group consisting of a compound represented by the formula (5), a compound represented by the formula (6), and tris (p-isocyanatophenyl) thiophosphate. An aqueous emulsion according to [9].
[11] The aqueous emulsion according to [9] or [10], comprising a compound represented by the formula (6) wherein p is 1 to 100.
[12] The aqueous emulsion according to any one of [1] to [11], which contains an aromatic polyisocyanate.
[13] The aqueous emulsion according to [12], wherein the content of the polymer (1) with respect to 1 part by mass of the aromatic polyisocyanate is 0.1 to 10 parts by mass.
[14] The aqueous emulsion according to any one of [1] to [13], further comprising an ethylenically unsaturated monomer.
[15] The aqueous emulsion according to any one of [1] to [14], wherein the polymer component further comprises polyurethane.
[16] The aqueous emulsion according to any one of [1] to [15], further comprising a surfactant represented by the formula (B).

(In the formula, n represents an integer of 1 to 3. m represents an integer of 1 to 100.)
[17] An aqueous adhesive containing the aqueous emulsion according to any one of [1] to [16].
[18] A laminate in which an adhesive layer obtained from the aqueous adhesive according to [17] is sandwiched between adherends.
[19] A laminate in which an adhesive layer obtained by irradiation with ultraviolet rays and obtained from the aqueous adhesive according to [17] is sandwiched between adherends.
[20] The laminate according to [18] or [19], wherein the adherend is a cellulosic material or a plastic material.
[21] The laminate according to [18] or [19], wherein the adherend is an ethylene-vinyl acetate copolymer.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous emulsion for obtaining the water-based adhesive which can adhere | attach an adherend with sufficient intensity | strength can be provided.

<Polymer (1)>
The content of the polymer (1) in the aqueous emulsion of the present invention can be appropriately adjusted depending on the type of the polymer (1), the purpose of use of the aqueous emulsion, the intended performance, and the like. From the viewpoints of stability, viscosity, film-forming ability and adhesiveness of the aqueous emulsion, the content of the polymer (1) is preferably 0.1 to 10% by mass, more preferably based on the total amount of the aqueous emulsion. Is higher than 1% by mass, more preferably 2-9% by mass.
The proportion of the polymer (1) in the polymer component contained in the aqueous emulsion of the present invention is preferably 5 to 100% by mass, more preferably 5 to 70% by mass, and further preferably 5 to 30% by mass. is there.

<Polymer (A)>
In the polymer (A), the proportion of carbon atoms in the atoms constituting the main chain is 95% or more. More preferably, it is 97% or more, More preferably, it is 99% or more. The ratio of carbon atoms constituting the main chain is the ratio of the number of carbon atoms to the number of atoms constituting the main chain itself, and hydrogen atoms etc. that are bonded to the atoms constituting the main chain itself constitute the main chain. It is not included in the atoms that do. For example, in the case of ideal polyethylene, the proportion of carbon atoms constituting the main chain is 100%.
Examples of the polymer constituting the main chain of the polymer (A) include polyolefin, polyvinyl and polyacrylate.

The polymer (A) is preferably a polymer in which either a hydroxyl group or a carboxy group is directly bonded to a carbon atom constituting the main chain. Preferably, it is a polymer in which at least one group selected from a hydroxyl group and a carboxy group is directly bonded to each of at least two carbon atoms constituting the end of the main chain. Moreover, it preferably has a carboxy group.
Examples of the polymer (A) include an aromatic polymer containing an aromatic group in the main chain, an aromatic polymer containing an aromatic group in the side chain, and an aliphatic polymer. These are random copolymers, Either a block copolymer or a graft copolymer may be used.

  Aromatic polymers containing aromatic groups in the main chain include aromatic polyethers, aromatic polyether ketones, aromatic polyether ether ketones, aromatic polyether sulfones, aromatic polyesters, aromatic polyamides, aromatic polyimides, Examples include polyphenylene and phenol resin.

Examples of the aliphatic polymer include polyolefin resins such as polyethylene, polypropylene, polybutadiene, polybutadiene hydrogenated product, polyisoprene, polyisoprene hydrogenated product, polypentadiene and polypentadiene hydrogenated product;
Polymethyl (meth) acrylate (hereinafter, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid, acrylate and methacrylate may be collectively referred to as (meth) acrylate), polyhydroxymethyl (meth) acrylate And poly (meth) acrylate resins such as polyhydroxyethyl (meth) acrylate;
Polyalkylene oxide resins such as polyethylene oxide and polypropylene oxide;
Polyvinyl resins such as polyvinyl acetate, saponified polyvinyl acetate, polyvinyl chloride, and polystyrene;
Polymers such as polyvinylidene chloride, aliphatic polyethers, aliphatic polyesters, aliphatic polyamides; and monomers that form these polymers and monomers that are copolymerizable with the monomers that form these polymers A polymer etc. are mentioned. Examples of the copolymer include acrylonitrile-butadiene-styrene copolymer and ethylene- (meth) acrylate-maleic anhydride copolymer. A copolymer with a monomer having an ester group or an acid anhydride group such as (meth) acrylate or maleic anhydride includes a saponified product and a partially saponified product.

As the polymer (A), an aliphatic polymer is preferable, and an aliphatic polymer containing no aromatic group in the main chain and side chain is more preferable. The polymer is preferable because an aqueous emulsion can be stably formed and the toughness of the adhesive layer is excellent when the adhesive layer is formed by being sandwiched between adherends.
Among them, the polymer (A) can be copolymerized with a polyolefin resin, a poly (meth) acrylate resin, a polyvinyl resin, a monomer that forms these polymers, and a monomer that forms these polymers. Copolymers with other monomers are preferred, more preferably hydrogenated polybutadiene, ethylene- (meth) acrylate-maleic anhydride copolymer and saponified polyvinyl acetate.

  As the polymer (A), a polymer containing at least one structural unit selected from structural units represented by the following formulas (10) and (20) is preferable.

（式（１０）及び（２０）中、Ｒは水素原子又は−ＣＨ_３を表す）

(In the formulas (10) and (20), R represents a hydrogen atom or —CH ₃ )

The content of the structural units represented by the formulas (10) and (20) in the polymer (A) is preferably 80% by mass or more with respect to all the structural units constituting the polymer (A). Preferably it is 90 mass% or more, More preferably, it is 95 mass% or more. The content of the structural unit represented by the formula (10) is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass with respect to all the structural units constituting the polymer (A). In addition, it is usually 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less. The content of the structural unit represented by the formula (20) is usually 60% by mass or more, preferably 65% by mass or more, more preferably 70% by mass with respect to all the structural units constituting the polymer (A). In addition, it is usually 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less.
When the structural unit represented by the formula (10) is 40% by mass or more with respect to all the structural units constituting the polymer (A), the adhesive layer is formed when the aqueous emulsion of the present invention forms the adhesive layer. There is a case where the strength of the is lowered. The ratio of these structural units can be determined by an organic analysis technique such as nuclear magnetic resonance spectroscopy (NMR method).
Examples of the polymer containing at least one structural unit selected from the structural units represented by the following formulas (10) and (20) include polybutadiene hydrogenated products, polyisoprene hydrogenated products, and butadiene and isoprene. Examples include a hydrogenated product of a copolymer of at least one selected monomer and a monomer copolymerizable with the monomer.

As (meth) acrylate which is a monomer that forms a poly (meth) acrylate-based resin and an ethylene- (meth) acrylate-maleic anhydride copolymer, (meth) acrylic acid, alcohol having 1 to 10 carbon atoms, The ester compound is preferred.
Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and glycidyl (meth) acrylate. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.

The substance amount ratio of structural units derived from ethylene constituting the ethylene- (meth) acrylate-maleic anhydride copolymer is usually 10 to 95 mol%, preferably 30 to 95 mol%, more preferably. Is 50 to 95 mol%, and the substance amount ratio of structural units derived from (meth) acrylate is usually 1 to 50 mol%, preferably 4 to 35 mol%, and is a structure derived from anhydrous male The substance amount ratio of the unit is usually 0.01 to 10 mol%, preferably 1 to 10 mol%.
Such a copolymer can be obtained by adjusting the use amount of each monomer with respect to the total use amount of the raw material monomers at the time of production.

  Examples of the monomer copolymerizable with the monomer having a carbon-carbon unsaturated bond include (meth) acrylic acid, (meth) acrylate, maleic anhydride, maleic acid, fumaric acid, acrylonitrile, a vinyl compound, and an α-olefin. It is done.

  The polystyrene equivalent weight average molecular weight of the polymer (A) is usually 1000 or more, preferably 2000 or more, more preferably 5000 or more, further preferably 10,000 or more, and usually 100,000 or less, preferably 20000 or less. is there. If the weight average molecular weight is less than 1000, sufficient adhesive strength as a water-based adhesive may not be obtained, and if it exceeds 100,000, the stability of the aqueous emulsion tends to be low. The weight average molecular weight in terms of polystyrene can be measured by gel permeation chromatography (GPC).

The hydroxyl value of the polymer (A) is preferably 3 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 50 mgKOH / g or more, preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less, 100 mgKOH / g or less is more preferable.
The hydroxyl value represents the amount of the hydroxyl group that the polymer (A) has, and can be determined according to JIS K-1557.

The acid value of the polymer (A) is preferably at least 0.1 mgKOH / g, more preferably at least 1 mgKOH / g, further preferably at least 5 mgKOH / g, more preferably at most 50 mgKOH / g, more preferably at most 30 mgKOH / g. 10 mgKOH / g or less is more preferable.
An acid value represents the quantity of the carboxy group which a polymer (A) has, and can be calculated | required according to Japanese Industrial Standard K0070.

The content of the carbon-carbon unsaturated bond in the polymer (A) is preferably 5% by mass or less, and more preferably 2% by mass or less. When the polymer (A) is a hydrogenated polybutadiene, a hydrogenated polyisoprene or a hydrogenated polypentadiene, the ratio of the carbon-carbon single bond after hydrogenation to the carbon-carbon unsaturated bond before hydrogenation Is preferably 95% or more, more preferably 98% or more. The hydrogenation rate can be determined by measuring iodine value.
When the ratio of the carbon-carbon unsaturated bond is high, the heat resistance and moisture resistance of the adhesive layer may be low.

  The polymer (A) may be one kind or a combination. Preferably, it is a combination of two or more polymers (A) having different structural units, and more preferably a combination of two types.

The polymer (A) has a structure that forms the main chain of the polymer, a hydroxyl group, a hydroxyl group protected by a protecting group, or a group such as a hydroxyl group precursor that becomes a hydroxyl group by oxidation-reduction reaction (hereinafter referred to as a hydroxyl group or the like). Or a group such as a carboxy group, a carboxylic acid anhydride structure, a carboxy group protected by a protecting group, or a carboxy group precursor that becomes a carboxy group by an oxidation-reduction reaction (hereinafter referred to as a carboxy group or the like). It may be obtained by polymerizing a monomer having (which may be described) and subjecting it to a deprotection reaction, hydrolysis reaction or oxidation-reduction reaction as necessary.
The carboxylic acid anhydride structure in this specification is a structure represented by -C (= O) -OC (= O)-.

  As a deprotection reaction (hydrolysis reaction) of a polymer having an ester bond such as (meth) acrylate and vinyl acetate, a homogeneous saponification method in which the polymer is dissolved in benzene or toluene and saponified with an alkali catalyst. And a non-uniform saponification method in which a polymer pellet or powder is dispersed in a lower alcohol or the like to saponify.

As a method for introducing a hydroxyl group into a carbon atom constituting the terminal of the main chain of a polymer, usually obtained by polycondensation or polyaddition of two component monomers, such as polyether and polyester, a monomer having a hydroxyl group is converted into a hydroxyl group. And a method in which the polymerization is carried out in excess of the monomer having a reactive group that reacts with the polymer.
In the case of a polymer composed of a monomer having no hydroxyl group, such as polyamide or polyimide, a polymer having a reactive group at the terminal is prepared in advance, and then has a hydroxyl group and a reactive group that reacts with the reactive group. It can be obtained by reacting a monomer with the reactive group.
As a method for introducing a carboxy group into the carbon atom constituting the end of the main chain of polyether, polyester, polyamide, polyimide, etc., the monomer having a carboxy group is used in excess of the monomer having a reactive group that reacts with the carboxy group. Examples of the method include charging polymerization.

As a method for introducing a hydroxyl group into a carbon atom constituting the terminal of the main chain of a polymer obtained from a monomer having a carbon-carbon unsaturated bond as a polymerizable group, in the case of radical polymerization, a radical polymerization initiator containing a hydroxyl group is used. The method of using and polymerizing is mentioned. Examples of the radical polymerization initiator containing a hydroxyl group include peroxides such as hydrogen peroxide and methyl ethyl ketone peroxide, and β-azobis (β-cyano) -n-propanol and δ, δ-azobis (δ-cyano) -n. -Azobis compounds having a hydroxyl group such as pentanol. Alternatively, a hydroxyl group can be introduced at the terminal by allowing a chain transfer agent such as thioglycerol to coexist during the polymerization reaction.
In the case of anionic polymerization, first, a living polymer in which an alkali metal is bonded to the end of the polymer using an alkali metal such as sodium or lithium or a complex of an alkali metal and a polycyclic aromatic compound as a polymerization initiator. And then reacting a monoepoxy compound, a polyepoxy compound, a haloepoxy compound, formaldehyde or the like with the terminal to introduce a hydroxyl group at the terminal.
Among them, a method by radical polymerization is preferable because it can efficiently introduce a hydroxyl group to the terminal.

  In addition, the polymer (A) having a hydroxyl group on at least two carbon atoms constituting the end of the main chain is, for example, a polymer having a carbon-carbon unsaturated bond in the main chain. A polymer having a carbonyl group at the terminal can be produced by oxidizing and cleaving the saturated bond with ozone or permanganic acid, etc., and then reduced with a reducing agent such as sodium borohydride.

  As a method for adding hydrogen to a polymer having a carbon-carbon unsaturated bond, such as polybutadiene, polyisoprene and polypentadiene, there can be mentioned a usual method such as the method described in JP-A-51-71391.

The ethylene-methacrylate-maleic anhydride copolymer can be produced by a method known in the art, for example, by polymerizing ethylene, methacrylate and maleic anhydride by radical polymerization or the like.
As a method for producing a maleic acid ring-opened product of an ethylene-methacrylate-maleic anhydride copolymer, an ethylene-methacrylate-maleic anhydride copolymer is dissolved in benzene, toluene, etc., water is added, and a base catalyst is used. The method of hydrolyzing is mentioned.

  The polymer (A) can be easily obtained from the market. Commercially available products include Mersen (registered trademark) H H-6410M, H-6051, H-6960, H-6820 and H-6822X (Tosoh Corp.), Eval (registered trademark) L171B, F171B, H171B, E105B and G156B (Kuraray Co., Ltd.), Soarnol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX, 16DX, D2908H4 (Nippon Synthetic Chemical Industry Co., Ltd.), Soresin (registered trademark) ) PG505 (Nippon Synthetic Chemical Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Soda Co., Ltd.), Polytail (registered trademark) H (Mitsubishi Chemical Corporation), Epaul (registered trademark) (Idemitsu Kosan Co., Ltd.) )), OREVAC (registered trademark) G 18211, OE 808 and OE825 (Arkema Corporation), LOTADAR MAH2210, 3200, P3 3200, 3210, 4210, 6200, 3410, 3430 and 4720 (Arkema Corporation), BONDINE (registered trademark) LX4110, HX8210, TX8030, HX8290, HX8410 And AX8390 (Arkema Inc.), OREVAC (registered trademark) T9314, T9318 and G1821 (Arkema Corp.), Umex (registered trademark) 2000 (Sanyo Chemical Industry Co., Ltd.), and Auroren (registered trademark) 100S and 200T (Nippon Paper Chemical Co., Ltd.) etc. are mentioned.

<Polymer (B)>
In the polymer (B), the proportion of carbon atoms in the atoms constituting the main chain is 95% or more. More preferably, it is 97% or more, More preferably, it is 99% or more.
Examples of the polymer constituting the main chain of the polymer (B) include polyolefin, polyvinyl and polyacrylate.

Examples of the polymer (B) include acid-modified chlorinated polyolefins, chloroprene resins, acid-modified chloroprene resins, and the like, and acid-modified chlorinated polyolefins are preferable.
The acid-modified chlorinated polyolefin is obtained by graft copolymerizing at least one selected from polypropylene and propylene-α-olefin copolymer with at least one selected from α, β-unsaturated carboxylic acid and its anhydride. After obtaining the modified polyolefin, it can be obtained by chlorinating the acid-modified polyolefin.

  Here, the propylene-α-olefin copolymer is obtained by copolymerizing propylene as a main component with an α-olefin. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1-pentene. Examples include α-olefins having 2 or 4 to 20 carbon atoms.

  As α, β-unsaturated carboxylic acid and its acid anhydride, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, Examples include hymic anhydride. Among these, maleic anhydride and itaconic anhydride are preferable.

  The content of the component derived from the α, β-unsaturated carboxylic acid and its acid anhydride in the acid-modified chlorinated polyolefin is preferably 0.6 to 10% by mass. If it exceeds 10% by mass, the hydrophilicity of the acid-modified chlorinated polyolefin becomes high, and the water resistance of the coating film obtained from the target composition may be lowered. On the other hand, when the content is less than 0.4% by mass, the dispersibility of the acid-modified chlorinated polyolefin in water is lowered, making it difficult to produce an aqueous emulsion.

  The chlorination can be performed, for example, by dissolving acid-modified polyolefin in a chlorinated solvent and blowing chlorine gas in the presence or absence of a radical generator.

The chloroprene-based resin is obtained by polymerizing chloroprene synthesized by dehydrochlorination of dichlorobutene obtained by chlorination of butadiene, or copolymerizing with other monomers. Examples of such other monomers include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid esters, methacrylic acid esters, acrylic acid, methacrylic acid, and itaconic acid.
The acid-modified chloroprene resin is obtained by graft-copolymerizing the chloroprene resin with at least one selected from α, β-unsaturated carboxylic acids and anhydrides thereof. Examples of the α, β-unsaturated carboxylic acid and its acid anhydride include the same ones used in the production of acid-modified chlorinated polyolefins.

The chlorine atom content of the polymer (B) is preferably 10 to 65% by mass.
If it is less than 10% by mass, it is difficult to produce an aqueous emulsion. If it exceeds 65% by mass, the adhesive strength may be reduced when the aqueous emulsion of the present invention is used as an aqueous adhesive.

  The polystyrene equivalent weight average molecular weight of the polymer (B) is usually 1000 or more, preferably 2000 or more, more preferably 5000 or more, further preferably 10,000 or more, and usually 200000 or less, preferably 100000 or less. is there. If the weight average molecular weight is less than 1000, sufficient adhesive strength may not be obtained when the aqueous emulsion of the present invention is used as an aqueous adhesive, and if it exceeds 200,000, the solubility in a solvent decreases and the aqueous emulsion Manufacturing becomes difficult. The weight average molecular weight in terms of polystyrene can be measured by gel permeation chromatography (GPC).

The polymer (B) may be one kind or a combination.
As a polymer (B), what was manufactured according to the commercial item and arbitrary well-known methods is mentioned. As a known method, for example, the method described in JP-A-2007-31474 can be mentioned. As commercial products, HARDREN (registered trademark) CY-9122P, CY-9124P, HM-21P, M-28P, F-2P, F-6P, F-69, 13-LP, 13-LLP, 14-LWP, 14-WL-P, 15-LP, 15-LLP, 16-LP, DX-526P, DX-530P and BS-40 (Toyobo Co., Ltd.), and Supercron (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE-510, HE-515, HE-910, HE-915, HE-1070, HE-1200, HP-205, HP-215 and HP-620 (Nippon Paper Chemicals ( Etc.).

The polymer (B) may be a commercially available aqueous emulsion or a solvent-substituted one of a commercially available solvent-based emulsion.
Commercially available aqueous emulsions include HARDLEN (registered trademark) EW-5303, EH-801, EW-5504, EZ-1000 and EZ-2000 (Toyobo Co., Ltd.), Supercron (registered trademark) E-604, E- 480T and E-415 (Nippon Paper Chemical Co., Ltd.), Skyprene (registered trademark) GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390, SL- 590 and SL-590 (Tosoh Corp.), Shoprene (Registered Trademark) 115, 571, 572, 650, 671A, 750, SD78 and SD77 (Showa Denko Co., Ltd.), and Denka Chloroprene (Registered Trademark) LA-50 And LC-501 (Electrochemical Industry Co., Ltd.).
Commercially available solvent-based emulsions include HARDLEN (registered trademark) BS-40, CY-1132, FX-918, FX-923, F-225, 163-LR, P-5528 and P-400 (Toyobo Co., Ltd.) ), And Supercron (registered trademark) 814B, 360T, 370M, 2027MB, C, L-206, 813A, 803M, 803MW, 803LT, 1026, and 803L (Nippon Paper Chemical Co., Ltd.).

<Photoinitiator>
The aqueous emulsion of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that generates an active species by the action of light, and preferably a compound that generates an active radical by the action of light.

  Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of benzophenone compounds include benzophenone, 4-methylbenzophenone, additional o-benzoylmethyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert -Butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane. -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one An oligomer etc. are mentioned.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3 , 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2 Such as (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

A commercially available photopolymerization initiator can be used. Commercially available photopolymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Sequol (registered trademark) BZ, Z And BEE (Seiko Chemical Co., Ltd.), Kayacure (registered trademark) BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 and SP-170 (( ADEKA), TAZ-A and TAZ-PP (Nihon Shibel Hegner Co., Ltd.), TAZ-104 (Sanwa Chemical Co., Ltd.), Darocur (registered trademark) 1173 and MBF (BASF Japan Co., Ltd.), etc. Is mentioned.
These photopolymerization initiators may be used alone or in combination.
Specific examples of the combination include Irgacure® 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone = 50/50%), Irgacure® 1700 (bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one = 25/75%) and Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2, 4,4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone = 25/75%) (BASF Japan Ltd.).

  The content of the polymer (1) with respect to 1 part by mass of the photopolymerization initiator is preferably more than 2 parts by mass, more preferably 3 to 1000 parts by mass, from the viewpoints of stability, reactivity and odor. Preferably it is 3-500 mass parts, Most preferably, it is 4-100 mass parts.

<Aromatic polyisocyanate>
The aqueous emulsion of the present invention preferably contains an aromatic polyisocyanate. By containing the aromatic polyisocyanate, the heat resistance of the adhesive layer obtained from the aqueous emulsion of the present invention is improved.

（式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して、アルキル基又はアリール基を表す。ｎは１又は２を表す。ｍは２又は３を表す。ｒは１又は２を表す。ｓは０〜２の整数を表す。ｐは０〜１００の整数を表す。） The aromatic polyisocyanate means a compound having a structure in which two or more isocyanate groups are bonded to an aromatic ring, such as 1,5′-naphthalene diisocyanate, 2,4-methoxyphenyl diisocyanate. Narate, 3,3′-dimethoxy-4,4-biphenylene diisocyanate, tolidine diisocyanate, 4,4′-biphenylene diisocyanate, tris (p-isocyanatophenyl) thiophosphate, triphenylmethane triisocyanate 3,3′-dimethyl-4,4-biphenylene diisocyanate, a compound represented by formula (5), a compound represented by formula (6), a compound represented by formula (5) or formula (6) ) Isocyanurate obtained from the compound represented by formula (5), biuret obtained from the compound represented by formula (5) or the compound represented by formula (6) And adduct of trimethylol propane obtained from the compounds represented by formula (5) compound represented by or formula (6) below. These may be used alone or in combination.

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group. N represents 1 or 2. m represents 2 or 3. r represents 1 or 2. S represents an integer of 0 to 2. p represents an integer of 0 to 100.)

  Preferably, the compound represented by the formula (5), the compound represented by the formula (6), and tris (p-isocyanatophenyl) thiophosphate, the compound represented by the formula (5) or the formula (6) Isocyanurate using the compound as a raw material, biuret using the compound represented by the formula (5) or the compound represented by the formula (6) as a raw material, and the compound or the formula (6) represented by the formula (5) ), And more preferably a compound represented by formula (5), a compound represented by formula (6), and tris (p-isocyanatophenyl). ) Thiophosphate.

Examples of the alkyl group represented by R ¹ , R ² and R ³ include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.

Examples of the aryl group represented by R ¹ , R ² and R ³ include aryl groups having 6 to 18 carbon atoms such as a phenyl group and a biphenyl group.
R ¹ is preferably a methyl group.
R ² and ^{R 3} are preferably hydrogen atom.
n is preferably 1, m is preferably 2.
r is preferably 1, s is preferably 0.
p is preferably 1 to 100.

（ｔは１〜１００の整数を表す。） Examples of the compound represented by the formula (5) include 1,3-phenylene diisocyanate, 2,4-toluylene diisocyanate (TDI), 2,6-toluylene diisocyanate (TDI), and the like. Examples of the compound represented by (6) include diphenylmethane-4,4′-diisocyanate (MDI), diphenylmethylmethane diisocyanate, 4,4-biphenylene diisocyanate, 3,3′-dimethyl-4, Examples include 4-biphenylene diisocyanate, tetraalkyldiphenylmethane diisocyanate, and polymethylene polyphenylene isocyanate. Preferably, it is represented by 2,4-toluylene diisocyanate (TDI), 2,6-toluylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI) and the following formula (7). Polymethylene polyphenylene isocyanate.

(T represents an integer of 1 to 100.)

  The polymethylene polyphenylene isocyanate represented by the formula (7) preferably has a polymerization degree such that the viscosity at 25 ° C. is about 20 to 7500 mPa · s. More preferably, the viscosity at 25 ° C. is 130 to 600 mPa · s.

  These aromatic polyisocyanates are commercially available.

  Content of aromatic polyisocyanate is 1-200 mass parts normally with respect to 100 mass parts of polymers (1), Preferably it is 5-100 mass parts, More preferably, it is 10-50 mass parts. More preferably, it is 10-30 mass parts.

<Ethylenically unsaturated monomer>
The aqueous emulsion of the present invention may contain an ethylenically unsaturated monomer. However, since ethylenically unsaturated monomers have problems such as odor, the aqueous emulsion of the present invention preferably does not contain ethylenically unsaturated monomers.
Examples of the ethylenically unsaturated monomer used in the present invention include monofunctional monomers, bifunctional monomers, and polyfunctional monomers.

Monofunctional monomers (monofunctional polymerizable diluents) include, for example, heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen such as N-methylpyrrolidone, N-vinylpyridine, N-vinylcaprolactam) Heterocyclic compounds such as heterocyclic (meth) acrylates such as morpholine (meth) acrylate and tetrahydrofurfuryl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate (eg Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.), N, N′-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (for example, methoxyethylene (meth) acrylate, methoxypolyethylene (meth)) Acryle , Butoxypolyethylene (meth) acrylate, etc.), alkylphenoxymethyl (meth) acrylate (eg, nonylphenoxyethyl (meth) acrylate), phenoxy (poly) alkylene glycol (meth) acrylate (eg, phenoxyethyl (meth) acrylate) , Phenoxypolyethylene glycol (meth) acrylate, etc.), alkyl (meth) acrylate (eg, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate , Isomyristyl (meth) acrylate, isostearyl (meth) acrylate, etc.), cycloalkyl (meth) acrylate (eg, cyclohexyl (meth) acrylate, etc.), aralkyl (meth) acrylate, etc. (For example, benzyl (meth) acrylate), (meth) acrylate having a bridged cyclic hydrocarbon group (for example, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyalkyl (meth)) Acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 3-acryloyloxy Glycerol mono (meta) Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc.), poly ε-caprolactone mono (meth) acrylate, glycidyl (meth) acrylate, mono [2- (meth) acryloyloxy Ethyl] acid phosphate, halogen-containing (meth) acrylate (eg, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorooctyl Chill (meth) acrylate and the like).

  Examples of the bifunctional monomer (difunctional polymerizable diluent) include 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate di (meth) acrylate, (polyoxy) alkylene Glycol di (meth) acrylate (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylol The Pandi (meth) acrylate, pentaerythritol di (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide (ethylene oxide, propylene oxide) adduct (for example, 2,2-bis (2-hydroxyethoxyphenyl) propane Di (meth) acrylates), di (meth) acrylates with bridged cyclic hydrocarbon groups (eg di (meth) acrylates of tricyclodecane dimethylol, dicyclopentadiene di (meth) acrylates) bifunctional (Meth) acrylic acid adducts of curable epoxy resins (for example, (meth) acrylic acid adducts of 2,2-bis (glycidyloxyphenyl) propane) and the like.

  Examples of the polyfunctional monomer (polyfunctional polymerizable diluent) include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth). ) Acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-hydroxyethyl) isocyanurate tri ( And (meth) acrylate, tris (hydroxypropyl) isocyanurate tri (meth) acrylate, triallyl trimellitic acid, triallyl isocyanurate, and the like.

  The ethylenically unsaturated monomer may be used alone or in combination of two or more. Of these ethylenically unsaturated monomers, water-soluble ethylenically unsaturated monomers having 5 to 10 carbon atoms and water-insoluble ethylenically unsaturated monomers having 4 to 20 carbon atoms are preferable, and more preferably They are a water-soluble (meth) acrylate having 5 to 10 carbon atoms and a water-insoluble (meth) acrylate having 4 to 20 carbon atoms.

  Content of an ethylenically unsaturated monomer is 0.1-2500 mass parts normally with respect to 100 mass parts of polymers (1), Preferably it is 1-1000 mass parts, More preferably, it is 1-150 mass. Part.

<Polyurethane>
The aqueous emulsion of the present invention may contain polyurethane as a polymer component. Polyurethane can be obtained by reacting a polyisocyanate compound, a polyol compound and, if necessary, other compounds. Examples of the reaction include a seton method, a prepolymer mixing method, a ketimine method, and a hot melt dispersion method. However, the polyurethane in this specification does not satisfy the requirements for the polymer (A) and the polymer (B).
Such polyurethane may be either water-soluble or water-insoluble, but is preferably water-insoluble.

  Examples of the polyisocyanate compound include organic polyisocyanate compounds having two or more isocyanate groups in the molecule, which are used for ordinary polyurethane production. For example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 3-isocyanate methyl-3,5,5- Trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexyl-2,4-diisocyanate, methylcyclohexyl-2,6-diisocyanate, xylylene diisocyanate (XDI), 1,3 -Aliphatic diisocyanates such as bis (isocyanate) methylcyclohexane, tetramethylxylylene diisocyanate, transcyclohexane-1,4-diisocyanate, lysine diisocyanate; 2,4-toluylene diisocyanate (TDI) ), 2,6-G Irene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), 1,5′-naphthene diisocyanate, tolidine diisocyanate, diphenylmethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate Aromatic diisocyanates such as 4,4′-dibenzyldiisocyanate, 1,3-phenylene diisocyanate; lysine ester triisocyanate, triphenylmethane triisocyanate, 1,6,11-undecantrie Isocyanates, 1,8-isocyanate 4,4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, adducts of trimethylolpropane and toluylene diisocyanate Such as tri isocyanates adducts such of trimethylol propane and 1,6-hexamethylene diisocyanate. You may use these individually or in combination of 2 or more types.

  Examples of the polyol compound include compounds having two or more hydroxyl groups in the molecule, which are used for the production of ordinary polyurethane. For example, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin; polyethylene glycol, polypropylene glycol, polytetramethylene ether Polyether polyols such as glycol; adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid Dicarboxylic acids such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,2-propanedio And 1,3-propanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 1,3-propanediol, tripropylene glycol, trimethylolpropane, glycerin and other polyol compounds. Polyester polyols such as polycaprolactone polyol and poly β-methyl-δ-valerolactone; polybutadiene polyol or hydrogenated product thereof, polycarbonate polyol, polythioether polyol, polyacrylate polyol and the like .

  The polyurethane preferably has a hydrophilic group in the molecule in order to improve dispersion stability in water. A polyurethane containing a hydrophilic group in its molecule is called an ionomer structure and has a surface-active ability in itself. Therefore, there exists a tendency which is easy to disperse | distribute in water, and there exists a tendency which improves the water resistance of the aqueous emulsion obtained by emulsion-polymerizing a monomer further to the polyurethane aqueous emulsion.

As the hydrophilic group, anionic groups such as a sulfonyl group and a carboxy group are preferable, and a sulfonyl group is more preferable. This is because there is a tendency to further improve the water resistance of an aqueous emulsion obtained by emulsion polymerization of monomers.
In general, the anionic group is preferably neutralized by a neutralizing agent.
Examples of the neutralizing agent include tertiary amine compounds such as triethylamine and trietalamine; inorganic alkali compounds such as sodium hydroxide; ammonia and the like.

In order to introduce a hydrophilic group into the molecule, it is preferable to use the following compounds during the production of polyurethane. Examples of the compound include a nonionic hydrophilic group such as a structural unit derived from polyethylene glycol in the molecule, and a sulfonyl group, a carboxy group, a hydroxyl group, a primary amino group (—NH ₂ ), a secondary amino group ( ═NH) and the like (hereinafter sometimes referred to as “hydrophilic group-containing compounds”) having at least one active hydrogen having reactivity with an isocyanate group.

  Examples of the hydrophilic group-containing compound include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, and N- (2-aminoethyl) -2. -Sulphonic acid-containing compounds such as aminoethylsulfonic acid; and carboxylic acid-containing compounds such as 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid and 2,2-dimethylolvaleric acid. You may use these individually or in combination of 2 or more types.

  When a polyurethane resin is produced as an aqueous emulsion, it is a compound different from a hydrophilic group-containing compound for the purpose of chain extension, molecular weight adjustment, etc., if necessary, and an active hydrogen capable of reacting with an isocyanate compound in the molecule. You may use the compound to contain together. Examples of such compounds include polyvalent amine compounds such as ethylenediamine, 1,4-butanediamine, and 1,6-hexanediamine; tertiary amine-containing polyhydric alcohols such as triethanolamine, methanol, ethanol, and butanol. And monoalcohols.

As the polyurethane resin, a commercially available polyurethane aqueous emulsion or a commercially available water-soluble urethane resin may be used as it is.
For example, a polyurethane dispersion (or polyurethane aqueous solution) in which a polyurethane resin is dispersed or dissolved in water can be mentioned. The content of the polyurethane resin in the polyurethane dispersion is usually 10 to 70% by mass, preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and still more preferably 30 to 55% by mass.
The polyurethane dispersion may further contain an organic solvent not containing an isocyanate reactive group, for example, ethyl acetate, acetone, methyl ethyl ketone, N-methylpyrrolidone and the like.

  A commercially available polyurethane can be used. Examples of commercially available water-soluble urethanes include Dispacol (registered trademark) U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA-8756, and KA-. 8766 (Sumitomo Bayer Urethane Co., Ltd.), Hydran (registered trademark) HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM and AP-80. (DIC Corporation), Uprene (registered trademark) UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310 and Ucourt UWS-145 (Sanyo Chemical Industries, Ltd.) )), Superflex (registered trademark) 107M, 110, 126, 130, 150, 160, 210, 00, 361, 370, 410, 420, 460, 500M, 700, 750, 820 and 860 (Daiichi Kogyo Seiyaku Co., Ltd.), and Adekabon titer (registered trademark) HUX-401, HUX-420A, HUX-380 , HUX-561, HUX-210, HUX-822, HUX-895, and HUX-830 (Adeka Co., Ltd.).

  The content of the polyurethane is usually 5 to 3000 parts by weight, preferably 10 to 2400 parts by weight, more preferably 40 to 1000 parts by weight, and still more preferably 100 parts by weight of the polymer (1). Is 50 to 500 parts by mass.

<Surfactant>
The aqueous emulsion of the present invention preferably contains a surfactant that acts as an emulsifier. The surfactant may be any of cationic, anionic, amphoteric and nonionic, preferably anionic or nonionic, and more preferably nonionic.

（式中、Ｘは水素原子又は−ＳＯ_３Ｍ（Ｍは水素原子、ＮＨ_４又はアルカリ金属）を示す。ｎは１〜３の整数を表す。ｍは１〜１００の整数を表す。）
式（１１）におけるＸとしては、水素原子、−ＳＯ_３Ｈ又は−ＳＯ_３ＮＨ_４が好ましく、Ｍで表されるアルカリ金属としては、ナトリウムが好ましい。 Anionic surfactants include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, and vinyl sulfosuccinates. And the like.
Examples of cationic surfactants include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt And allyltrialkylammonium salt and diallyldialkylammonium salt.
Nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, and ethylene oxide. -A compound having a polyoxyethylene structure such as a propylene oxide copolymer and a sorbitan derivative such as a polyoxyethylene sorbitan fatty acid ester.
Examples of amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide.
Among these, as the surfactant, a compound represented by the following formula (11) is preferable, and a compound represented by the following formula (B) is more preferable.

(In the formula, X represents a hydrogen atom or —SO ₃ M (M is a hydrogen atom, NH ₄ or an alkali metal). N represents an integer of 1 to _3. m represents an integer of 1 to 100.)
X in formula (11) is preferably a hydrogen atom, —SO ₃ H or —SO ₃ NH ₄ , and the alkali metal represented by M is preferably sodium.

The surfactants may be used alone or in combination of two or more, but preferably two or more are combined. Especially, it is preferable to combine 2 or more types of compounds represented by Formula (11).
A combination of two or more compounds represented by the formula (11) may be a combination of n, m or X, but it is preferable to combine a combination of different X. Specifically, X is preferably a combination of a hydrogen atom and —SO ₃ H, a combination of a hydrogen atom and —SO ₃ NH ₄ , or a combination of —SO ₃ H and —SO ₃ NH ₄ . Among these, a combination of a hydrogen atom and —SO ₃ NH ₄ is more preferable.

（式中、ｎは１〜３の整数を表す。ｍは１〜１００の整数を表す。） Surfactants are readily available from the market. As the surfactant represented by the formula (11), Latemu (registered trademark) AD-25 (Kao Corporation), Latemu (registered trademark) E-1000A represented by the following formula (A) (Kao Corporation) )) And Neugen (registered trademark) EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) represented by the following formula (B). Examples of commercially available surfactants include New Coal 714 (Nippon Emulsifier Co., Ltd.).

(In the formula, n represents an integer of 1 to 3. m represents an integer of 1 to 100.)

  Content of surfactant is 0.1-150 mass parts normally with respect to 100 mass parts of polymers (1), Preferably it is 1-100 mass parts, More preferably, it is 10-50 mass parts. It is.

<water>
As water contained in the aqueous emulsion of the present invention, tap water or deionized water is usually used.

<Other ingredients>
The aqueous emulsion of the present invention is a cross-linking agent; an organic solvent; other resin; a basic compound; Stabilizers such as stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, anti-settling agents, antioxidants, heat stabilizers and light stabilizers; thixotropic agents, thickeners, dispersions, antifoaming agents , Viscosity modifiers, weathering agents, pigments, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oil agents, dyes and curing agents, etc .; transition metals such as titanium oxide (rutile type) and zinc oxide Compound: Pigment such as carbon black; glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, fine powder Rica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, inorganic, such as alumina and Celite, may contain optional components such as organic fillers. In order to further improve the stability of the aqueous emulsion, a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose may be contained.

(Crosslinking agent)
The aqueous emulsion of the present invention may contain a crosslinking agent. However, the above-mentioned aromatic polyisocyanate is not included in the crosslinking agent in this specification.
By including the cross-linking agent, properties such as adhesiveness, water resistance of the adhesive layer and solvent resistance of the adhesive layer are further improved.
Examples of the crosslinking agent include epoxy compounds, aliphatic polyisocyanate compounds, oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelates and the like.
Preferred are aliphatic polyisocyanate compounds, carbodiimide compounds, and oxazoline group-containing compounds. Of these, aqueous (water-soluble or water-dispersible) ones are more preferable. These crosslinking agents may be used alone or in combination.

Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate (HDI) and oligomers or polymers thereof.
Specifically, Sumidur (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487 and XP-2547 made by Sumika Bayer Urethane, Sumitomo Bayer Urethane Death Module (registered trademark) N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and DA-L, manufactured by Sumitomo Bayer Urethane Co., Ltd. (Registered trademark) 304 and XP2655, BASON manufactured by BASONAT (registered trademark) PLR8878 and HW-100, Takeda (registered trademark) WD720, WD725, and WD730 manufactured by Asahi Kasei Kogyo Co., Ltd. Registered merchant ) WB40-100, include WB40-80D and WX-1741 or the like.

Specific examples of the carbodiimide-based crosslinking agent include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02) and the like. Can be mentioned.
Content of a crosslinking agent is 0.1-20 mass parts normally with respect to 100 mass parts of aqueous emulsion, Preferably it is 0.1-10 mass parts.

(Organic solvent)
The aqueous emulsion of the present invention preferably contains no organic solvent, but may contain it. Organic solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, n-propanol Alcohols such as isopropyl alcohol and n-butanol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether) and butyl carbitol Cellosolve solvents; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methyl And glycol solvents such as xyl-3-methyl-1-butanol; and glycol ester solvents such as ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate. It is done. These may be used alone or in combination.
When the aqueous emulsion of this invention contains the organic solvent, the content is 0.01-30 mass parts normally with respect to 100 mass parts of polymers (1), Preferably it is 0.01-10 masses. Part.

(Other resins)
The aqueous emulsion of the present invention may contain a resin other than the polymer (1) and the above-described polyurethane as a polymer component. Other resins include ethylene-vinyl ester resin, polyolefin resin, polyvinyl chloride, polyvinylidene chloride, styrene-maleic acid resin, styrene- (meth) acrylic acid resin, styrene-butadiene, resin, butadiene resin, acrylonitrile Examples thereof include butadiene resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, polyester resin, modified nylon resin, urethane resin, acrylic resin, phenol resin, silicone resin, and epoxy resin.

The ethylene-vinyl ester resin is a copolymer containing a polymer composed of ethylene units and vinyl ester units. Examples of the vinyl ester unit include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl esters of tertiary carboxylic acid having 8 to 10 carbon atoms, and so-called vinyl versatate (for example, trade name: Veova (registered trademark) manufactured by Shell Chemical Co., Ltd.). And alkyl acid vinyl esters such as 10). Of the vinyl ester units, vinyl acetate is preferred. When vinyl acetate is used as the vinyl ester unit, the copolymer is an ethylene-vinyl acetate copolymer (hereinafter abbreviated as “EVA”).
In addition to the ethylene unit and vinyl ester unit, a monomer unit copolymerizable with these may be contained. Examples of the monomer unit include vinyl halides such as vinyl chloride, monomers having a small amount of a functional group such as an amide group, and (meth) acrylic acid esters.
An emulsion of an ethylene-vinyl ester resin copolymer can be usually produced by emulsion polymerization of monomers constituting the ethylene unit and the vinyl ester unit. The emulsion of ethylene-vinyl ester resin copolymer includes Sumikaflex (registered trademark) 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ, 470HQ, 478HQ. , 510HQ, 520HQ, 710, 752, 755, SDX-5100, 801HQ, 808HQ, 830, 850HQ, 900HL and 3950 (above, manufactured by Sumitomo Chemical Co., Ltd.), Banflex OM-4000 and OM-4200 (above, ( Kuraray Co., Ltd.), Polyzole (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa Polymer ( DENKA EV) Uses an aqueous emulsion of a commercially available ethylene-vinyl ester copolymer such as A-Tex (registered trademark) # 20, # 30, # 40M, # 60, # 81 and # 82 (above, manufactured by Denki Kagaku Kogyo Co., Ltd.) May be.

  Moreover, as other resin, resin which has a function as an adhesion resin or a tackifier is mentioned. Examples of such resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof. Examples thereof include resins, other petroleum resins, coumarone resins, and indene resins. Specifically, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and ester thereof Terpenes such as terpenes; terpene polymers, terpene phenols, β-pinene polymers, aromatic-modified terpene polymers, α-pinene polymers, terpene-based hydrogenated resins, etc .; petroleum fractions having 5 carbon atoms And petroleum resins polymerized from petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof; petroleum resins such as maleic acid modified products and fumaric acid modified products.

Examples of terpene resins include Yasuhara Chemical Co., Ltd .: YS Resin PX / PXN, YS Polyster, Mighty Ace, and YS Resin TO / TR and Clearon P / M / K, Arakawa Chemical Industries, Ltd .: Tamanol 803L / 901, and Nippon Terpene Chemical Co., Ltd .: Teltac 80 etc. are mentioned.
Other resin may be individual and may be contained in combination of 2 or more type.
Other resins can be easily obtained from the market.

  When the aqueous emulsion of this invention contains other resin, the content is 0.1-2000 mass parts normally with respect to 100 mass parts of polymers (1), Preferably it is 100-2000 mass parts. Yes, more preferably 1000 to 2000 parts by mass. Other resins may be mixed with the polymer (1) in an emulsion state, or may be emulsified with the polymer (1) to form an aqueous emulsion.

(Basic compounds)
The aqueous emulsion of the present invention may contain a basic compound.
As a basic compound, what can neutralize a carboxy group is preferable, for example, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned. Preferably, it is ammonia or an organic amine compound. In particular, an organic amine compound having a boiling point of 200 ° C. or lower is preferable. Organic amine compounds having a boiling point of 200 ° C. or less tend to evaporate easily by ordinary drying, and tend to maintain and improve the water resistance and alkali resistance of the coating film when forming a coating film with an aqueous emulsion. It is preferable in that it is.
Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3- Examples include diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. N, N-dimethylethanolamine is preferable.
Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide and sodium hydroxide.
Basic compounds are readily available from the market.

  When the aqueous emulsion of this invention contains a basic compound, the content is 0.1-30 mass parts normally with respect to 100 mass parts of polymers (1), Preferably it is 1-20 mass parts. More preferably, it is 2-10 mass parts.

(Thickener)
Thickeners can be used to adjust the viscosity of the aqueous emulsion. As a thickener, Adecanol (registered trademark) UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH-541VF, UH-550, UH-752 and H-756VF (ADEKA), and SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636 and 4050 (San Nopco Co., Ltd.).

(Dispersant)
The dispersant can be used for improving the wettability of the adherend. As a dispersing agent, Adeka Coal (registered trademark) W-193, W-287, W-288 and W-304 (BYK Corporation), BYK-333, BYK-345, BYK-346, BYK-347, BYK- 348, BYK-349 and BYK-378 (ADEKA Corporation), Nopco Wet 50, SN Wet 366 and Nopco 38-C (San Nopco Corporation), and SN Dispersand 5468, 5034, 5027, 5040 and 5020 ( San Nopco Co., Ltd.).

<Method for producing aqueous emulsion>
The aqueous emulsion of the present invention can be produced by a known method. For example, it can be produced by a post-emulsification method (for example, a forced emulsification method, a self-emulsification method, a phase inversion emulsification method, etc.) in which the polymer (1) is dispersed in an aqueous medium.
Specifically, the following method is mentioned, for example.
(I) Polymer (1) and a solvent are charged into a reactor, heated and stirred, dissolved, and water and / or a solvent and optionally a surfactant are charged into the reactor, heated and stirred, and optionally Water and / or a solvent is added and stirred, and after cooling to room temperature, a photopolymerization initiator and / or aromatic polyisocyanate, and optionally an ethylenically unsaturated monomer and / or polyurethane are added. Add and stir. The photopolymerization initiator, aromatic polyisocyanate, ethylenically unsaturated monomer, and polyurethane may be dissolved in an organic solvent and added.
(II) The polymer (1) is charged into a kneader, heated and stirred, melted, and water and / or a solvent and a surfactant are added thereto, heated and stirred, and optionally water and / or Add solvent and stir, then cool and return to ambient temperature, add photoinitiator and / or aromatic polyisocyanate, and optionally ethylenically unsaturated monomer and / or polyurethane, stir how to. The photopolymerization initiator, aromatic polyisocyanate, ethylenically unsaturated monomer, and polyurethane may be dissolved in an organic solvent and added.

As the reactor of the production method (I), a container (preferably a sealed and / or pressure-resistant container) provided with a heating device capable of being heated and a stirrer capable of giving a shearing force or the like to the contents. ) And the like.
A common agitator can be used. Examples of such a pressure vessel include a pressure-resistant autoclave with a stirrer. Stirring may be performed at normal pressure or reduced pressure. Moreover, the rotation speed of a stirrer is about 50-1000 rpm normally. If necessary, it is preferable to increase the rotation speed as the dispersion / stirring of the aqueous emulsion proceeds.
The heating is usually performed at 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 70 to 100 ° C.
After stirring, the solvent is preferably distilled off from the obtained aqueous emulsion. Examples of the distillation method include methods known in the art. The pressure condition for distilling off the solvent is usually about 0.001 to 1 MPa, preferably about 0.001 to 0.5 MPa.

  Examples of the kneader in the production method (II) include a roll mill, a kneader, an extruder, an ink roll, and a Banbury mixer. In particular, an extruder or a multi-screw extruder having one or more screws in the casing is preferable.

  As a method of stirring in the extruder, the molten polymer (1) and optionally a surfactant are mixed, and this is continuously fed from the hopper or feed port of the extruder, and this is heated, melted and kneaded, Examples include a method of supplying water from at least one supply port provided in a compression zone, a metering zone, a deaeration zone, and the like of the extruder, kneading with a screw, and continuously extruding from a die.

In the production of the aqueous emulsion, other components other than the polymer (1), the solvent, the surfactant, water, the ethylenically unsaturated monomer, and the photopolymerization initiator can be appropriately added at any time.
In the production of the aqueous emulsion, the amount of the surfactant used is preferably an amount necessary and sufficient for emulsification of the polymer (1). However, when the surfactant is excessive, an excess amount of the surfactant is obtained from the obtained aqueous emulsion. The surfactant may be separated and removed. Separation and removal of the surfactant is, for example, a centrifugal filter, a filtration filter having an average pore size smaller than the average particle size of the aqueous emulsion (preferably having an average pore size of 0.05 to 0.5 μm). A microfiltration membrane) or an ultrafiltration membrane.
Furthermore, it is preferable to cool the obtained aqueous emulsion. By cooling, an aqueous emulsion composed of a fine dispersoid can be obtained. It is preferable that the cooling be performed slowly, for example, by leaving it at room temperature instead of rapid cooling. Thereby, a fine and homogeneous aqueous emulsion can be obtained without aggregation of resin or the like during the cooling process.

The average particle size of the dispersoid in the aqueous emulsion of the present invention is usually 10 μm or less, preferably 0.01 to 10 μm, more preferably 0.01 to 2 μm, and still more preferably 0.01 to 1 μm on a number basis. is there. Within the above range, the stationary stability is good.
Here, the number-based average particle size is a particle size corresponding to 50% of the integrated particle size distribution value on the number basis, and the volume-based median size is 50% of the integrated particle size distribution value on the volume basis. The particle diameter corresponding to. Unless otherwise specified, it means a median diameter value measured on a number basis.
The average particle diameter of the dispersoid can be measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation.

<Usage method of aqueous emulsion>
The aqueous emulsion of the present invention is useful as an aqueous adhesive. The aqueous adhesive containing the aqueous emulsion of the present invention is a material such as a film, a sheet, a structural material, a building material, an automobile part, an electric / electronic product, a packaging material, clothing or shoes (hereinafter referred to as an adherend). .) Can be used for bonding.

As adherends, woody materials such as wood, plywood, medium density fiberboard (MDF), particleboard, fiberboard; cellulosic materials such as cotton, cotton-containing fiber, linen, rayon; polyethylene (derived from ethylene) Polyolefins such as polyolefins having structural units as main components), polypropylenes (polyolefins having structural units derived from propylene as main components), polystyrenes (polyolefins having structural units derived from styrene as main components), polycarbonates, acrylonitrile- Butadiene-styrene copolymer (ABS resin), (meth) acrylic resin polyester, polyether, polyvinyl chloride, polyurethane, foamed urethane, ethylene-vinyl acetate copolymer (EVA), foamed EVA, nylon 6, nylon 66, etc. Polyamide resin The plastics material of the foam, and the like; polyurethanes, polyamide and synthetic leather polyamino acid; glass, ceramic materials and ceramic and the like; iron, stainless steel, copper, a metal material such as aluminum and the like. These may be composite materials composed of a plurality of components. Further, it may be a kneaded molded product of an inorganic filler such as talc, silica or activated carbon, carbon fiber, and the like and a plastic material.
Among them, the aqueous emulsion of the present invention can be suitably used for adhesion between cellulosic materials and plastic materials, and adhesion of ethylene-vinyl acetate copolymers, cotton-containing fibers, nylon resins, polyolefins, synthetic leather, and the like. it can.

  Polyurethane is a polymer composed of urethane bonds, and is usually obtained by reaction of alcohol (—OH) and isocyanate (—NCO). The urethane foam is a polyurethane foamed with a volatile solvent such as carbon dioxide or freon produced by a reaction between an isocyanate and water. Semi-rigid polyurethane is used for automobile interiors, and hard polyurethane is used for paints.

  The ethylene-vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and has different properties depending on the vinyl acetate content and the like. Such ethylene-vinyl acetate copolymers include those having various vinyl acetate contents and shapes (films, blocks, fibers, foams). The ethylene-vinyl acetate copolymer may contain a polymer such as polyolefin. Preferred polyolefins include ethylene-octene copolymers, ethylene-butene copolymers, polypropylene and polyethylene.

The cotton-containing fibers may be 100% cotton fibers, or may be blended fibers of cotton and other natural fibers and / or chemical fibers. Other natural fibers include wool, silk and hemp. Chemical fibers include synthetic fibers (for example, polyamide fibers such as polyester and nylon), semi-synthetic fibers (cellulose fibers such as acetate, protein fibers such as promix), and regenerated fibers (rayon, cupra, polynosic, etc.) Cellulosic fibers) and inorganic fibers (carbon fibers, glass fibers) and the like.
Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape.

  Nylon resin is a so-called polyamide resin, and is a polymer composed of amide bonds. Specific examples include nylon 6, nylon 6,6, nylon 4,6, nylon 11, and nylon 12. The nylon resin may have any shape such as a film, a block, a fiber, or a foam.

The polyolefin is a thermoplastic resin obtained by polymerizing an olefin, and examples thereof include homopolymers and copolymers having structural units derived from an α-olefin having 2 to 20 carbon atoms.
Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and vinylcyclohexane. Ethylene and propylene are preferable. The copolymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms may be a homopolymer such as polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, and polypropylene. An α-olefin copolymer such as propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer or a modified copolymer thereof, and a copolymerizable monomer Or a modified copolymer thereof, or a mixture of two or more thereof. In the copolymer with the copolymerizable monomer, the copolymerizable monomer and the α-olefin may be used alone or in combination of two or more.
Depending on the molecular weight, polyethylene has various properties such as high density polyethylene, medium density polyethylene, low density polyethylene, ultra low density polyethylene, linear low density polyethylene, and ultra high molecular weight polyethylene. The polyethylene as the adherend of the aqueous emulsion of the present invention includes any of these.
Polypropylene is a thermoplastic resin obtained by polymerizing propylene, and there are isotactic (isotactic) polypropylene, syndiotactic polypropylene, atactic polypropylene, and the like having different stereoregularities. Polypropylene as a body includes any of these.

Synthetic leather includes both synthetic leather and artificial leather in the narrow sense.
In other words, it may be a synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric, or may be an artificial leather obtained by impregnating a synthetic resin into a fabric (usually non-woven fabric) such as a microfiber, or a microfiber. Artificial leather obtained by impregnating a synthetic resin into a fabric (usually a non-woven fabric) and then applying the synthetic resin may be used. Examples of these synthetic resins include polyurethane resins, polyamide resins, and polyamino acid resins. A polyurethane resin is preferable. Examples of the shape of the synthetic leather include various types such as a film, a sheet, or a block shape, and preferably a film and a sheet shape.

  In particular, the construction materials (adherents) such as the hood, the midsole, and the outer bottom of the footwear such as men's shoes such as sports shoes, town shoes, and business shoes, women's shoes, and industrial work shoes are adhered. It is suitable as an adhesive.

  In addition, the surface of these adherends may be smooth or may have irregularities.

As a method of manufacturing a laminate in which the adherend is bonded and the adhesive layer is sandwiched between the adherends, that is, a laminate in which the adherend, the adhesive layer, and the adherend are laminated in this order, For example, a method of forming a water-based adhesive coating film on one or both of the adherends, preferably both, and sandwiching the obtained coating film (adhesive layer) between the adherends and bonding them can be mentioned. .
You may pressurize or heat at the time of adhesion | attachment. Examples of the method for forming the coating film include a method in which the aqueous adhesive of the present invention is applied to one or both surfaces of the adherend, dried as necessary, and then irradiated with ultraviolet rays as necessary. . When the aqueous adhesive of the present invention contains a photopolymerization initiator, it is preferably irradiated with ultraviolet rays.
That is, as a method for producing a laminate in which an adhesive layer irradiated with ultraviolet rays is sandwiched between adherends, a water-based adhesive is applied to one or both of the adherends, preferably both, and as necessary. After drying, the coated aqueous adhesive is irradiated with ultraviolet rays to form a coating film, and the resulting coating film (adhesive layer) is sandwiched between adherends and adhered. .

  Examples of the application method include gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating and spatula coating.

Examples of the drying method include natural drying, non-thermal drying such as air drying, and hot air circulation type oven treatment. Drying can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous emulsion of the present invention, and the like. A drying temperature is 30-150 degreeC normally, Preferably it is 40-85 degreeC. The drying time is usually 1 second to 1 hour, preferably 5 seconds to 30 minutes, and more preferably 5 seconds to 10 minutes.
The application and drying of the aqueous emulsion may be performed only once, or may be performed twice or more. At that time, the coating method and the drying method may be combined with each other, or may be combined with different methods.

Examples of the ultraviolet light source include a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, and a laser. Irradiation dose is usually 20~2000mJ / cm ² integrated irradiation amount is preferably 100~1500mJ / cm ^2.

In addition, you may perform a primer process to the to-be-adhered body surface before apply | coating an aqueous adhesive. Examples of the primer treatment include blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and anchor layer formation treatment.
In particular, in the case of a substrate that can absorb water, such as cotton-containing fibers, a water-based adhesive may be applied and dried as a primer treatment. The aqueous adhesive can be applied and dried by the above method. One type of water-based adhesive used for the primer treatment may be used, or two or more types may be laminated. Moreover, the same thing may be sufficient in both to-be-adhered bodies, and a different thing may be sufficient.

  The thickness of the coating film (adhesive layer) is usually 0.01 to 300 μm, preferably 0.01 to 200 μm.

When the heat treatment is performed when the coating film formed on the adherend is sandwiched and adhered between the adherends, it is necessary to set the temperature range in which the adherend and the adhesive layer composed of the coating film do not deteriorate. The temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower. The heat treatment can be performed by hot air circulation type oven treatment, infrared treatment, far infrared heater treatment, microwave treatment, or the like. The pressure for the pressure treatment is preferably 100 g / cm ² or more and less than the pressure at which the shape of the adherend is deformed.
Further, after the adherends are bonded together, the above-described drying, heat treatment, and pressure treatment are performed on the laminate in which the obtained adherend, the adhesive layer, and the adherend are laminated in this order. May be performed.

Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise indicated, the part and% in an example mean a mass reference | standard.
The nonvolatile content concentration was measured by a measurement method according to JIS K-6828.
The average particle diameter of the dispersoid is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation. Unless otherwise specified, it is a median diameter value measured on a number basis.

<Production Example 1>
In a separable flask reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 200 parts of toluene, 50 parts of polymer A1 (Mersen (registered trademark) H-6410M), polymer A2 (BONDINE (registered trademark) HX8290, Arkema (Co)) 50 parts was added and dissolved by stirring at 80 ° C. In the obtained solution, 15.2 parts of Latemuru (registered trademark) E-1000A (30% aqueous solution, Kao Corporation) and Neugen (registered trademark) EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) 5.0 And a mixed solution of 5 parts of n-propanol were added dropwise over 10 minutes. After stirring for another 5 minutes, 5 parts of dimethylethanolamine was added, and the mixture was further stirred for 5 minutes to obtain a mixed solution.
Next, the stirrer was changed to TK Robotics (manufactured by PRIMIX Co., Ltd.), and the resulting mixture was stirred with a disper blade, and a mixture of 100 parts of n-propanol and 100 parts of ion-exchanged water was applied for 30 minutes. And dripped. When fluidity was recognized in the mixture, the stirring blade was changed to a homomixer, and 300 parts of ion-exchanged water was added dropwise while stirring to obtain a milky white aqueous emulsion.
The obtained aqueous emulsion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered with a 200 mesh nylon net to obtain an aqueous emulsion (E-1) containing a polymer A1 and a polymer A2. The average particle diameter (number basis) of the dispersoid of the obtained aqueous emulsion (E-1) was 0.1 μm, and the nonvolatile content concentration was 38%.

<Production Examples 2 to 4>
An aqueous emulsion (E-2) was obtained in the same manner as in <Production Example 1> using parts by mass of the polymer shown in Table 1 and a surfactant.
The polymers and surfactants in Table 1 are as follows.
Polymer A1: EVA partial saponification product (Mersen H6410M, manufactured by Tosoh Corporation, hydroxyl value: 121 mgKOH / g)
Polymer A2: BONDINE (registered trademark) HX8290, Arkema Co., Ltd.
Surfactant 1: LATEMUL (registered trademark) E-1000A, 30% aqueous solution, Kao Corporation
Surfactant 2: Neugen (registered trademark) EA-177, Daiichi Kogyo Seiyaku Co., Ltd.

<Examples 1-8>
The water-based emulsion (the mass part of the non-volatile content is described), the ethylenically unsaturated monomer, the photopolymerization initiator, and the dispersant of the mass part shown in Table 2-1 are mixed, and the non-volatile content concentration of the mixture is 10 Water was added so that it might become the mass%, and it stirred with the three one motor, and obtained the water-system adhesives (F1)-(F8) containing the aqueous emulsion of this invention.

The ethylenically unsaturated monomers and photopolymerization initiators in Table 2-1 are as follows.
Ethylenically unsaturated monomer 1: Isobornyl acrylate, Aldrich reagent Ethylenically unsaturated monomer 2: 2-ethylhexyl acrylate (special grade reagent), Kanto Chemical Co., Inc.
Ethylenically unsaturated monomer 3: 4-hydroxybutyl acrylate (special grade reagent), Tokyo Chemical Industry Co., Ltd.
Photopolymerization initiator 1: 1-hydroxy-cyclohexyl phenyl ketone (special grade reagent), Tokyo Chemical Industry Co., Ltd.
Photopolymerization initiator 2: 4-methylbenzophenone (special grade reagent), Tokyo Chemical Industry Co., Ltd.
Dispersant: Nopco Wet 50, Sannopco Corporation

<Production Example 3>
Aqueous emulsion (E-2), polyurethane emulsion (Dispacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), isocyanate (Desmodur (registered trademark) N3300, Sumika Bayer Urethane Co., Ltd.), A dispersant (Nopco Wet 50, San Nopco Co., Ltd.) and a thickener (Adecanol (registered trademark) UH-756VF, ADEKA Co., Ltd.) in a nonvolatile content ratio of 100 parts: 200 parts: 10 parts: 6 parts : It mixed so that it might become 0.6 parts, and the aqueous emulsion (E-100) was obtained.

<Production Example 4>
Polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), Isocyanate (Baihijoule (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.), Dispersant (Nopco Wet 50, San Nopco ( Co.)) and a thickener (Adecanol (registered trademark) UH-756VF, ADEKA Co., Ltd.) in a non-volatile content ratio of 100 parts: 15 parts: 5 parts: 0.3 parts and mixed to be aqueous An emulsion (E-101) was obtained.

<Example 9>
The water-based adhesive (F1) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 10 g / m ² after drying), and 10% at 50 ° C. After drying for a minute, M-EVA (A) was obtained by irradiating ultraviolet rays with a conveyor-type UV irradiation device (Eye Grandage ECS-4011GX, manufactured by Eye Graphics Co., Ltd.). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 300 m / min, integrated light quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan K K.)
Subsequently, the aqueous emulsion (E-100) was applied to the M-EVA (A) using a brush (M-EVA coating amount: weight after drying: about 70 g / m ² ), and oven-dried at 80 ° C. for 5 minutes. As a result, M-EVA (B) was obtained.
Subsequently, an aqueous emulsion (E-101) was applied to soft vinyl chloride and M-EVA (B) using a brush, and oven-dried at 80 ° C. for 5 minutes. Thereafter, the coated surfaces of the aqueous emulsion (E-101) of the obtained soft polyvinyl chloride and M-EVA (B) were bonded together, pressure bonded by hand, and further pressure bonded at 0.1 MPa for 60 seconds with a press. . Thus, a laminate (1) was obtained in which soft polyvinyl chloride, an adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order.

The obtained laminate (1) was allowed to stand at room temperature for 24 hours. The adhesion between M-EVA and soft vinyl chloride in the laminate was evaluated by measuring peel strength. The results are shown in Table 2-2.
○: Peel strength of 70 N / inch or more.
X: Peel strength is less than 70 N / inch.

<Examples 10 to 16>
Laminates (2) to (8) were obtained in the same manner as in Example 9, except that the aqueous adhesive (F1) of Example 9 was changed to any of the aqueous adhesives (F2) to (F8).
In the same manner as in Example 9, the adhesion of the laminate was evaluated. The results are shown in Table 2-2.

積層体（１）〜（８）は総じて、７０Ｎ／ｉｎｃｈ以上の十分に高い剥離強度を示した。

The laminates (1) to (8) generally exhibited sufficiently high peel strength of 70 N / inch or more.

<Production Example 5>
In a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 200 parts of toluene, a polymer A4 as a copolymer (Polytail (registered trademark) H, Mitsubishi Chemical Corporation, hydroxyl value: 45 to 50 mgKOH / g) 100 parts were added and dissolved by stirring at 90 ° C. In the obtained solution, 12 parts of Latemuru (registered trademark) E-1000A (30% aqueous solution, Kao Corporation), 4 parts of Neugen (registered trademark) EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.), n -A mixed solution of 5 parts of propanol was added dropwise over 10 minutes. After stirring for another 5 minutes, 5 parts of dimethylethanolamine was added, and the mixture was further stirred for 5 minutes to obtain a mixed solution.
Next, the stirrer was changed to TK Robotics (PRIMIX) and the resulting mixture was stirred with a disper blade while adding 100 parts of n-propanol and 100 parts of ion-exchanged water over 30 minutes. It was dripped. When fluidity was recognized in the mixture, the stirring blade was changed to a homomixer, and 300 parts of ion-exchanged water was added dropwise while stirring to obtain a milky white aqueous emulsion.
The obtained dispersion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered with a 200 mesh nylon net to obtain an aqueous emulsion (E-3) containing a polymer A4. The average particle diameter (number basis) of the dispersoid of the obtained aqueous emulsion (E-3) was 0.2 μm, and the non-volatile content concentration was 30%.

<Examples 17 to 21>
The water-based adhesive (the mass part of nonvolatile content is described), the ethylenically unsaturated monomer, the photopolymerization initiator, the dispersing agent, and the crosslinking agent in mass parts shown in Table 3-1 are mixed, and the nonvolatile content concentration Water was added so that it might become 10 mass%, and it stirred with the three one motor, and obtained the water-system adhesives (F9)-(F13) containing the aqueous emulsion of this invention.

表３−１におけるエチレン性不飽和モノマー及び光重合開始剤は以下のとおりである。
エチレン性不飽和モノマー１：イソボニルアクリレート、Ａｌｄｒｉｃｈ試薬
エチレン性不飽和モノマー２：２−エチルヘキシルアクリレート（特級試薬）、関東化学（株）
エチレン性不飽和モノマー３：４−ヒドロキシブチルアクリレート（特級試薬）、東京化成（株）
光重合開始剤１：１−ヒドロキシ−シクロヘキシルフェニルケトン
光重合開始剤２：４−メチルベンゾフェノン
分散剤：ノプコウェット５０、サンノプコ（株）
架橋剤：スミジュールＮ３３００、住化バイエルウレタン（株）
＜製造例６＞
ポリウレタンエマルション（ディスパコール（登録商標）Ｕ−５４、住化バイエルウレタン（株））、イソシアナート（バイヒジュール（登録商標）ＸＰ２６５５、住化バイエルウレタン（株））及び分散剤（ノプコウェット５０、サンノプコ（株））を不揮発分比で１００部：４０部：５部になるように混合して水性エマルション（Ｅ−１０２）を得た。

The ethylenically unsaturated monomers and photopolymerization initiators in Table 3-1 are as follows.
Ethylenically unsaturated monomer 1: Isobornyl acrylate, Aldrich reagent Ethylenically unsaturated monomer 2: 2-ethylhexyl acrylate (special grade reagent), Kanto Chemical Co., Inc.
Ethylenically unsaturated monomer 3: 4-hydroxybutyl acrylate (special grade reagent), Tokyo Chemical Industry Co., Ltd.
Photopolymerization initiator 1: 1-hydroxy-cyclohexyl phenyl ketone Photopolymerization initiator 2: 4-methylbenzophenone Dispersant: Nopco Wet 50, Sannopco Corporation
Cross-linking agent: Sumidur N3300, Sumika Bayer Urethane Co., Ltd.
<Production Example 6>
Polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), isocyanate (Baihydur (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.) and a dispersant (Nopco Wet 50, San Nopco ( The aqueous emulsion (E-102) was obtained by mixing so that the non-volatile content ratio was 100 parts: 40 parts: 5 parts.

<Example 22>
The aqueous adhesive (F9) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight after drying: about 10 g / m ² ), and 10% at 50 ° C. After drying for a minute, M-EVA (C) was obtained by irradiating with ultraviolet rays using a conveyor type UV irradiation apparatus (Eye Grandage ECS-4011GX, Eye Graphics Co., Ltd.). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 300 m / min, integrated light quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan K K.)
Subsequently, the aqueous emulsion (E-100) was applied to the M-EVA (C) using a brush (M-EVA coating amount: weight after drying: about 70 g / m ² ), and oven-dried at 80 ° C. for 5 minutes. As a result, M-EVA (D) was obtained.
Subsequently, an aqueous emulsion (E-101) was applied to soft vinyl chloride and M-EVA (D) using a brush and oven-dried at 80 ° C. for 5 minutes. Thereafter, the coated surfaces of the aqueous emulsion (E-101) of the obtained soft polyvinyl chloride and M-EVA (D) were bonded together, pressure-bonded by hand, and further pressure-bonded by press at 0.1 MPa for 60 seconds. . Thus, a laminate (9) was obtained in which soft polyvinyl chloride, an adhesive layer irradiated with ultraviolet rays, and M-EVA were laminated in this order.

The obtained laminate (9) was allowed to stand at room temperature for 24 hours. The adhesion between M-EVA and soft vinyl chloride in the laminate was evaluated by measuring peel strength. The results are shown in Table 3-2.
○: Peel strength of 70 N / inch or more.
X: Peel strength is less than 70 N / inch.

<Examples 23 to 26>
Example 22 except that the aqueous adhesive (F9) of Example 22 was changed to any of the aqueous adhesives (F10) to (F13) and the aqueous emulsion (E-100) was changed to the aqueous emulsion (E-102). In the same manner as in Example No. 22, laminates (10) to (13) were obtained.
In the same manner as in Example 22, the adhesion of the laminate was evaluated. The results are shown in Table 3-2.

積層体（９）〜（１３）は総じて、７０Ｎ／ｉｎｃｈ以上の十分に高い剥離強度を示した。

The laminates (9) to (13) generally exhibited a sufficiently high peel strength of 70 N / inch or more.

<Production Example 7>
In a separable flask reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 200 parts of toluene and 100 parts of a polymer A5 (BONDINE (registered trademark) HX8290, Arkema Co., Ltd.) as a copolymer were placed at 90 ° C. Keep warm, stir and dissolve. In the obtained solution, as a surfactant, Latemul (registered trademark) E-1000A (30% aqueous solution, Kao Corporation) 0.34 parts, Neugen (registered trademark) EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) )) A mixed solution of 0.1 part and 5 parts of isopropanol was added dropwise over 10 minutes, and then stirred for 5 minutes. To the obtained solution, 4 parts of dimethylethanolamine was added and stirred for 5 minutes to obtain a mixed solution.
Next, the stirrer was changed to TK Robotics (PRIMIX) equipped with a disper blade, and a mixed solution of 100 parts of n-propanol and 100 parts of ion-exchanged water was dropped over 30 minutes while stirring the mixed solution. did. When fluidity was observed in the obtained reaction mixture, the disper blade was changed to a homomixer, and 300 parts of ion-exchanged water was added dropwise with stirring to obtain a milky white solution.
The obtained solution was put into an eggplant flask, concentrated under reduced pressure using an evaporator, and filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-4). The average particle diameter (number basis) of the dispersoid of the obtained aqueous emulsion (E-4) was 0.2 μm, and the nonvolatile content concentration was 42%.

<Production Example 8>
A copolymer and a surfactant in parts by mass shown in Table 4-1 were mixed, and an aqueous emulsion (E-5) was obtained in the same manner as in <Production Example 9>.
The copolymers and surfactants in Table 4-1 are as follows.
Copolymer A5: BONDINE (registered trademark) HX8290 (acid value: 10 mgKOH / g), Arkema Co., Ltd.
Copolymer A6: Polytail (registered trademark) H (hydroxyl value: 45 to 50 mgKOH / g), Mitsubishi Chemical Corporation
Surfactant 1: LATEMUL (registered trademark) E-1000A (30% aqueous solution), Kao Corporation
Surfactant 2: Neugen (registered trademark) EA-177, Daiichi Kogyo Seiyaku Co., Ltd.

<Production Examples 9 and 10>
Aqueous emulsion (E-4), aqueous emulsion (E-5) (Dispacol (registered trademark) U54, Sumika Bayer Urethane Co., Ltd.), thickener, dispersant, in parts by mass shown in Table 4-2 And a crosslinking agent were mixed and stirred with a three-one motor to obtain aqueous emulsions (E-103) and (E-104).
The thickeners, dispersants, and crosslinking agents in Table 4-2 are as follows.
Thickener: Adecanol (registered trademark) UH-756VF, ADEKA Corporation
Dispersant: Nopco Wet 50, Sannopco Corporation
Cross-linking agent: Bayhijoule (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.

芳香族ポリイソシアナート２：スミジュール（登録商標）４４Ｖ２０（粘度：２００ｍＰａ・ｓ（２５℃））、住化バイエルウレタン（株）

芳香族ポリイソシアナート３：ミリオネート（登録商標）ＭＲ−２００（粘度：１５０〜２５０ｍＰａ・ｓ（２５℃）、日本ポリウレタン工業（株）
芳香族ポリイソシアナート４：ＳＢＵ（登録商標）イソシアナート Ｊ２４３（粘度：２５ｍPａ・ｓ（２５℃）、住化バイエルウレタン（株）

芳香族ポリイソシアナート５：コロテート Ｔ−１００、日本ポリウレタン工業（株）

芳香族ポリイソシアナート６：ミリオネート ＭＴ（日本ポリウレタン工業（株））の４０質量％トルエン溶液

芳香族ポリイソシアナート７：ミリオネート ＭＴ−Ｆ（日本ポリウレタン工業（株））の４０質量％トルエン溶液

芳香族ポリイソシアナート８：デスモジュール（登録商標）ＲＦＥ（住化バイエルウレタン（株））の酢酸エチルを留去（エバポレーターを使用）した後、トルエンに溶解し、４０質量％トルエン溶液としたもの。

<Examples 27 to 45>
A water-based emulsion (E-5), a thickener, a dispersant and an aromatic polyisocyanate in parts by mass shown in Table 5-1 and Table 5-2 were mixed, and the resulting mixture had a nonvolatile content of 10 It prepared with water so that it might become mass%, and it stirred with the three one motor, and obtained the water-system adhesives (F14)-(F32) containing the aqueous emulsion of this invention.
The thickeners, dispersants, and aromatic polyisocyanates in Table 5-1 are as follows.
Thickener: Adecanol (registered trademark) UH-756VF, ADEKA Corporation
Dispersant: Nopco Wet 50, Sannopco Corporation
Aromatic polyisocyanate 1: Sumidur (registered trademark) 44V10 (viscosity: 130 mPa · s (25 ° C.), Sumika Bayer Urethane Co., Ltd.)

Aromatic polyisocyanate 2: Sumidur (registered trademark) 44V20 (viscosity: 200 mPa · s (25 ° C.)), Sumika Bayer Urethane Co., Ltd.

Aromatic polyisocyanate 3: Millionate (registered trademark) MR-200 (viscosity: 150 to 250 mPa · s (25 ° C.), Nippon Polyurethane Industry Co., Ltd.)
Aromatic polyisocyanate 4: SBU (registered trademark) isocyanate J243 (viscosity: 25 mPa · s (25 ° C.), Sumika Bayer Urethane Co., Ltd.)

Aromatic polyisocyanate 5: Corotate T-100, Nippon Polyurethane Industry Co., Ltd.

Aromatic polyisocyanate 6: Millionate 40% by mass toluene solution of MT (Nippon Polyurethane Industry Co., Ltd.)

Aromatic polyisocyanate 7: Millionate MT-F (Nihon Polyurethane Industry Co., Ltd.) 40% by weight toluene solution

Aromatic polyisocyanate 8: Desmodur (registered trademark) RFE (Sumika Bayer Urethane Co., Ltd.) in which ethyl acetate was distilled off (using an evaporator), and then dissolved in toluene to give a 40% by mass toluene solution .

<Comparative Examples 1-12>
A water-based emulsion (E-5) (nonvolatile content ratio), a thickener, a dispersant and an aliphatic polyisocyanate in parts by mass shown in Table 5-3 were mixed, and the resulting mixture had a nonvolatile content of 10 % Was prepared with water and stirred with a three-one motor to obtain aqueous adhesives (F33) to (F44).
The thickeners, dispersants, and aliphatic polyisocyanates in Table 5-3 are as follows.
Thickener: Adecanol (registered trademark) UH-756VF, ADEKA Corporation
Dispersant: Nopco Wet 50, Sannopco Corporation
Aliphatic polyisocyanate 1: Sumidur (registered trademark) N3300, Sumika Bayer Urethane Co., Ltd.
Aliphatic polyisocyanate 2: Desmodur (registered trademark) N3400, Sumika Bayer Urethane Co., Ltd.
Aliphatic polyisocyanate 3: Desmodur (registered trademark) DA-L, Sumika Bayer Urethane Co., Ltd.
Aliphatic polyisocyanate 4: Bihijoule (registered trademark) 304, Sumika Bayer Urethane Co., Ltd.
Aliphatic polyisocyanate 5: Bayhijoule (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.

<Example 46>
Apply the water-based adhesive (F14) to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: non-volatile content: about 5 g / m ² ) and dry at 80 ° C. As a result, M-EVA (E) was obtained. Thereafter, the aqueous emulsion (E-103) was applied to M-EVA (E) using a glass rod (non-volatile content: about 55 g / m ² ), dried in an oven at 70 ° C., and M-EVA (F) was Obtained. Thereafter, the aqueous emulsion (E-104) was applied to soft polyvinyl chloride and M-EVA (F) using a glass rod (soft polyvinyl chloride coating amount: nonvolatile content mass: about 55 g / m ^2, M-EVA ( F) Application amount: non-volatile content mass of about 55 g / m ² ) and drying in an oven at 70 ° C. The surfaces of the obtained soft polyvinyl chloride and M-EVA (F) coated with an aqueous adhesive (E-104) were bonded together and pressure bonded by hand. This obtained the laminated body (14) which laminated | stacked soft polyvinyl chloride, the contact bonding layer, and M-EVA in this order.

The obtained laminate (14) was allowed to stand at room temperature for 24 hours, and thereafter, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), a peeling rate of 50 mm / min, a peeling angle of 180 degrees, at room temperature, The adhesion between M-EVA and soft vinyl chloride in the laminate was evaluated by measuring peel strength. The results are shown in Table 6-1.
○: Peel strength of 70 N / inch or more.
X: Peel strength is less than 70 N / inch.

The obtained laminate (14) was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Toyo Seiki, Strograph T), the set temperature in the tank was 60 ° C., the peeling speed was 50 mm / min, and the peeling angle. The heat resistance of the adhesive layer was evaluated by measuring the peel strength between M-EVA and soft vinyl chloride in the laminate at 180 degrees. The results are shown in Table 6-1.
○: Peel strength of 70 N / inch or more.
X: Peel strength is less than 70 N / inch.

<Examples 47 to 66, Comparative Examples 13 to 26>
The aqueous adhesive (F14) of Example 46 was changed to any of the aqueous adhesives (F15) to (F44), and the drying temperature of the aqueous adhesives (F15) to (F44) was 80 ° C. or 90 ° C. Except for the above, laminates (15) to (48) were obtained in the same manner as in Example 46.
In the same manner as in Example 46, the adhesiveness of the laminate and the heat resistance of the adhesive layer were evaluated. The results are shown in Table 6-1, Table 6-2 or Table 6-3.

積層体（１４）〜（３４）は総じて、十分に高い剥離強度を示した。

The laminates (14) to (34) generally exhibited sufficiently high peel strength.

<Examples 67 to 87, Comparative Examples 27 to 40>
Apply the aqueous emulsion (E-104) to a 100% cotton canvas in place of the soft polyvinyl chloride coated with the aqueous emulsion (E-104) and dry it (coating amount: non-volatile matter mass: about 130 g / m ² ). A laminate (49) to (83) in which a cotton fabric, an adhesive layer, and M-EVA were laminated in this order were the same as in Example 20 except that cotton fabric-A dried at 80 ° C. for 20 minutes was used. Obtained.
In the same manner as in Example 46, the adhesiveness of the laminate and the heat resistance of the adhesive layer were evaluated. The results are shown in Table 7-1, Table 7-2 or Table 7-3.

積層体（４９）〜（６９）は総じて、十分に高い剥離強度を示した。

The laminates (49) to (69) generally exhibited sufficiently high peel strength.

<Production Example 11>
In a separable flask reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 200 parts of toluene as a solvent and 100 parts of a polymer B1 (Hardylene (registered trademark) F-6P, Toyobo Co., Ltd.) as a copolymer are placed. The solution was stirred and dissolved at 90 ° C. Then, as a surfactant, Latemul (registered trademark) E-1000A (30% aqueous solution, Kao Corporation) 16.8 parts, Neugen (registered trademark) EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts, A mixture of 5 parts of isopropanol was added. Next, the stirring apparatus was changed to TK Robotics (PRIMIX), and the reaction mixture was stirred with a disper blade and kept at 90 ° C., while maintaining a mixture of 100 parts isopropanol and 100 parts ion-exchanged water for 10 minutes. It was dripped over. When fluidity was recognized in the reaction mixture, the stirring blade was changed to a homomixer, and 300 parts of ion-exchanged water was added dropwise while stirring to obtain a milky white dispersion. After further stirring for 5 minutes, the dispersion was cooled to room temperature, and 0.8 parts of dimethylethanolamine was added while stirring with a homomixer, and further stirred for 5 minutes.
The obtained dispersion was put into an eggplant flask, distilled off under reduced pressure with an evaporator, and filtered with a 200 mesh nylon net to obtain an aqueous emulsion (E-6) containing a polymer B1 and a surfactant. The average particle diameter (number basis) of the dispersoid of the obtained aqueous emulsion (E-6) was 0.2 μm, and the non-volatile content concentration was 30%.

<Production Example 12>
In a separable flask reaction vessel equipped with a stirrer, thermometer and reflux condenser, 100 parts of polymer B1 (Hardylene (registered trademark) F-6P, Toyobo Co., Ltd.) as a copolymer, 190 parts of tetrahydrofuran, Neugen (registered) 20 parts of DKS NL-180 (Daiichi Kogyo Seiyaku Co., Ltd.) was added, stirred and heated to 65 ° C. Next, 300 parts of ion-exchanged water and 2 parts of dimethylethanolamine were further added and stirred for 2 hours to obtain a pale yellow dispersion. The obtained dispersion was put into an eggplant flask and distilled off under reduced pressure with an evaporator to obtain a concentrated dispersion. The obtained concentrated liquid was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-7) containing a polymer B1 and a surfactant. The resulting aqueous emulsion (E-7) had an average particle size (number basis) of the dispersoid of 0.2 μm and a non-volatile content concentration of 30%.

<Production Example 13>
To a separable flask reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 200 parts of toluene and 100 parts of polymer B2 (Hardylene (registered trademark) HM-21P, Toyobo Co., Ltd.) are added and stirred at 90 ° C. Then, the polymer B2 was dissolved. Subsequently, a mixed solution of 20 parts of New Coal 714 (Nippon Emulsifier Co., Ltd.) and 5 parts of n-propanol was added to obtain a mixed solution. Next, the stirrer was changed to TK Robotics (PRIMIX), and the mixed solution was stirred with a disper blade of the stirrer and mixed with 100 parts of n-propanol and 100 parts of ion-exchanged water while keeping the temperature at 90 ° C. The liquid was added dropwise to the mixed solution over 10 minutes. When fluidity was recognized in the mixed solution, the stirring blade was changed to a homomixer, and 300 parts of ion-exchanged water was added dropwise with stirring to obtain a milky white dispersion. After stirring for another 5 minutes, the dispersion was cooled to room temperature, 0.8 parts of dimethylethanolamine was added while stirring with a homomixer, and the mixture was further stirred for 5 minutes.
The obtained dispersion was put into an eggplant flask and distilled off under reduced pressure with an evaporator to obtain a concentrated dispersion. The obtained concentrated liquid was filtered through a 200 mesh nylon net to obtain an aqueous emulsion (E-8) containing a polymer B2 and a surfactant. The average particle size (number basis) of the dispersoid of the obtained aqueous emulsion (E-8) was 0.3 μm, and the nonvolatile content concentration was 30%.

<Production Example 14>
An aqueous emulsion (E-9) was obtained in the same manner as in Production Example 11 except that the polymer B3 (Hardlen (registered trademark) CY-9122P, Toyobo Co., Ltd.) was used instead of the polymer B1. The average particle diameter (number basis) of the dispersoid was 0.2 μm, and the non-volatile content was 30%.

<Production Example 15>
An aqueous emulsion (E-10) was obtained in the same manner as in Water Production Example 11, except that the polymer B4 (Hardlen (registered trademark) F-2P, Toyobo Co., Ltd.) was used instead of the polymer B1. The average particle size (number basis) of the dispersoid was 1.0 μm, and the non-volatile content was 30%.

<Production Example 16>
An aqueous emulsion (E-11) was obtained in the same manner as in Water Production Example 11 except that the polymer B5 (Hardlen (registered trademark) EW-8511, Toyobo Co., Ltd.) was used instead of the polymer B1.

<Production Example 17>
An aqueous emulsion (E-12) was obtained in the same manner as in Water Production Example 11 except that the polymer B6 (Hardlen (registered trademark) EW-5303, Toyobo Co., Ltd.) was used instead of the polymer B1.

<Production Example 18>
An aqueous emulsion (E-13) was obtained in the same manner as in Water Production Example 11, except that the polymer B7 (Hardlen (registered trademark) EW-5515, Toyobo Co., Ltd.) was used instead of the polymer B1.

<Production Example 19>
An aqueous emulsion (E-14) was obtained in the same manner as in Water Production Example 11 except that the polymer B8 (Hardlen (registered trademark) EW-5513-4, Toyobo Co., Ltd.) was used instead of the polymer B1.

<Production Example 20>
Instead of polymer B1, polymer B5 (Hardlen (registered trademark) EW-5303, Toyobo Co., Ltd.), polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.) and isocyanate Aqueous emulsion (E-15) in the same manner as in Production Example 12 except that a mixture of 60 parts: 40 parts: 10 parts was used in a nonvolatile content ratio of (Baihijoule (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.). Got.

<Production Example 21>
Instead of polymer B1, polymer B9 (Hardren (registered trademark) EH-801J, Toyobo Co., Ltd.), polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.) and isocyanate A water-based emulsion (E-16) was prepared in the same manner as in Water Production Example 12 except that a mixture of 60 parts: 40 parts: 10 parts in a nonvolatile content ratio of (Baihijoule (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.) was used. )

<Production Example 22>
In place of the polymer B1, an aqueous emulsion (E-7), a polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.) and an isocyanate (Baihydur (registered trademark) XP2655, Sumika Bayer) An aqueous emulsion (E-17) was obtained in the same manner as in Water Production Example 12 except that a mixture of 60 parts: 40 parts: 10 parts in a nonvolatile content ratio of Urethane Co., Ltd. was used.

<Production Example 23>
In place of the polymer B1, an aqueous emulsion (E-8), a polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.) and an isocyanate (Baihydur (registered trademark) XP2655, Sumika Bayer) An aqueous emulsion (E-18) was obtained in the same manner as in Water Production Example 12 except that a mixture of 60 parts: 40 parts: 10 parts in a nonvolatile content ratio of Urethane Co., Ltd. was used.

<Examples 88 to 106>
An aqueous emulsion (the mass part of the nonvolatile content is described), an ethylenically unsaturated monomer, a photopolymerization initiator, and a dispersing agent of parts by mass shown in Table 8-1 and Table 8-2 are mixed, and the mixture is further mixed. Water was added so that the non-volatile content concentration of the aqueous solution became 20% by mass, and the mixture was stirred with a three-one motor to obtain aqueous adhesives F45 to F63 containing the aqueous emulsion of the present invention.

表８−１及び２におけるエチレン性不飽和モノマー及び光重合開始剤は以下のとおりである。
エチレン性不飽和モノマー１：イソボニルアクリレート（Ａｌｄｒｉｃｈ試薬）
光重合開始剤１：２−ヒドロキシ-2-エチルプロピオフェノン（東京化成（株）、特級試薬）
光重合開始剤２：２，２−ジエトキシアセトフェノン（東京化成（株）、特級試薬）
架橋剤１：デスモジュール（登録商標）ＸＰ２６５５（住化バイエルウレタン（株））
架橋剤２：カルボジライト（登録商標）Ｖ−０４（日清紡ケミカル（株））
分散剤１：ノプコウェット５０（サンノプコ株式会社）、
分散剤２：ＢＹＫ（登録商標）−３４９、ビックケミー.ジャパン（株）

The ethylenically unsaturated monomers and photopolymerization initiators in Tables 8-1 and 2 are as follows.
Ethylenically unsaturated monomer 1: isobornyl acrylate (Aldrich reagent)
Photopolymerization initiator 1: 2-hydroxy-2-ethylpropiophenone (Tokyo Kasei Co., Ltd., special grade reagent)
Photopolymerization initiator 2: 2,2-diethoxyacetophenone (Tokyo Kasei Co., Ltd., special grade reagent)
Cross-linking agent 1: Desmodur (registered trademark) XP2655 (Sumika Bayer Urethane Co., Ltd.)
Crosslinking agent 2: Carbodilite (registered trademark) V-04 (Nisshinbo Chemical Co., Ltd.)
Dispersant 1: Nopco Wet 50 (San Nopco Co., Ltd.)
Dispersant 2: BYK (registered trademark) -349, Big Chemie Japan Co., Ltd.

<Production Example 24>
Aqueous emulsion (E-9), polyurethane emulsion (Dispacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), isocyanate (Baihydur (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.), dispersion An aqueous emulsion (E-105) was obtained by mixing the agent (Nopco Wet 50, San Nopco Co., Ltd.) in a nonvolatile content ratio of 100 parts: 100 parts: 20 parts: 20 parts.

<Production Example 27>
Polyurethane emulsion (Disquacol (registered trademark) U-54, Sumika Bayer Urethane Co., Ltd.), Isocyanate (Baihijoule (registered trademark) XP2655, Sumika Bayer Urethane Co., Ltd.), Dispersant (Nopco Wet 50, San Nopco ( The aqueous emulsion (E-106) was obtained by mixing so that the non-volatile content ratio was 100 parts: 15 parts: 5 parts.

<Example 107>
The water-based adhesive (F45) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 10 g / m ² after drying), and 10% at 50 ° C. After drying for a minute, M-EVA (G) was obtained by irradiating with ultraviolet rays using a conveyor-type UV irradiation device (Eye Graphics Inc., Eye Grandage ECS-4011GX). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 300 m / min, integrated light quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan K K.)
Subsequently, an aqueous emulsion (E-105) was applied to M-EVA (G) using a brush (M-EVA coating amount: weight after drying: about 70 g / m ² ), and oven-dried at 70 ° C. for 5 minutes. As a result, M-EVA (H) was obtained.
Subsequently, an aqueous emulsion (E-106) was applied to soft vinyl chloride and M-EVA (H) using a brush and oven-dried at 70 ° C. for 5 minutes. Thereafter, the coated surfaces of the aqueous emulsion (E-106) of the obtained soft polyvinyl chloride and M-EVA (H) were bonded together, pressure-bonded by hand, and further pressure-bonded by press at 0.1 MPa for 10 seconds. . This obtained the laminated body (84) which laminated | stacked soft polyvinyl chloride, the contact bonding layer irradiated with the ultraviolet-ray, and M-EVA in this order.

The obtained laminate (84) was allowed to stand at room temperature for 24 hours, and thereafter, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), a peeling rate of 50 mm / min, a peeling angle of 180 degrees, at room temperature, The adhesion between M-EVA and soft vinyl chloride in the laminate was evaluated by measuring peel strength. The results are shown in Table 8-3.
○: Peel strength of 70 N / inch or more.
X: Peel strength is less than 70 N / inch.

<Examples 108 to 122>
Laminated bodies (85) to (99) were obtained in the same manner as in Example 107 except that the aqueous adhesive (F45) of Example 107 was changed to any of the aqueous adhesives (F46) to (F60).
In the same manner as in Example 107, the adhesiveness of the laminate was evaluated. The results are shown in Table 8-3.

<Example 123>
The water-based adhesive (F61) was applied to M-EVA (ethylene-vinyl acetate copolymer foam) using a brush (coating amount: weight about 10 g / m ² after drying), and 10% at 50 ° C. After drying for a minute, M-EVA (G) was obtained by irradiating with ultraviolet rays using a conveyor type UV irradiation apparatus (Eye Graphics, Inc., Eye Grandage ECS-4011GX). (Lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 300 m / min, integrated light quantity: 1100 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measurement value, FusionUV Systems Japan K K.)
Subsequently, the aqueous emulsion (E-106) was applied to soft vinyl chloride and M-EVA (H) using a brush and oven dried at 70 ° C. for 5 minutes. Thereafter, the coated surfaces of the aqueous emulsion (E-106) of the obtained soft polyvinyl chloride and M-EVA (H) were bonded together, pressure-bonded by hand, and further pressure-bonded by press at 0.1 MPa for 10 seconds. . This obtained the laminated body (100) which laminated | stacked soft polyvinyl chloride, the contact bonding layer irradiated with the ultraviolet-ray, and M-EVA in this order.

<Examples 124 and 125>
Laminates (101) and (102) were obtained in the same manner as in Example 123 except that the aqueous adhesive (F61) of Example 123 was changed to either the aqueous adhesive (F62) or (F63).
In the same manner as in Example 123, the adhesiveness of the laminate was evaluated. The results are shown in Table 8-3.

積層体（８４）〜（１０２）は総じて、７０Ｎ／ｉｎｃｈ以上の十分に高い剥離強度を示した。

The laminates (84) to (102) generally exhibited a sufficiently high peel strength of 70 N / inch or more.

  The aqueous emulsion of the present invention is useful for bonding adherends with sufficient strength.

Claims (21)

A polymer component containing at least one polymer (1) selected from the group consisting of the following polymer (A) and polymer (B), at least selected from the group consisting of a photopolymerization initiator and an aromatic polyisocyanate. An aqueous emulsion containing one kind.
Polymer (A): having at least one kind selected from a hydroxyl group and a carboxy group, all the hydroxyl groups and carboxy groups to be bonded are directly bonded to the carbon atoms constituting the main chain, and the carbon atoms in the atoms constituting the main chain The polymer whose ratio is 95% or more Polymer (B): The ratio of the carbon atom in the atom which has at least 1 sort (s) chosen from a carboxy group and a carboxylic anhydride structure, and a chlorine atom, and comprises a principal chain Whose polymer is 95% or more   The aqueous emulsion according to claim 1, wherein the content of the polymer (1) is 0.1 to 10% by mass.   The aqueous emulsion according to claim 1 or 2, comprising a photopolymerization initiator.   The aqueous emulsion according to claim 3, wherein the content of the polymer (1) is from 3 to 1000 parts by mass with respect to 1 part by mass of the photopolymerization initiator.   The water-based emulsion in any one of Claims 1-4 containing 2 or more types of polymers (A) from which a structural unit differs.   The polymer (A) is a polymer having at least one structure selected from a hydroxyl group and a carboxy group at each of at least two carbon atoms constituting the terminal of the main chain. An aqueous emulsion according to 1.   The aqueous emulsion according to any one of claims 1 to 6, wherein the polymer (A) has a carboxy group.   The water-based emulsion in any one of Claims 1-7 containing a polymer (B). The aromatic polyisocyanate is a compound represented by formula (5), a compound represented by formula (6), tris (p-isocyanatophenyl) thiophosphate, a compound represented by formula (5) or a formula ( The isocyanurate obtained from the compound represented by 6), the biuret obtained from the compound represented by formula (5) or the compound represented by formula (6), and the compound or formula represented by formula (5) The aqueous emulsion according to any one of claims 1 to 8, which is at least one selected from the group consisting of adducts of trimethylolpropane obtained from the compound represented by (6).

(In the formula, R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group. N represents 1 or 2. m represents 2 or 3. r represents 1 or 2. S represents an integer of 0 to 2. p represents an integer of 0 to 100.)   The aromatic polyisocyanate is at least one selected from the group consisting of a compound represented by the formula (5), a compound represented by the formula (6) and tris (p-isocyanatophenyl) thiophosphate. 9. The aqueous emulsion according to 9.   The aqueous emulsion according to claim 9 or 10, comprising a compound represented by the formula (6), wherein p is 1 to 100.   The aqueous emulsion according to claim 1, comprising an aromatic polyisocyanate.   The aqueous emulsion according to claim 12, wherein the content of the aromatic polyisocyanate with respect to 100 parts by mass of the polymer (1) is 1 to 200 parts by mass.   Furthermore, the aqueous emulsion in any one of Claims 1-13 containing an ethylenically unsaturated monomer.   Furthermore, the aqueous | water-based emulsion in any one of Claims 1-14 in which a polymer component contains a polyurethane. Furthermore, the aqueous emulsion in any one of Claims 1-15 containing surfactant represented by Formula (B).

(In the formula, n represents an integer of 1 to 3. m represents an integer of 1 to 100.)   An aqueous adhesive comprising the aqueous emulsion according to claim 1.   A laminate in which an adhesive layer obtained from the aqueous adhesive according to claim 17 is sandwiched between adherends.   The laminated body which pinched | interposed between the to-be-adhered bodies the contact bonding layer obtained from the aqueous adhesive of Claim 17 irradiated with the ultraviolet-ray.   The laminate according to claim 18 or 19, wherein the adherend is a cellulosic material or a plastic material.   The laminate according to claim 18 or 19, wherein the adherend is an ethylene-vinyl acetate copolymer.