JP2013151141A - Method for producing laminate structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a laminate structure having superior adhesion.SOLUTION: A method for producing a laminate structure by laminating a first base material, an adhesive layer and a second base material in this order includes the steps of: applying an aqueous adhesive to the surface of the first base material, and subjecting the first base material with the aqueous adhesive applied thereon to electromagnetic wave processing using electromagnetic waves in a frequency band of 2.45±0.02 GHz; applying the aqueous adhesive to the surface of the second base material, and drying the second base material with the aqueous adhesive applied thereon; and pasting a surface of the first base material with the aqueous adhesive applied thereon and subjected to the electromagnetic wave treatment to a surface of the dried second base material with the aqueous adhesive applied thereon.

Description

  The present invention relates to a method for manufacturing a laminated structure.

Non-Patent Document 1 describes a method of obtaining a laminated structure in which a base material and a base material are bonded to each other with a water-based adhesive and are firmly bonded.
Various studies have been made on a method for obtaining a laminated structure in which a base material and a base material are bonded to each other with a water-based adhesive and are firmly bonded.

Sei Ogata, Yukio Doi, “Physical Properties and Applications of Synthetic Resin Emulsions,” published by Kobunshi Shuppankai, August 20, 1978, p107

  When bonding a base material and a base material with a water-based adhesive agent, there were cases where satisfactory adhesiveness could not always be obtained.

The present invention includes the following inventions.
[1] A method for producing a laminated structure in which a first substrate, an adhesive layer, and a second substrate are laminated in this order,
(A) applying a water-based adhesive to the surface of the first base material, subjecting the first base material coated with the water-based adhesive to an electromagnetic wave with an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz;
(B) applying a water-based adhesive to the surface of the second substrate and drying the second substrate coated with the water-based adhesive;
(C) A method of manufacturing a laminated structure including a step of bonding a surface of the first base material to which the aqueous adhesive has been applied and a surface of the second base material to which the aqueous base material has been applied, which has been dried. .
[2] The method for producing a laminated structure according to [1], wherein both the first base material and the second base material are treated with electromagnetic waves having a frequency band of 2.45 ± 0.02 GHz. .
[3] Further, before the bonding step, an aqueous adhesive is applied again to at least one surface of the adhesive layer applied to the first base material and the second base material, and the obtained base The manufacturing method of the laminated structure as described in [1] or [2] including the process of drying a material.
[4] The laminated structure obtained by bonding the first base material and the second base material is further treated with electromagnetic waves having a frequency band of 2.45 ± 0.02 GHz. The manufacturing method of the laminated structure as described in any one.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated structure which can adhere | attach a base material and a base material firmly can be provided.

The method for producing a laminated structure of the present invention is a method for producing a laminated structure in which a first substrate, an adhesive layer, and a second substrate are laminated in this order,
(A) applying a water-based adhesive to the surface of the first base material, subjecting the first base material coated with the water-based adhesive to an electromagnetic wave with an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz;
(B) applying a water-based adhesive to the surface of the second substrate and drying the second substrate coated with the water-based adhesive;
(C) The process which bonds the surface by which the aqueous adhesive of the 1st base material by which the electromagnetic wave process was applied and the surface by which the aqueous adhesive of the 2nd base material dried was bonded together is included.

<First base material and second base material>
Examples of the first base material and the second base material include films and sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing, shoes, and the like.
Specific materials include wood-based materials such as wood, plywood, medium density fiberboard (MDF), particleboard, and fiberboard; cellulosic materials such as cotton cloth, cotton-containing fibers, linen, and rayon; polyethylene (derived from ethylene) Polyolefins having a structural unit as a main component), polypropylene (polyolefin having a structural unit derived from propylene as a main component), polystyrene (polyolefin having a structural unit derived from styrene as a main component), polycarbonate, 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 Polyamide etc. Resin or plastic material of the foam, and the like; polyurethanes, polyamide and synthetic leather polyamino acid; glass, ceramic material, ceramic or the like; iron, stainless steel, copper, a metal material such as aluminum and the like. The first base material and the second base material may be a composite material composed of a plurality of materials. Further, an inorganic filler such as talc, silica and activated carbon, a kneaded molded product of carbon fiber or the like and a plastic material may be used.

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

  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, hemp and the like. 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), inorganic fibers (carbon fibers, glass fibers) and the like.

The first base material and the second base material can take various forms such as a film, a block, a fiber (for example, a woven fabric, a knitted fabric, a non-woven fabric, a knitted fabric, a felt), and a foam.
Among them, preferably, the footwear, the insole, the outer bottom, etc. of footwear including men's shoes and women's shoes such as sports shoes, town shoes, business shoes, and industrial work shoes, etc. Form and material (eg, polyolefin, EVA, nylon, cotton-containing fiber, synthetic leather, etc.).
The surface of the first base material and / or the second base material may be smooth or may have irregularities. Moreover, you may give the primer process for improving adhesion | attachment, such as an adhesive agent, to those surfaces. Examples of the primer treatment include blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, anchor layer formation, and the like.

<Process (a)>
Any known coating method can be used to apply the aqueous adhesive to the surface of the first substrate. Examples 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, spatula coating, and the like.

In addition, before apply | coating a water-based adhesive, you may give a primer process to the surface of a 1st base | substrate as mentioned above.
In particular, when using 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 application of the water-based adhesive here can use the above-mentioned method, and the drying can be performed by any of the methods described below, natural drying, non-thermal drying such as air drying, or normal hot air circulation Drying using a mold oven, infrared or far-infrared heater is preferred. When performing the primer treatment, only one type of aqueous adhesive may be used, or two or more types may be used. Further, the primer treatment may be performed only once, or may be performed twice or more.
The thickness of the aqueous adhesive to be applied can be appropriately adjusted depending on the composition of the aqueous adhesive to be used, the material and form of the substrate, and the like. For example, the thickness after the electromagnetic wave treatment is about 0.01 to 300 μm, preferably about 0.01 to 200 μm, more preferably about 0.2 to 200 μm.

  Usually, after apply | coating a water-based adhesive to a 1st base material, it dries. In the method for producing a laminated structure of the present invention, as this drying or heat treatment, the first substrate is subjected to electromagnetic wave treatment with electromagnetic waves having a frequency band of 2.45 ± 0.02 GHz. By this electromagnetic wave treatment, the water contained in the aqueous adhesive (as will be described later, the solvent if present) can be removed to form an adhesive layer.

  As long as the electromagnetic wave treatment uses an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz, any method capable of irradiating the surface of the first substrate with the electromagnetic wave can be used. Typically, for example, an electromagnetic wave device that can emit an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz, specifically, a microwave oven or the like can be used. The output and time of the electromagnetic wave treatment can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous adhesive used, and the like. For example, the output is in the range of about 1 W to 20 kW, preferably about 100 W to 20 kW, and more preferably about 300 W to 20 kW. The time may be about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes. The electromagnetic wave treatment may be performed only once or may be performed twice or more. In this case, different frequency bands may be combined.

Before and after the electromagnetic wave treatment, the first treatment may be performed by non-thermal drying such as standing (natural drying) or air drying, or by heat drying such as drying using a normal hot air circulation oven, infrared or far infrared heater. You may perform preliminary drying of a base material. In this case, the temperature and time for preliminary drying can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous adhesive used in the present invention, and the like. For example, as temperature, about 30-150 degreeC is mentioned, Preferably it is about 40-85 degreeC. The time may be about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.
The adhesive layer after the electromagnetic wave treatment usually does not contain water (or a solvent, if present) as described below, or 3% of the total weight of the adhesive layer even if it is contained. % Or less.

<Process (b)>
Any of the above-described known coating methods can be used for applying the aqueous adhesive to the surface of the second substrate. Before applying the aqueous adhesive layer, as described above, the surface of the second substrate may be subjected to a primer treatment. In this primer treatment, different aqueous adhesives may be used in the first and second substrates, but it is preferable to use the same one.
The thickness of the aqueous adhesive to be applied can be appropriately adjusted depending on the composition of the aqueous adhesive to be used, the material and form of the substrate, and the like. For example, the thickness after drying is about 0.01 to 300 μm, preferably about 0.01 to 200 μm.

  After applying the aqueous adhesive to the second substrate, the second substrate is dried. Drying may be natural drying, non-thermal drying such as air drying, or drying using a normal hot-air circulating oven, infrared or far-infrared heater, electromagnetic waves (for example, electromagnetic waves having a frequency band of 2.45 ± 0.02 GHz) It can be performed by heat drying such as drying using an irradiation apparatus or a microwave oven. The drying temperature and time can be appropriately adjusted according to the characteristics of the substrate, the composition of the aqueous adhesive used, and the like. For example, as temperature, about 30-150 degreeC is mentioned, Preferably it is about 40-85 degreeC. The heating time is about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes. The drying of the second substrate is preferably performed by electromagnetic wave treatment. That is, preferably, the electromagnetic wave treatment is performed with an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz as in the case of the first base material. However, the conditions and the like do not necessarily have to be set in the same manner as the first substrate, and the output and / or processing time may be changed depending on the thickness of the applied aqueous adhesive. For example, when performing electromagnetic wave treatment on both the first base material and the second base material, different frequency bands may be combined. The electromagnetic wave treatment may be performed only once or may be performed twice or more. In this case, different frequency bands may be combined.

Application of the water-based adhesive and electromagnetic wave treatment or drying may be performed first on either the first base material or the second base material. That is, either step (a) or step (b) may be performed first.
Moreover, the water-based adhesive applied to the first base material and the second base material may not be the same water-based adhesive, but considering the adhesiveness of both, it is preferable to use the same water-based adhesive.
The adhesive layer after drying usually does not contain water (or a solvent if present, as will be described later) or even if it is contained, it is usually 3% of the total weight of the adhesive layer. It becomes about weight% or less.

<Process (c)>
As a method of bonding the surface of the first base material coated with the aqueous adhesive and the dried surface of the second base material coated with the aqueous adhesive, a mechanical operation or a manual method is used. Either of these may be used.
When bonding, heat, pressure or both may be applied. In the case of applying heat, it is necessary to set the temperature range in which the first base material, the second base material, and the adhesive layer do not deteriorate, preferably about 120 ° C. or less, more preferably about 100 ° C. or less. is there. The heat load may be performed using the above-described normal hot air circulation type oven, infrared heater, microwave oven, or the like. As a pressure in the case of applying a pressure, about 100 g / cm < ² > or more is mentioned, and less than the pressure which the shape of a 1st base material and a 2nd base material deform | transforms. In the case of applying heat and / or pressure, the time is, for example, about 1 second to 10 days.
In addition, it is preferable to perform the electromagnetic wave process mentioned above again with respect to the obtained laminated structure after performing such bonding. In this case, the electromagnetic wave treatment conditions are the same as described above.

In addition, in the manufacturing method of the laminated structure of this invention, in process (a) and process (b), an aqueous adhesive is apply | coated to the surface of a 1st base material and a 2nd base material, and electromagnetic wave treatment or drying is carried out. After performing (that is, the first time), before the step (c), the aqueous adhesive is again applied to the surface on which the aqueous adhesive of at least one of the first base material and the second base material is applied. It is preferable to apply and dry the obtained substrate (that is, the second time).
Here, the second (second) application of the water-based adhesive and the drying are performed in the same manner as described above, that is, the conditions for the first application of the water-based adhesive applied to the first substrate and the electromagnetic wave treatment. Alternatively, it may be performed in the same manner as in the first application and drying of the aqueous adhesive applied to the second substrate. However, it is not always necessary to select the same conditions for the application (first time) of the aqueous adhesive and the electromagnetic wave treatment or drying and the application (electromagnetic wave treatment or drying) of the second time (second time). The application method, application thickness, drying method, output and time of electromagnetic wave treatment, presence / absence of preheating before and after electromagnetic wave treatment, conditions thereof, and the like may be appropriately changed.
The application of the aqueous adhesive and the electromagnetic wave treatment or drying again (second time) may be performed only once on at least one of the first base material and the second base material. In addition, at least one of the second base material or both of them may be subjected to one or more application of the aqueous adhesive and electromagnetic wave treatment or drying (that is, the third and subsequent times). However, in addition to the step (a) and the step (b), when further application of the aqueous adhesive (after the second time) is performed, the above-mentioned leaving (natural drying) is not performed without applying the electromagnetic wave treatment, or Or, a normal hot air circulation type oven, an infrared heater or the like may be performed.

Among them, preferably, the application of the aqueous adhesive (first time) and the surface of both the first substrate and the second substrate subjected to the application of the aqueous adhesive and the electromagnetic wave treatment (first time) Similar to the electromagnetic wave treatment, the surface of both the first base material and the second base material is coated with an aqueous adhesive and subjected to the electromagnetic wave treatment.
By performing such application of the aqueous adhesive again and electromagnetic wave treatment or drying, the adhesive layer can be reliably disposed with a sufficient thickness on the entire surface of the first base material and the second base material. By laminating the first base material and the second base material, it is possible to reliably manufacture a laminated structure in which both are firmly bonded.

<Water-based adhesive>
As long as the water-based adhesive used in the method for producing a laminated structure of the present invention contains water as a solvent, an adhesive, a pressure-sensitive adhesive and an adhesive modifier, a heat sealant, a paint, a primer for coating, and an ink Any material capable of exhibiting the functions of a binder, an adhesive, an emulsion modifier and the like can be used. Especially, what contains the polymer which has adhesiveness is preferable, and what contains a thermoplastic polymer is preferable. Examples of the polymer include polyolefin resin, acrylic resin (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), acrylonitrile. Examples thereof include polymers and copolymers such as butadiene styrene resin (ABS resin) and AS resin, and modified products. These may be used alone or in combination of two or more.

<Polymer>
The polymer contained in the aqueous adhesive is more preferably one containing a polymer having one or more 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 (C2), propylene (C3), 1-butene (C4), 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene, Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, vinylcyclohexane, etc. Can be mentioned. Preferred are ethylene, propylene, 1-butene and the like.

  Polymers containing structural units derived from α-olefins having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), polypropylene (PP), etc. Homopolymer or modified product thereof; ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer An α-olefin copolymer such as ethylene-propylene-1-butene copolymer or a modified product thereof; a copolymer with a copolymerizable monomer or a modified product thereof; or a mixture of two or more of these. It is preferable. In a copolymer with a copolymerizable monomer, the copolymerizable monomer and α-olefin may be used alone or in combination of two or more. The form of the copolymer may be any of random copolymerization, block copolymerization, graft copolymerization, and the like. These may be those having a low molecular weight or a high molecular weight such as peroxide.

  As the α-olefin polymer, the total structural unit is 100 mol%, for example, the structural unit derived from propylene: the structural unit derived from 1-butene, preferably 71 to 99 mol%: 1 to 29 mol%. Copolymer or modified product thereof, more preferably 80 to 99 mol%: copolymer or modified product contained in 1 to 20 mol%, more preferably 90 to 99 mol%: 1 to 10 mol% Or a modified product thereof. This copolymer is preferably a copolymer in which substantially no melting peak is observed. The fact that the melting peak is not substantially observed means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed by differential scanning calorimetry (DSC) in the temperature range of −100 to 200 ° C.

  A structural unit derived from ethylene: a copolymer containing propylene-derived structural units, preferably 5 to 20 mol%: 80 to 95 mol%, or a modified product thereof, more preferably 5 to 19 mol%: 81 to 81 The copolymer or modified product thereof contained at 95 mol%, more preferably, the copolymer or modified product thereof contained at 10 to 19 mol%: 81 to 90 mol%. This copolymer is preferably a copolymer in which a melting peak is observed. A melting peak is observed by means of differential scanning calorimetry (DSC) in the temperature range of −100 to 200 ° C., a crystal melting peak with a crystal melting heat of 1 J / g or more or a crystal with a crystallization heat of 1 J / g or more. This means that a chemical peak is observed.

  Structural unit derived from ethylene: Structural unit derived from propylene: A copolymer containing 1-butene derived structural unit, preferably 1 to 99 mol%: 99 to 1 mol%: 99 to 1 mol% or a modification thereof A copolymer, or a modified product thereof, more preferably 10 to 40 mol%: 85 to 5 mol%, more preferably 5 to 80 mol%: 90 to 2 mol%: 90 to 1 mol%. Examples thereof include a copolymer containing 60 to 2 mol% or a modified product thereof. This copolymer is preferably a copolymer in which no melting peak is observed.

  These copolymers can be produced using, for example, a known single site catalyst (metallocene, etc., for example, see Japanese Patent Application Laid-Open Nos. 58-19309 and 60-35005). For example, see European Patent Publication No. 12111287).

  Further, the above-described propylene-1-butene copolymer or a modified product thereof and the ethylene-propylene copolymer or the modified product thereof are preferably 1 to 99:99 to 1, more preferably 5 to 95 by weight ratio. : 95 to 5, more preferably 10 to 90: 90 to 10 may be blended.

Examples of the modified product of the α-olefin polymer include modified products of α, β-unsaturated carboxylic acids. The amount of modification in this case is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 4 parts by weight with respect to 100 parts by weight of the α-olefin polymer. It is.
Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate). , Citraconic acid methyl, etc.), α, β-unsaturated carboxylic acid anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). Further, these α, β-unsaturated carboxylic acids may be used in combination. Of these, α, β-unsaturated carboxylic acid anhydride is preferable, and maleic anhydride is more preferable.

  Such a modified product is a method in which an α-olefin polymer is melted and then modified by adding α, β-unsaturated carboxylic acids or the like, and the α-olefin polymer is dissolved in a solvent such as toluene or xylene. A known method such as a method in which an α, β-unsaturated carboxylic acid or the like is added and modified after dissolution is exemplified. In addition, when the modified product contains a structural unit derived from an α, β-unsaturated carboxylic acid anhydride, the acid anhydride group may be retained or the ring-opened one may be retained. Both the formed and ring-opened ones may be contained.

  Among these, the α-olefin polymer is preferably a copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms, a modified product thereof, or a mixture thereof.

Examples of the copolymerizable monomer include unsaturated carboxylic acid or its anhydride, metal salt of α, β-unsaturated carboxylic acid, α, β-unsaturated carboxylic acid ester, vinyl ester, vinyl ester saponified product, cyclic olefin, Examples include vinyl aromatic compounds, polyene compounds (such as dienes), (meth) acrylonitrile, halogenated vinyls, and halogenated vinylidenes. You may use these individually or in combination of 2 or more types.
In this specification, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid, and acrylate and methacrylate are collectively referred to as (meth) acrylate.

Examples of unsaturated carboxylic acids or anhydrides include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and unsaturated dicarboxylic acid half esters and half amides. Is mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.
Examples of the metal salt of α, β-unsaturated carboxylic acid include sodium salt and magnesium salt of (meth) acrylic acid.
As α, β-unsaturated carboxylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, Examples include esterified products of methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.

Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, and the like. Of these, vinyl acetate is preferred.
Examples of the vinyl ester saponified product include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.

  Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphth 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene Xene, 4-methylsic Examples include lohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, and vinylcyclohexane.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, Examples include vinyl naphthalene.

  Examples of polyene compounds include linear or branched aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, aliphatic non-conjugated polyene compounds, alicyclic non-conjugated polyene compounds, and aromatic non-conjugated polyene compounds. Can be mentioned. These may have a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.

  Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3- Hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-hexadiene, 2,3- Examples include dimethyl-1,3-octadiene and 2,3-dimethyl-1,3-decadiene.

  Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3- Dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene 2-chloro-1,3-cyclopentadiene, 2-chloro-1,3-cyclohexadiene, and the like.

  Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9 -Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4 -Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4 -Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4- Octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5- Octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6- Octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1 4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1, 5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1, 7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1, 5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1, 6-decadiene, 7-methyl -1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl -1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl -1,8-undecadiene, 6,10-dimethyl-1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 8,14,16-trimethyl-1,7 , 14-Hexadeca Lien, 4-ethylidene-12-methyl-1,11-penta decadiene, and the like.

  Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-isopropenyl-2-norbornene. Cyclohexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1 , 5-Divinylcyclooct 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl Examples include -4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and methyltetrahydroindene.

  Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.

  Examples of the modified product of the copolymer with the copolymerizable monomer include a modified product of α, β-unsaturated carboxylic acids as described above. The amount of modification in this case is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the copolymer with the copolymerizable monomer. 4 parts by weight.

  The polymer having one or more kinds of structural units derived from an α-olefin having 2 to 20 carbon atoms is preferably a structural unit derived from an α-olefin having 2 to 20 carbon atoms and the α-olefin having 2 to 20 carbon atoms. It is derived from one or more monomers selected from the group consisting of α-olefins having 2 to 20 carbon atoms, α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acid anhydrides, and vinyl acetate different from the above. A copolymer having a structural unit, more preferably a structural unit derived from ethylene, an α-olefin having 3 to 20 carbon atoms, an α, β-unsaturated carboxylic acid ester, an α, β-unsaturated carboxylic acid anhydride. And a copolymer having a structural unit derived from one or more monomers selected from the group consisting of vinyl acetate, and more preferably a structural unit derived from ethylene and an α, β-unsaturated carboxylic acid ester. Le and alpha, is a copolymer having a structural unit derived from one or more monomers selected from the group consisting of β- unsaturated carboxylic acid.

As a copolymer of a monomer copolymerizable with α-olefin, specifically,
(i) ethylene-vinyl acetate copolymer, saponified product or partially saponified product thereof, or maleic anhydride-modified product of ethylene-vinyl acetate copolymer,
(ii) an ethylene- (meth) acrylic acid copolymer,
(iii) ethylene- (meth) acrylate copolymers such as ethylene-glycidyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer,
(iv) an ethylene-alicyclic α-olefin copolymer such as ethylene-vinylcyclohexane,
(v) ethylene-vinyl acetate copolymer (glycidyl (meth) acrylate), ethylene-vinyl acetate copolymer (ethylene) -vinyl acetate- (meth) acrylate copolymer such as methyl (meth) acrylate,
(vi) ethylene- (meth) acrylate-maleic anhydride copolymers such as ethylene-ethyl (meth) acrylate-maleic anhydride copolymers,
(vii) ethylene- (meth) acrylate- (meth) acrylate copolymers such as ethylene-glycidyl (meth) acrylate-methyl (meth) acrylate copolymer,
(viii) copolymers of these metal salts, and
(ix) A blend of two or more of these copolymers may be mentioned.

A polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, particularly a copolymer of the above (i) to (vii) has a melt flow rate of 0.01 to 500 g at 190 ° C. under a load of 2160 g. / 10 minutes are preferable, and more preferably 0.01 to 400 g / 10 minutes.
A polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, particularly a copolymer of the above (i) to (vii), preferably has a melting point of 60 to 200 ° C. ° C is more preferable, and 60 to 110 ° C is more preferable. When a polymer having a melting point in this range is used, the permeability or adhesion of the aqueous adhesive to the adherend can be further improved.

  Specifically, preferably, (i) ethylene-vinyl acetate copolymer, saponified product or partially saponified product thereof, or maleic anhydride-modified product of ethylene-vinyl acetate copolymer, (ii) ethylene- (meth) acrylic Acid copolymer, (iii) ethylene- (meth) acrylate copolymer, (v) ethylene-vinyl acetate- (meth) acrylate copolymer, (vi) ethylene- (meth) acrylate-maleic anhydride copolymer (Vii) an ethylene- (meth) acrylate- (meth) acrylate copolymer, more preferably (ia) an ethylene-vinyl acetate copolymer, (ii) an ethylene- (meth) acrylic acid copolymer, (iii) an ethylene- (meth) acrylate copolymer, (v) an ethylene-vinyl acetate- (meth) acrylate copolymer, and (vi) an ethylene- (meth) acrylate-maleic anhydride copolymer. . Among these, a copolymer containing a structural unit derived from an α-olefin having 2 to 20 carbon atoms (more preferably, ethylene) is particularly preferable.

  In the aqueous adhesive, the content of the polymer can be appropriately adjusted depending on, for example, the type of polymer to be used, the purpose of use, the performance to be obtained, and the like. For example, from the viewpoint of maintaining the stability of the aqueous adhesive, maintaining the viscosity moderately and / or developing good coating film forming ability and adhesiveness, preferably 1 to 60 weights with respect to the total amount of the aqueous adhesive %, More preferably 3 to 60% by weight and 3 to 50% by weight, still more preferably 5 to 55% by weight.

<Other resins>
The water-based adhesive may contain other resins other than the polymer having the structural unit derived from the α-olefin having 2 to 20 carbon atoms.
Examples of other resins include polyolefin resins, acrylic resins (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), Examples thereof include various polymers and copolymers such as acrylonitrile butadiene styrene resin (ABS resin) and AS resin, and modified products thereof. These may be used alone or in combination of two or more.
Moreover, you may use resin which exhibits the function as an adhesive resin or a tackifier.
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 Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins, and indene resin polyurethane 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 phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, terpene hydrogenated resins, etc. Petroleum resins obtained by polymerizing petroleum resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof; petroleum resins such as maleic acid-modified products and fumaric acid-modified products; polyisocyanate compounds and polyol compounds described later Polyureta obtained by further reacting with other compounds as necessary Resin.

  Of these, terpene resins and polyurethane resins are preferable. Terpene resins are YS Resin PX / PXN, YS Polyster, Mighty Ace, YS Resin TO / TR, Clearon P / M / K (manufactured by Yashara Chemical Co., Ltd.), Tamanol 803L / 901 (manufactured by Arakawa Chemical Co., Ltd.), Teltac 80 (Japan) Any of those commercially available as Terpen Chemical Co., Ltd.) can be used.

The polyurethane resin is preferably in the form of an aqueous emulsion in which polyurethane is dispersed in water. That is, the polyurethane may be either water-soluble or water-insoluble, but is preferably water-insoluble.
Usually, the polyurethane resin can be obtained by reacting a polyisocyanate compound and a polyol compound, and if necessary, other compounds. Examples of the reaction include methods such as an acetone method, a prepolymer mixing method, a ketimine method, and a hot melt dispersion method.

  Examples of the polyisocyanate compound include organic polyisocyanate compounds having two or more isocyanate groups in the molecule, which are used in the production of ordinary polyurethanes. 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-bis (isocyanate) methylcyclohexane, tetramethylxylylene diisocyanate, trans Aliphatic diisocyanates such as cyclohexane-1,4-diisocyanate and lysine diisocyanate; 2,4-toluylene diisocyanate (TDI), 2,6-toe Irene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), 1,5′-naphthene diisocyanate, tolidine diisocyanate, diphenylmethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, 1, Aromatic diisocyanates such as 3-phenylene diisocyanate; lysine ester triisocyanate, triphenylmethane triisocyanate, 1,6,11-undecane triisocyanate, 1,8-isocyanate-4,4-isocyanate methyloctane, 1,3, 6-hexamethylene triisocyanate, bicycloheptane triisocyanate, adduct of trimethylolpropane and toluylene diisocyanate And triisocyanates 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 resin preferably has a hydrophilic group in the molecule in order to improve dispersion stability in water. A polyurethane containing a hydrophilic group in the 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 carboxyl 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 carboxyl group, a hydroxyl group, a primary amino group (—NH ₂ ), a secondary amino group ( ═NH) and the like (hereinafter also referred to as “hydrophilic group-containing compound”) 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 the polyurethane resin is produced as an aqueous emulsion, it is a compound different from the hydrophilic group-containing compound for the purpose of chain extension, molecular weight adjustment, etc., if necessary, and contains active hydrogen capable of reacting with an isocyanate compound in the molecule. A compound to be used may be used in combination. 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, and as a commercially available water-soluble polyurethane resin, a commercially available polyurethane aqueous emulsion and a commercially available water-soluble urethane resin may be used as they are.
For example, a polyurethane dispersion (or polyurethane aqueous solution) in which a polyurethane resin is dispersed or dissolved in water can be mentioned. As for content of the polyurethane resin in a polyurethane dispersion liquid, about 10 to 70 weight% is mentioned, About 20 to 60 weight% is preferable, About 30 to 60 weight% is more preferable, About 30 to 55 weight% is further more preferable.
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. The amount of the organic solvent is not particularly limited, but can be 0.1 to 100 parts by weight with respect to 100 parts by weight of the nonvolatile content in the polyurethane dispersion.

  As a water-soluble urethane resin, for example, manufactured by Sumitomo Bayer Urethane Co., Ltd .; DISPARALL U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA-8756 KA-8766, manufactured by DIC Corporation; Hydran HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP-60LM, AP-80, Sanyo Chemical Manufactured by Kogyo Co., Ltd .; Uprene UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310, Yukot UWS-145, Daiichi Kogyo Seiyaku Co., Ltd .; Super Flex 107M, 110, 126, 130, 150, 160, 300, 361, 370, 410, 420, 4 0, 700, 750, 820, manufactured by ADEKA; Adekabon titer HUX-401, HUX-420A, HUX-380, HUX-561, HUX-210, HUX-822, HUX-895, HUX-830, etc. .

When the water-based adhesive contains other resins, the content thereof is preferably 1 to 99% by weight, more preferably 3 to 99% by weight, and still more preferably based on the total amount of the water-based adhesive. 5 to 90% by weight.
The polymer: other resin (non-volatile content weight ratio) is preferably 5:95 to 95: 5, more preferably 5:95 to 90:10, and still more preferably 10:50 to 80: 20.
These resins may be emulsions or emulsified together with a polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms.

<Surfactant>
The aqueous adhesive preferably further contains a surfactant that generally acts as an emulsifier. Examples of such surfactants include cationic, anionic, amphoteric and nonionic surfactants. Among them, anionic or nonionic surfactants are preferable. In particular, those having the structure of the following formula (I) are preferred. Surfactants may be used alone or in combination of two or more, but it is preferable to use two or more in combination. Among these, it is more preferable to use two or more kinds of surfactants having the structure of the formula (I).

（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（Ｉ）におけるＸは、水素原子、−ＳＯ_３Ｍ（Ｍは水素原子、−ＮＨ_４又はアルカリ金属）、つまり、硫酸、硫酸塩（例えば、アンモニウム塩、ナトリウム等のアルカリ金属塩等）等が挙げられるが、なかでも、好ましくは、水素原子、−ＳＯ_３Ｈ又は−ＳＯ_３ＮＨ_４である。
２種類以上の界面活性剤の組み合わせとしては、Ｘが同じでｎ及び／又はｍが異なるものを組み合わせてもよいが、ｎ及び／又ｍが同じ又は異なって、Ｘが異なるものを組み合わせることが好ましい。具体的には、Ｘが水素原子と−ＳＯ_３Ｈとの組み合わせ、水素原子と−ＳＯ_３ＮＨ_４との組み合わせ、−ＳＯ_３Ｈと−ＳＯ_３ＮＨ_４との組み合わせが挙げられる。なかでも、水素原子と−ＳＯ_３ＮＨ_４との組み合わせが好ましい。
式（Ｉ）で表される界面活性剤としては、ラテムルＡＤ−２５（花王株式会社製）、下記式（Ａ）で表されるラテムルＥ−１０００Ａ（花王株式会社製）、下記式（Ｂ）で表されるノイゲンＥＡ−１７７（第一工業製薬株式会社製）等が挙げられる。

(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 the formula (I) is a hydrogen atom, —SO ₃ M (M is a hydrogen atom, —NH ₄ or an alkali metal), that is, sulfuric acid, sulfate (for example, an alkali metal salt such as ammonium salt or sodium), and the like. Among them, a hydrogen atom, —SO ₃ H or —SO ₃ NH ₄ is preferable.
As a combination of two or more kinds of surfactants, those having the same X and different n and / or m may be combined, but those having the same or different n and / or m and different X may be combined. preferable. Specifically, X is 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 preferable.
As the surfactant represented by the formula (I), Latemul AD-25 (manufactured by Kao Corporation), Latemuru E-1000A (manufactured by Kao Corporation) represented by the following formula (A), the following formula (B) And Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) represented by

The aqueous adhesive may contain a surfactant other than the surfactant represented by the formula (I).
For example, the anionic surfactants include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyls. Examples include sulfosuccinate.
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 , Allyl trialkyl ammonium salt, diallyl dialkyl ammonium salt and the like.
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.

The content of the surfactant is usually 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 0 to 100 parts by weight of the resin constituting the aqueous adhesive. .1 to 10 parts by weight.
When the aqueous adhesive used in the present invention contains a surfactant other than the surfactant represented by the formula (I), the surfactant represented by the formula (I) and the formula (I) The total content with surfactants other than the surfactant represented is usually 0.1 to 50 parts by weight, preferably 0.1 to 100 parts by weight of the resin constituting the aqueous adhesive. 20 parts by weight, more preferably 0.1 to 10 parts by weight.
When the surfactant represented by the formula (A) and the surfactant represented by the formula (B) are used in combination, the weight ratio is preferably 1 to 99:99 to 1, more preferably 5 to 5. 95: 95-5, More preferably, it is 10-90: 90-10, 30: 70-90: 10, 40: 60-90: 10, 50: 50-90: 10 are mentioned especially.

<Basic compound>
The aqueous adhesive preferably further contains a basic compound.
As a basic compound, what can neutralize a carboxyl 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 less can be easily dispersed by ordinary drying, and when forming a coating film using an aqueous adhesive, the water resistance and alkali resistance of the coating film are maintained / It can be improved and is preferable.
Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, and N-ethylmorpholine. Of these, N, N-dimethylethanolamine and the like are preferable.
Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.

  When the aqueous adhesive contains a basic compound, the content thereof is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight with respect to 100 parts by weight of the resin constituting the aqueous adhesive. Part, more preferably 2 to 10 parts by weight.

<solvent>
The water-based adhesive used in the present invention preferably does not contain a solvent, but in some cases, in addition to water, for example, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; acetic acid Esters such as ethyl and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol and n-butanol, ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol Cellulose solvents such as glycol solvents, methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary butyl ether), butyl carbitol, diethylene glycol monomethyl ether, triethylene glycol Glycol solvents such as methyl monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Organic solvents such as glycol ester solvents such as ether acetate; You may use these individually or in combination of 2 or more types.
When the aqueous adhesive used in the present invention contains a solvent, the content is usually 0.01 to 30 parts by weight, preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the resin constituting the aqueous adhesive. 10 parts by weight.

<Other ingredients>
The water-based adhesive used in the present invention usually contains water. Furthermore, phenol stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, anti-settling agents, as required, without compromising the intended properties of the water-based adhesive. Stabilizers, antioxidants, heat stabilizers, light stabilizers, etc .; thixotropic agents, thickeners, dispersants, antifoaming agents, viscosity modifiers, weathering agents, pigments, pigment dispersants, antistatic agents, Additives such as lubricants, nucleating agents, flame retardants, oil agents, dyes, curing agents, crosslinking agents; transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, titanium Potassium acid fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide , Aluminum oxide, magnesium oxide, alumina, inorganic, such as celite, may contain optional components such as organic fillers.

(water)
As water contained in the aqueous adhesive used in the present invention, tap water, ion-exchanged water or the like is generally used. In order to further improve the stability of the aqueous adhesive, a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, or hydroxyethyl cellulose may be added.
The water content is, for example, 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, further preferably 45% by weight or more, and preferably 45% by weight or more based on the total amount of the water-based adhesive. It is 85 weight% or less, More preferably, it is 80 weight% or less, More preferably, it is 70 weight% or less.

(Thickener)
Thickeners can be used to adjust the viscosity of the formulation. As a thickener, manufactured by ADEKA Corporation; Adecanol UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH -541VF, UH-550, UH-752, H-756VF, manufactured by San Nopco; 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, 4050 and the like.

(Dispersant)
The dispersant can be used for improving the wettability of the coated substrate. As a dispersing agent, ADEKA Co., Ltd. make; Adeka call W-193, W-287, W-288, W-304, BYK make; BYK-333, BYK-345, BYK-346, BYK-347, BYK -348, BYK-349, BYK-378, manufactured by San Nopco; Nopco wet 50, SN wet 366, Nopco 38-C, SN disperse sand 5468, 5034, 5027, 5040, 5020 and the like.

(Curing agent)
Examples of the curing agent include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), and oligomers or polymers thereof, which are isocyanate curing agents. Specifically, Sumika Bayer Urethane Sumidur 44V20, Sumidur N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and the like can be mentioned. .
0.1-20 weight part is preferable with respect to 100 weight part of resin which comprises a water-based adhesive, and, as for a hardening | curing agent, 0.1-10 weight part is more preferable. The curing agent may be added after being dissolved in an organic solvent.

<Method for producing water-based adhesive>
As a method for producing an aqueous adhesive, a method known in the art, for example, a post-emulsification method (for example, forced emulsification method, self-emulsification method, phase inversion emulsification method) after polymerizing the resin and dispersing the resin in an aqueous medium. Etc.).
Specifically, (1) A resin and a solvent to be emulsified are charged into a reactor, stirred and heated to dissolve, and a surfactant, water and / or solvent are added to the reactor, and heated and stirred. Further, a method of adding water and / or a solvent arbitrarily and stirring, (2) A resin to be emulsified, and optionally a solvent are added to a kneader, stirring, heating and melting, and a surfactant, water and / or Examples thereof include a method of adding a solvent, heating and stirring, and optionally adding water and / or a solvent before and after this and stirring. However, in any of the methods (1) and (2), water is added at least once.

In the production method of (1) described above, as the reactor, a container (preferably sealed and / or sealed) provided with a heating device capable of being heated and a stirrer capable of applying a shearing force or the like to the contents. Pressure vessel) is used.
A normal stirrer can be used. Examples of such a pressure vessel include a pressure-resistant autoclave with a stirrer. Stirring may be performed, for example, at normal pressure or reduced pressure. Moreover, the rotation speed of a stirrer can be performed with the rotation speed of about 50-1000 rpm, for example. If necessary, it is preferable to increase the rotational speed as the dispersion / stirring of the aqueous adhesive 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 dispersion (preferably reduced pressure or pressurized distillation). As the distillation method here, a method known in the art can be used. The degree of pressure reduction or pressurization is about ± 0.001 to 1 MPa, preferably about ± 0.001 to 0.5 MPa.

  In the production method (2) described above, examples of the kneader 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 may be used.

  As a method for emulsification using an extruder, a resin to be emulsified and 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, and further compressed by the extruder. Water is supplied from at least one supply port provided in a zone, a metering zone, a deaeration zone, and the like, and after being kneaded with a screw, it is continuously extruded from a die.

In addition, it is preferable to add suitably other components mentioned above, such as components other than the above, other resin, an antifoamer, a viscosity modifier, in the manufacture process of an aqueous adhesive.
Further, in the production process of the water-based adhesive, the surfactant is preferably used within a desired range. However, when the surfactant is used in excess, it is optionally excessive from the obtained water-based adhesive. The surfactant may be separated and removed. Separation and removal of the surfactant may be performed, for example, by using a centrifuge, a filtration filter having an average pore size smaller than the average particle size of the aqueous adhesive (preferably an average pore size of 0.05 to 0.5 μm). And a method using an ultrafiltration membrane).
Furthermore, it is preferable to cool the obtained water-based adhesive. Thereby, the water-based adhesive containing the fine particle of a resin composition is obtained. The cooling is not particularly required to be performed at a low temperature, and a method of leaving it at room temperature can be mentioned. Thereby, a fine and homogeneous aqueous adhesive can be obtained without aggregation of resin or the like during the cooling process.

The particle size of the dispersoid contained in the aqueous adhesive 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, based on the number. The standing stability is good.
Here, the number-based particle diameter is a particle diameter corresponding to 50% of the cumulative particle diameter distribution value based on the number, and the volume-based median diameter is 50% of the cumulative particle diameter distribution value based on the volume. Corresponding particle size. Unless otherwise specified, it means a median diameter value measured on a number basis.
Moreover, you may filter using the filter etc. which have various hole diameters as needed, for example.
When a plurality of types of dispersoids are contained in the aqueous adhesive (for example, a polymer having a structural unit derived from an α-olefin and a polyurethane resin), it is preferable that the particle sizes of the dispersoids are approximately the same. As the same degree, for example, it is preferably within ± 50% of the particle size of the polymer having a structural unit derived from α-olefin, more preferably within ± 30%.

（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。）
本発明の積層構造の製造方法では、水性接着剤が、下記（Ａ）、（Ｂ）及び（Ｃ）を含むことが好ましい。
（Ａ）２種類以上の下記式（Ｉ）で表される界面活性剤
（Ｂ）熱可塑性樹脂
（Ｃ）水
本発明の積層構造の製造方法では、前記界面活性剤が、Ｘが水素原子である界面活性剤と、Ｘが−ＳＯ_３Ｍである界面活性剤との２種類以上を含むか、Ｘが水素原子である界面活性剤と、Ｘが−ＳＯ_３ＮＨ_４である界面活性剤との２種類以上を含むことが好ましい。
本発明の積層構造の製造方法では、前記熱可塑性樹脂が、
（１）炭素数２〜２０のα−オレフィン由来の構造単位を１種類以上有する重合体、
（２）炭素数２〜２０のα−オレフィン由来の構造単位と、炭素数２〜２０のα−オレフィンと異なる炭素数２〜２０のα−オレフィン、α、β−不飽和カルボン酸エステル、α、β−不飽和カルボン酸無水物、酢酸ビニルよりなる群から選ばれる１種以上のモノマーを由来とする構造単位とを有する共重合体、
（３）エチレン由来の構造単位と、炭素数３〜２０のα−オレフィン、α、β−不飽和カルボン酸エステル及びα、β−不飽和カルボン酸無水物、酢酸ビニルよりなる群から選ばれる１種以上のモノマーを由来とする構造単位とを有する共重合体、
（４）エチレン由来の構造単位と、α、β−不飽和カルボン酸エステル及びα、β−不飽和カルボン酸よりなる群から選ばれる１種以上のモノマーを由来とする構造単位とを有する共重合体、
（５）エチレン−プロピレン共重合体、プロピレン−１−ブテン共重合体、エチレン−１−ブテン共重合体、エチレン−１−オクテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−プロピレン−１−ブテン共重合体等のα−オレフィン系共重合体又はその変性物；あるいはこれらの２種以上の混合物、
（６）エチレン−プロピレン共重合体、プロピレン−１−ブテン共重合体、エチレン−１−ブテン共重合体、エチレン−１−オクテン共重合体、エチレン−１−ヘキセン共重合体、エチレン−プロピレン−１−ブテン共重合体等のα−オレフィン系共重合体又はその無水マレイン酸変性物；あるいはこれらの２種以上の混合物、
（７）α−オレフィンと酢酸ビニルとの共重合体又はその変性物；あるいはこれらの２種以上の混合物、
（８）α−オレフィンと（メタ）アクリレートとα，β−カルボン酸との共重合体又はその変性物；あるいはこれらの２種以上の混合物、及び
（９）α−オレフィンと（メタ）アクリレートと無水マレイン酸との共重合体又はその変性物；あるいはこれらの２種以上の混合物
からなる群から選択される少なくとも１種であることが好ましい。
本発明の積層構造の製造方法では、熱可塑性樹脂が、６０〜１１０℃の融点を有することが好ましい。
本発明の積層構造の製造方法では、水性接着剤が、さらに、ポリウレタン樹脂又は非水溶性のポリウレタン樹脂を含有することが好ましい。
本発明の積層構造の製造方法では、水性接着剤が、さらに、テルペン重合体、テルペンフェノール、β−ピネン重合体、芳香族変性テルペン重合体、α−ピネン重合体、テルペン系水素添加樹脂からなる群から選択されるテルペン系樹脂を含有することが好ましい。
本発明の積層構造の製造方法では、水性接着剤が、さらに、ポリウレタン樹脂と、テルペン重合体、テルペンフェノール、β−ピネン重合体、芳香族変性テルペン重合体、α−ピネン重合体、テルペン系水素添加樹脂からなる群から選択されるテルペン系樹脂とを含有することが好ましい。
本発明の積層構造の製造方法では、水性接着剤が、さらに、ポリウレタン樹脂とテルペンフェノール又は非水溶性のポリウレタン樹脂とテルペンフェノールとを含有することが好ましい。
本発明の積層構造の製造方法では、水性接着剤が、さらに、イソシアネートを含有することが好ましい。
本発明の積層構造の製造方法では、水性接着剤が、さらに、ジフェニルメタンジイソシアネート（ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、キシレンジイソシアネート（ＸＤＩ）及びこれらのオリゴマー又はポリマーからなる群から選択されるイソシアネートを含有することが好ましい。
本発明の積層構造の製造方法では、水性接着剤が、さらに、塩基性化合物を含有することが好ましい。
本発明の積層構造の製造方法では、前記界面活性剤が、水性エマルションを構成する全樹脂１００重量部に対して、０．１〜５０重量部、０．１〜２０重量部又は０．１〜１０重量部含むことが好ましい。
本発明の積層構造の製造方法では、前記界面活性剤は、式（Ａ）で表される界面活性剤と式（Ｂ）で表される界面活性剤とを、重量比で、１〜９９：９９〜１、５〜９５：９５〜５、１０〜９０：９０〜１０、３０：７０〜９０：１０、４０：６０〜９０：１０又は５０：５０〜９０：１０で含むことが好ましい。 本発明の積層構造の製造方法では、熱可塑性樹脂の重合の後、該樹脂が水性媒体中に分散させられた後乳化法、強制乳化法、自己乳化法又は転相乳化法によって得られた水性接着剤を用いることが好ましい。 In the manufacturing method of the laminated structure of this invention, it is preferable to perform bonding of a 1st base material and a 2nd base material, applying a heat | fever, a pressure, or both.
In the method for producing a laminated structure of the present invention, the water-based adhesive is a thermoplastic resin (B) containing a polymer having at least one structural unit derived from an α-olefin having 2 to 20 carbon atoms, and a formula (I) It is preferable that surfactant (A) represented is included.

(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.)
In the manufacturing method of the laminated structure of this invention, it is preferable that a water-based adhesive contains the following (A), (B) and (C).
(A) Two or more kinds of surfactants represented by the following formula (I) (B) Thermoplastic resin (C) Water In the method for producing a laminated structure of the present invention, the surfactant is a hydrogen atom. A surfactant containing two or more of a surfactant and X is —SO ₃ M, or a surfactant where X is a hydrogen atom, and a surfactant where X is —SO ₃ NH ₄ It is preferable that two or more of these are included.
In the method for producing a laminated structure of the present invention, the thermoplastic resin is
(1) a polymer having at least one structural unit derived from an α-olefin having 2 to 20 carbon atoms,
(2) a structural unit derived from an α-olefin having 2 to 20 carbon atoms, an α-olefin having 2 to 20 carbon atoms different from the α-olefin having 2 to 20 carbon atoms, α, β-unsaturated carboxylic acid ester, α , A copolymer having a structural unit derived from one or more monomers selected from the group consisting of β-unsaturated carboxylic acid anhydride and vinyl acetate,
(3) 1 selected from the group consisting of a structural unit derived from ethylene, an α-olefin having 3 to 20 carbon atoms, an α, β-unsaturated carboxylic acid ester, an α, β-unsaturated carboxylic acid anhydride, and vinyl acetate. A copolymer having a structural unit derived from a monomer of at least one species,
(4) Copolymer having a structural unit derived from ethylene and a structural unit derived from one or more monomers selected from the group consisting of α, β-unsaturated carboxylic acid esters and α, β-unsaturated carboxylic acids. Coalescence,
(5) Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene- An α-olefin copolymer such as 1-butene copolymer or a modified product thereof; or a mixture of two or more of these,
(6) Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene- An α-olefin copolymer such as 1-butene copolymer or a maleic anhydride modified product thereof; or a mixture of two or more thereof;
(7) Copolymer of α-olefin and vinyl acetate or a modified product thereof; or a mixture of two or more of these,
(8) Copolymer of α-olefin, (meth) acrylate and α, β-carboxylic acid or a modified product thereof; or a mixture of two or more of these; and (9) α-olefin and (meth) acrylate It is preferably at least one selected from the group consisting of a copolymer with maleic anhydride or a modified product thereof; or a mixture of two or more thereof.
In the manufacturing method of the laminated structure of this invention, it is preferable that a thermoplastic resin has melting | fusing point of 60-110 degreeC.
In the manufacturing method of the laminated structure of this invention, it is preferable that a water-based adhesive contains a polyurethane resin or a water-insoluble polyurethane resin further.
In the method for producing a laminated structure of the present invention, the aqueous adhesive further comprises a terpene polymer, a terpene phenol, a β-pinene polymer, an aromatic modified terpene polymer, an α-pinene polymer, and a terpene-based hydrogenated resin. It is preferable to contain a terpene resin selected from the group.
In the method for producing a laminated structure of the present invention, the water-based adhesive further comprises a polyurethane resin, a terpene polymer, a terpene phenol, a β-pinene polymer, an aromatic modified terpene polymer, an α-pinene polymer, and a terpene hydrogen. It is preferable to contain a terpene resin selected from the group consisting of additive resins.
In the method for producing a laminated structure of the present invention, it is preferable that the aqueous adhesive further contains a polyurethane resin and terpene phenol or a water-insoluble polyurethane resin and terpene phenol.
In the manufacturing method of the laminated structure of this invention, it is preferable that an aqueous adhesive contains an isocyanate further.
In the method for producing a laminated structure of the present invention, the aqueous adhesive further comprises diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), and oligomers or polymers thereof. It preferably contains an isocyanate selected from the group.
In the manufacturing method of the laminated structure of this invention, it is preferable that a water-based adhesive contains a basic compound further.
In the method for producing a laminated structure of the present invention, the surfactant is 0.1 to 50 parts by weight, 0.1 to 20 parts by weight, or 0.1 to 0.1 parts by weight with respect to 100 parts by weight of the total resin constituting the aqueous emulsion. It is preferable to contain 10 parts by weight.
In the method for producing a laminated structure of the present invention, the surfactant is a surfactant represented by the formula (A) and a surfactant represented by the formula (B) in a weight ratio of 1 to 99: 99 to 1, 5 to 95:95 to 5, 10 to 90:90 to 10, 30:70 to 90:10, 40:60 to 90:10, or 50:50 to 90:10 is preferable. In the method for producing a laminated structure of the present invention, after polymerization of a thermoplastic resin, the resin is dispersed in an aqueous medium, and then an aqueous solution obtained by an emulsification method, a forced emulsification method, a self-emulsification method or a phase inversion emulsification method. It is preferable to use an adhesive.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Parts and% in the examples mean weight basis unless otherwise specified.

In the following examples, physical properties were measured by the following method.
(1) Content of structural unit of polymer Based on measurement results of ¹ H-NMR spectrum and ¹³ C-NMR spectrum measured under the following conditions using a nuclear magnetic resonance apparatus (trade name AC-250 manufactured by Bruker). Calculated. Specifically, in the ¹³ C-NMR spectrum, from the ratio of the spectral intensity of the methyl carbon of the structural unit derived from propylene to the spectral intensity of the methyl carbon of the structural unit derived from 1-butene, The composition ratio of the structural unit derived from 1-butene was calculated, and then in the ¹ H-NMR spectrum, from the ratio of the spectral intensity of hydrogen derived from the methine unit and the methylene unit and the spectral intensity of hydrogen derived from the methyl unit, The composition ratio of the structural unit derived from ethylene, the structural unit derived from propylene, and the structural unit derived from 1-butene was calculated.
¹³ C-NMR (H decoupling)
¹³ C frequency: 150.9 MHz
Pulse width: 6.00 μs Pulse repetition time: 4.0 seconds Number of integrations: 256 Measurement temperature: 137 ° C.
Solvent: orthodichlorobenzene-d4 (concentration about 20%)

(2) Intrinsic viscosity [η]
The measurement was performed at 135 ° C. using an Ubbelohde viscometer. A polymer tetralin solution having a polymer concentration c per unit volume of tetralin of 0.6, 1.0, and 1.5 mg / ml was prepared, and the intrinsic viscosity at 135 ° C. was measured. The measurement was repeated three times at each concentration. The average value of the three values obtained was defined as the specific viscosity (ηsp) at that concentration, and the value obtained by extrapolating c of ηsp / c to zero was defined as the intrinsic viscosity [η]. Asked.

(3) Molecular weight distribution It measured by the gel permeation chromatograph (GPC) method on the following conditions.
Device: HLC-8121GPC / HT manufactured by Tosoh Corporation
Column: 4 TSKgel GMH _HR- H (S) HT manufactured by Tosoh Corporation Temperature: 145 ° C
Solvent: o-dichlorobenzene Elution solvent flow rate: 1.0 ml / min Sample concentration: 1 mg / ml
Measurement injection volume: 300 μl
Molecular weight reference material: Standard polystyrene Detector: Differential refraction

(4) Crystal melting peak and crystallization peak Using a differential scanning calorimeter (Seiko Denshi Kogyo's DSC220C: input compensation DSC), measurement was performed under the following conditions.
(I) About 5 mg of the sample was heated from room temperature to 200 ° C. at a rate of temperature increase of 30 ° C./min, and held for 5 minutes after completion of the temperature increase.
(Ii) Next, the temperature was decreased from 200 ° C. to −100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed. The peak observed in (ii) was a crystallization peak, and the presence or absence of a crystallization peak having a peak area of 1 J / g or more was confirmed.
(Iii) Subsequently, the temperature was increased from −100 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min. The peak observed in (iii) is the melting peak of the crystal, and the presence or absence of a melting peak having a peak area of 1 J / g or more was confirmed.

(5) Melt flow rate (MFR)
According to JIS-K-7210, the measurement was performed under the conditions of a load of 2.16 kgf and a temperature of 130 ° C.

(6) Modified amount The modified amount of maleic anhydride is obtained by dissolving 1.0 g of a sample in 20 ml of xylene, dropping the sample solution into 300 ml of methanol while stirring to reprecipitate the sample, and then collecting the sample. After vacuum drying (80 ° C., 8 hours), a film having a thickness of 100 μm was prepared by hot pressing, the infrared absorption spectrum of the obtained film was measured, and the amount of maleic anhydride modification was determined by absorption near 1780 cm ^−1. Was quantified.

(7) Non-volatile content It measured by the measuring method according to JISK-6828.
(8) Particle size of aqueous emulsion This is a value measured with a laser diffraction particle size measuring device LA-950V2 manufactured by HORIBA. Unless otherwise specified, the particle diameter is a median diameter value measured on a number basis.

<Production Example of Copolymer (B-1-1)>
386 parts of vinylcyclohexane (hereinafter sometimes referred to as VCH) and 3640 parts of toluene were charged into a SUS reactor substituted with argon. After raising the temperature to 50 ° C., ethylene was charged while being pressurized at 0.6 MPa. 10 parts of a toluene solution of triisobutylaluminum (TIBA) [TIBA concentration 20% manufactured by Tosoh Akzo Co., Ltd.] was charged, followed by diethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl- 2-phenoxy) titanium dichloride 0.001 part dissolved in 87 parts dehydrated toluene and dimethylanilinium tetrakis (pentafluorophenyl) borate 0.03 part dissolved in 122 parts dehydrated toluene were added and stirred for 2 hours. did. The resulting reaction solution was poured into about 10,000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 300 parts of copolymer (B-1-1) was obtained. [Η] of the copolymer is 0.48 dl / g, Mn is 15,600, molecular weight distribution (Mw / Mn) is 2.0, melting point (Tm) is 57 ° C., glass transition point (Tg) is − At 28 ° C., the content of VCH units in the copolymer was 13 mol%.

<Example of production of copolymer (B-1-2)>
To 100 parts of the obtained copolymer (B-1-1) copolymer, 0.4 part of maleic anhydride and 0.04 part of 1,3-bis (t-butylperoxyisopropyl) benzene were added. After sufficiently premixing, the mixture was supplied from a supply port of a twin screw extruder and melt kneaded to obtain a copolymer (B-1-2). The temperature of the part of the extruder where the melt kneading was performed was divided into two stages, the first half and the latter half, and the melt kneading was performed at a temperature setting of 180 ° C. in the first half and 260 ° C. in the second half. The copolymer (B-1-2) had a maleic acid graft amount of 0.2% and an MFR of 180 g / 10 min (190 ° C., load: 2.16 kgf).

<Example of production of copolymer (B-2-2)>
A 1 L separable flask reactor was equipped with a stirrer, thermometer, dropping funnel and reflux condenser, and the gas in the reactor was replaced with nitrogen. Here, 600 parts of xylene as a solvent, 100 parts of a polymer (B-2-1) [ethylene / propylene copolymer (LICOCENE PP1602, manufactured by Clariant Japan KK, ethylene: propylene = 15 mol%: 85 mol%)], maleic anhydride 50 parts 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] 1 part of dioxaphosphepine (Sumilyzer GP, manufactured by Sumitomo Chemical Co., Ltd.) was added and heated to 140 ° C. and stirred to obtain a solution. The reaction was continued with stirring. An oil bath was used for heating. After completion of the reaction, the content was lowered to room temperature, poured into 1000 parts of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, a polymer (B-2-2) modified with maleic anhydride was obtained. The obtained polymer had Mw of 45362, Mn of 23354, molecular weight distribution (Mw / Mn) of 1.9, and maleic acid modification amount of 0.93%.
In the polymer (B-2-1), a crystal melting peak with a heat of crystal fusion of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more were observed in the temperature range of −100 to 200 ° C. It was.

<Example of production of copolymer (B-2-4)>
The polymer (B-2-2) except that the polymer (B-2-3) [ethylene / propylene copolymer (LICOCENE PP2602, manufactured by Clariant Japan KK, ethylene: propylene = 13 mol%: 87 mol%)] is used. In the same manner as in the above production example, a polymer (B-2-4) modified with maleic anhydride was obtained. Mw of the obtained polymer was 55115, Mn was 25836, molecular weight distribution (Mw / Mn) was 2.2, and maleic acid modification amount was 0.84%.
In the polymer (B-2-3), a crystal melting peak with a heat of crystal fusion of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more were observed in the temperature range of −100 to 200 ° C. It was.

<Example of production of copolymer (B-3-1)>
A 2 l separable flask reactor was equipped with a stirrer, thermometer, dropping funnel and reflux condenser to reduce the pressure, and the gas in the reactor was replaced with nitrogen. Into this flask, 1 l of dried toluene was introduced as a polymerization solvent. Here, propylene 8 NL / min and 1-butene 0.5 NL / min were continuously fed at normal pressure, and the solvent temperature was 30 ° C. After adding 1.25 mmol of triisobutylaluminum (hereinafter sometimes referred to as TIBA) to the reactor, dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-) was used as a polymerization catalyst. 0.005 mmol of 5-methyl-2-phenoxy) titanium dichloride was added to the reactor. 15 seconds later, 0.025 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added to the reactor to initiate polymerization. As a result of polymerization for 30 minutes, 155.8 g of a propylene-1-butene copolymer (B-3-1) having a propylene content of 96 mol% was obtained. The obtained polymer had an intrinsic viscosity [η] of 2.1 dl / g and a molecular weight distribution (Mw / Mn) of 2.5. In addition, neither a crystal melting peak with a heat of crystal fusion of 1 J / g or more nor a crystallization peak with a heat of crystallization of 1 J / g or more was observed in the temperature range of −100 to 200 ° C.

<Example of production of copolymer (B-3-2)>
Except for using the polymer (B-3-1), a polymer (B-3-2) modified with maleic anhydride was obtained in the same manner as in the production example of the polymer (B-2-2). . Mw of the obtained polymer was 49043, Mn was 14267, molecular weight distribution (Mw / Mn) was 3.4, and maleic acid modification amount was 1.79%.

<Production Example 1 of Aqueous Emulsion>
In a 2 l separable flask reaction vessel equipped with a stirrer, thermometer and reflux condenser, 200 parts of toluene as a solvent and 100 parts of a polymer (B-1-2) as a copolymer were stirred at 80 ° C. Dissolved. Next, as a surfactant, a mixed solution of Latemuru E-1000A (30% aqueous solution, manufactured by Kao Corporation), 5 parts of Neugen EA-177 (Daiichi Kogyo Seiyaku Co., Ltd.) and 5 parts of isopropanol is applied for 10 minutes. And dripped. After further stirring for 5 minutes, 5 parts of dimethylethanolamine was added, and the mixture was further stirred for 5 minutes.
Subsequently, the stirring apparatus was changed to TK Robotics (manufactured by PRIMIX Co., Ltd.), and a mixture of 100 parts of isopropanol and 100 parts of ion-exchanged water was added dropwise over 30 minutes while stirring the reaction mixture with a disper blade. 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.
The obtained dispersion was put into a 2 L eggplant flask, distilled under reduced pressure with an evaporator, and filtered with a 200 mesh nylon net to obtain an aqueous emulsion containing a polymer (B-1-2) and a surfactant. It was. The obtained aqueous emulsion (E-1) had a particle size (number basis) of 0.61 μm and a nonvolatile content concentration of 36%.

<Production Example 2 of aqueous emulsion>
An aqueous emulsion was produced in the same manner as <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-1) was used as the copolymer. The obtained aqueous emulsion (E-2) had a particle size (number basis) of 0.25 μm and a nonvolatile content concentration of 38%.

<Production Example 3 of aqueous emulsion>
An aqueous emulsion was produced in the same manner as <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-2) was used as the copolymer. The obtained aqueous emulsion (E-3) had a particle size (number basis) of 0.22 μm and a nonvolatile content concentration of 39%.

<Production Example 4 of Aqueous Emulsion>
An aqueous emulsion was produced in the same manner as <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-3) was used as the copolymer. The obtained water-based emulsion (E-4) had a particle size (number basis) of 0.21 μm and a nonvolatile content concentration of 36%.

<Production Example 5 of aqueous emulsion>
An aqueous emulsion was produced in the same manner as in <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-2-4) was used as the copolymer. The obtained water-based emulsion (E-5) had a particle size (number basis) of 0.13 μm and a nonvolatile content concentration of 36%.

<Production Example 6 of Aqueous Emulsion>
An aqueous emulsion was produced in the same manner as <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-3-2) was used as the copolymer. The obtained aqueous emulsion (E-6) had a particle size (number basis) of 0.33 μm and a nonvolatile content concentration of 34%.

<Production Example 7 of Aqueous Emulsion>
An aqueous emulsion was produced in the same manner as <Aqueous emulsion production example 1> except that 50 parts of the polymer (B-2-2) and 50 parts of the polymer (B-3-2) were used as the copolymer. The obtained aqueous emulsion (E-7) had a particle size (number basis) of 0.21 μm and a nonvolatile content concentration of 35%.

<Production Example 8 of Aqueous Emulsion>
An aqueous emulsion was produced in the same manner as in <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-4-1) [BONDINE HX8140 (manufactured by ARKEMA)] was used as the copolymer. The obtained aqueous emulsion (E-8) had a particle size (number basis) of 0.09 μm and a nonvolatile content concentration of 40%.

<Production Example 9 of aqueous emulsion>
An aqueous emulsion was produced in the same manner as <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-4-2) [BONDINE AX8390 (manufactured by ARKEMA)] was used as the copolymer. The obtained aqueous emulsion (E-9) had a particle size (number basis) of 0.11 μm and a nonvolatile content concentration of 42%.

<Production Example 10 of Aqueous Emulsion>
<Aqueous emulsion except that instead of 100 parts of polymer (B-1-2), 67 parts of polymer (B-4-2) and 33 parts of adhesive resin (terpene phenol, Tamanol 803L, manufactured by Arakawa Chemical Co., Ltd.) are used. An aqueous emulsion (E-10) was produced in the same manner as in Production Example 1>. The obtained aqueous emulsion had a particle size (on a number basis) of 0.10 μm and a nonvolatile content concentration of 41%.

<Production Example 11 of Aqueous Emulsion>
An aqueous emulsion (E-11) was produced in the same manner as in <Aqueous emulsion production example 1> except that 100 parts of the polymer (B-4-3) [BONDINE HX8290 (manufactured by ARKEMA)] was used as the copolymer. . The obtained aqueous emulsion had a particle size (number basis) of 0.18 μm and a nonvolatile content concentration of 39%.

<Production Example 12 of aqueous emulsion>
Instead of using 100 parts of the polymer (B-1-2), 50 parts of the polymer (B-4-3) and 50 parts of an adhesive resin (terpene phenol, Tamanol 803L, manufactured by Arakawa Chemical Co., Ltd.) are used. Emulsion Production Example 1> An aqueous emulsion (E-12) was produced in the same manner. The obtained aqueous emulsion had a particle size (number basis) of 0.20 μm and a nonvolatile content concentration of 33%.
<Production Example 13 of aqueous emulsion>
An aqueous emulsion (as in Production Example 1 of an aqueous emulsion) except that 100 parts of a polymer (B-4-4) [BONDINE LX4110 (manufactured by ARKEMA)] is used as a copolymer and the reaction temperature is 90 ° C. E-13) was produced. The obtained aqueous emulsion had a particle size (number basis) of 0.08 μm and a nonvolatile content concentration of 44%.

<Production Example 14 of Aqueous Emulsion>
Instead of 100 parts of the polymer (B-1-2), 75 parts of the polymer (B-4-4) and 25 parts of an adhesive resin (terpene phenol, Tamanol 803L, manufactured by Arakawa Chemical Co., Ltd.) were used, and the reaction temperature was 90. An aqueous emulsion (E-14) was produced in the same manner as <Aqueous Emulsion Production Example 1> except that the temperature was changed to ° C. The obtained aqueous emulsion had a particle size (on a number basis) of 0.20 μm and a nonvolatile content concentration of 34%.

<Aqueous emulsion (E-15)>
An aqueous emulsion of ethylene / methacrylic acid copolymer (AC-3100, manufactured by Chuo Rika Kogyo Co., Ltd.) (E-15). The particle size of this aqueous emulsion was 0.7 μm, and the nonvolatile content concentration was 45%.

<Aqueous emulsion (E-16)>
An aqueous emulsion of ethylene / vinyl acetate (EVA) copolymer (HA-1100, manufactured by Chuo Rika Kogyo Co., Ltd.) (E-16). The particle size of this aqueous emulsion was 0.8 μm, and the nonvolatile content concentration was 45%.

<Aqueous emulsion (E-17)>
An aqueous emulsion of EVA copolymer (EC-1800, manufactured by Chuo Rika Kogyo Co., Ltd.) (E-17). The particle size of this aqueous emulsion was 1.7 μm, and the nonvolatile content concentration was 45%.

<Aqueous emulsion (E-18)>
An aqueous emulsion of an ethylene / glycidyl methacrylate copolymer (Separjon G415, manufactured by Sumitomo Seika Co., Ltd.) (E-18). The particle size of this aqueous emulsion was 1.7 μm, and the nonvolatile content concentration was 50%.

<Production Example 19 of Aqueous Emulsion>
An aqueous emulsion (E-19) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were mixed so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Aqueous emulsion (E-20)>
An aqueous emulsion of an ethylene / vinyl acetate copolymer (Sumikaflex 400HQ, manufactured by Sumitomo Chemical Co., Ltd.) (E-20). The particle size of this aqueous emulsion was 0.7 μm, and the nonvolatile content concentration was 55%.

<Production Example 21 of Aqueous Emulsion>
An aqueous emulsion (E-21) was formulated by blending an aqueous emulsion (E-20) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) in a nonvolatile content ratio of 67 parts: 33 parts. Manufactured.

<Aqueous emulsion (E-22)>
An aqueous emulsion of an ethylene / vinyl acetate copolymer (Sumikaflex 401HQ, manufactured by Sumitomo Chemical Co., Ltd.) (E-22). The particle size of this aqueous emulsion was 0.8 μm, and the nonvolatile content concentration was 55%.

<Production Example 23 of Aqueous Emulsion>
An aqueous emulsion (E-23) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were mixed so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Aqueous emulsion (E-24)>
An aqueous emulsion of an ethylene / vinyl acetate copolymer (Sumikaflex 408HQE, manufactured by Sumitomo Chemical Co., Ltd.) (E-24). The particle size of this aqueous emulsion was 0.9 μm, and the nonvolatile content concentration was 50%.

<Production Example 25 of Aqueous Emulsion>
An aqueous emulsion (E-25) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were mixed so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Aqueous emulsion (E-26)>
An aqueous emulsion of an ethylene / vinyl acetate copolymer (Sumikaflex 500, manufactured by Sumitomo Chemical Co., Ltd.) (E-26). The particle size of this aqueous emulsion was 0.7 μm, and the nonvolatile content concentration was 55%.

<Production Example 27 of aqueous emulsion>
An aqueous emulsion (E-27) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Production Example 28 of Aqueous Emulsion>
An aqueous emulsion (E-11) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were mixed so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Production Example 29 of Aqueous Emulsion>
An aqueous emulsion (E-29) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Production Example 30 of Aqueous Emulsion>
An aqueous emulsion (E-30) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were mixed so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Aqueous emulsion (E-31)>
An aqueous emulsion of ethylene / vinyl acetate / special ester copolymer (Sumikaflex S-950HQ, manufactured by Sumitomo Chemical Co., Ltd.) (E-31). The particle size of this aqueous emulsion was 0.6 μm, and the nonvolatile content concentration was 52%.

<Production Example 32 of Aqueous Emulsion>
An aqueous emulsion (E-31) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Production Example 33 of Aqueous Emulsion>
Instead of using 100 parts of the polymer (B-1-2), 50 parts of a propylene / butylene copolymer (B-3-2) and 50 parts of an ethylene / propylene copolymer (B-2-4), An aqueous emulsion (E-33) was produced in the same manner as in <Preparation Example 1 of Aqueous Emulsion>. The obtained aqueous emulsion (E-33) had a particle size of 0.2 μm (number basis) and a nonvolatile content of 34%.

<Production Example 34 of Aqueous Emulsion>
An aqueous emulsion (E-34) and an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) were blended so that the nonvolatile content ratio was 67 parts: 33 parts. Manufactured.

<Production Example 35 of Aqueous Emulsion>
The temperature in the cell of Labo Plast Mill Micro (manufactured by Toyo Seiki) was set to 95 ° C. In this cell, 3.12 g of copolymer (B-1-2) was sealed and stirred at 300 rpm for 3 minutes. The maximum shear rate at this time was 1173 sec- ¹ . Thereafter, 0.46 g of oxyethyleneoxypropylene block copolymer (weight average molecular weight 15500: Pluronic F108: manufactured by Asahi Denka Co., Ltd.) is added as an emulsifier together with 0.21 g of water, and the temperature in the cell is kept at 95 ° C. Further, the mixture was kneaded at 300 rpm for 3 minutes (shear speed 1173 sec- ¹ ). After kneading, the content was taken out and stirred and dispersed in a container containing warm water at about 70 ° C. to obtain an aqueous emulsion (E-35) having a volume-based median diameter of dispersoid of 0.43 μm.

<Production Examples 36 to 38 of aqueous emulsion>
Using the copolymer and surfactant shown in Table 1 in the weight ratio shown in Table 1, emulsions (E-36) to (E-38) were obtained in substantially the same manner as in <Example 1 of production of aqueous emulsion>. Obtained.
The copolymers and surfactants in Table 1 are as follows.
Copolymer U1: Ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8290, manufactured by ARKEMA, melting point: 81 ° C.)
Copolymer U2: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE LX4110, manufactured by ARKEMA, melting point: 107 ° C.)
Copolymer U3: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8210, manufactured by ARKEMA, melting point: 100 ° C.)
Surfactant 1: Compound represented by the above formula (A) (Latemul E-1000A, 30% aqueous solution, manufactured by Kao Corporation)
Surfactant 2: Compound represented by the above formula (B) (Neugen EA-177, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

<Production Example 39 of Aqueous Emulsion>
An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), polyurethane emulsion (manufactured by SBU, Dispacol U-54), isocyanate (manufactured by SBU, Desmodur N3300) An aqueous emulsion (E-39) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 5 parts.

<Production Example 40 of Aqueous Emulsion>
An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), polyurethane emulsion (manufactured by SBU, Dispacol U-54), isocyanate (manufactured by SBU, Desmodur N3300) An aqueous emulsion (E-40) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 200 parts: 10 parts.

<Production Example 41 of Aqueous Emulsion>
An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), polyurethane emulsion (manufactured by SBU, Dispacol U-54), isocyanate (manufactured by SBU, Desmodur N3300) An aqueous emulsion (E-41) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 1600 parts: 41 parts.

<Production Example 42 of Aqueous Emulsion>
An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), polyurethane emulsion (manufactured by SBU, Dispacol U-54), isocyanate (manufactured by SBU, Desmodur N3300) An aqueous emulsion (E-42) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 100 parts: 15 parts.

<Production Example 43 of Aqueous Emulsion>
An aqueous emulsion (E-36), an aqueous emulsion of terpene phenol (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.), polyurethane emulsion (manufactured by SBU, Dispacol U-54), isocyanate (manufactured by SBU, Desmodur N3300) An aqueous emulsion (E-43) was obtained by blending such that the nonvolatile content ratio was 100 parts: 100 parts: 200 parts: 20 parts.

<Production Example 44 of Aqueous Emulsion>
An aqueous emulsion (E-44) is obtained by blending polyurethane emulsion (manufactured by SBU, Dispacol U-54) and isocyanate (manufactured by SBU, Desmodur N3300) such that the nonvolatile content ratio is 100 parts: 5 parts. It was.

<Production Example 45 of Aqueous Emulsion>
Aqueous emulsion (E-36), polyurethane emulsion (manufactured by SBU, Dispacol U-54) and isocyanate (manufactured by SBU, Desmodur N3300) are blended so that the nonvolatile content ratio is 100 parts: 100 parts: 5 parts. Thus, an aqueous emulsion (E-45) was obtained.

<Production Example 46 of Aqueous Emulsion>
Aqueous emulsion (E-36), polyurethane emulsion (manufactured by SBU, Dispacol U-54) and isocyanate (manufactured by SBU, Desmodur N3300) are blended so that the nonvolatile content ratio is 100 parts: 200 parts: 10 parts. Thus, an aqueous emulsion (E-46) was obtained.

<Production Examples 47 to 63 of aqueous emulsion>
Using the copolymers and surfactants shown in Tables 2 to 3 in the weight ratios shown in Tables 2 to 3, an aqueous emulsion (E-47) substantially in the same manner as <Production Example 1 of an aqueous emulsion> To (E-63).
The copolymers and surfactants in the table are as follows.
Copolymer P1: C ₂ (ethylene) / EVA (ethylene / vinyl acetate copolymer) / MAH (maleic anhydride) copolymer (OREVAC T9314, manufactured by ARKEMA)
Copolymer P2: C ₂ / EVA / MAH copolymer (OREVAC T9318, manufactured by ARKEMA)
Copolymer Q1: MAH-modified EVA (OREVAC G18211, manufactured by ARKEMA)
Copolymer R1: EVA part saponified product (Mersen H6051, manufactured by Tosoh Corporation)
Copolymer R2: EVA part saponification product (Mersen H6410M, manufactured by Tosoh Corporation)
Copolymer R3: EVA partly saponified product (Mersen H6820, manufactured by Tosoh Corporation)
Copolymer R4: EVA part saponification product (Mersen H6822X, manufactured by Tosoh Corporation)
Copolymer R5: EVA partly saponified product (Mersen H6960, manufactured by Tosoh Corporation)
Copolymer S1: EVA (EVATEATE KA-40, manufactured by Sumitomo Chemical Co., Ltd.)
Copolymer T1: heat-degraded polyethylene (UMX2000, manufactured by Sanyo Chemical Industries, Ltd.)
Copolymer U1: Ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE HX8290, manufactured by ARKEMA)
Copolymer U2: ethylene-acrylic acid-maleic anhydride terpolymer (BONDINE LX4110, manufactured by ARKEMA)
Surfactant 1: Compound represented by the above formula (A) (Latemul E-1000A, 30% aqueous solution, manufactured by Kao Corporation)
Surfactant 2: Compound represented by the above formula (B) (Neugen EA-177, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Adhesive resin 1: terpene phenol (Tamanol 803L, manufactured by Arakawa Chemical Co., Ltd.)

The following tests were conducted on the aqueous emulsions obtained in the above production examples of aqueous emulsions.
<Standing stability for 5 days>
The obtained aqueous emulsion was put into a 250 mL plastic container and allowed to stand at room temperature for 5 days, and then the appearance change was observed. The evaluation criteria were as follows. The results are shown in Tables 4-1 and 4-2.
○: Aggregation, precipitation, and phase separation were not observed, and the condition was good.
X: Aggregation, precipitation, and phase separation occurred.

Test Examples 15-63
In addition, all of the aqueous emulsions (E-15) to (E-35) are homogeneously dispersed by visual observation, and no aggregation, precipitation, phase separation or the like occurs even during long-term storage. Showed good stability.
Furthermore, when the aqueous emulsions (E-36) to (E-63) were evaluated for stability for 5 days in the same manner as described above, no aggregation, precipitation, or phase separation was observed. State.

<Example A: Evaluation 1 of adhesion of water-based adhesive to M-EVA>
Table 5 shows Adecanol UH-420 (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant in each aqueous emulsion (non-volatile ratio) obtained in the production example of an aqueous emulsion. The stated amount (non-volatile content ratio, unit: parts by weight) was added, and the mixture was prepared with water so that the non-volatile content of the formulation was 40%, and stirred with a three-one motor to obtain an aqueous adhesive.
The obtained water-based adhesive was applied to 100% cotton canvas using a glass rod (coating amount: weight after drying of about 60 g / m ² ), and then air-dried for 20 minutes. It put into the range (The product made by panasonic, NE-EH212, frequency 2.455GHz), and electromagnetic waves treatment was performed for 30 second at 750W.
In addition, each water-based adhesive was bonded to a bar coater No. 75 (coil diameter: 75 × 25 μm) was applied to M-EVA (ethylene / vinyl acetate copolymer foam) (coating amount: weight after drying about 70 g / m ² ), and obtained. M-EVA was put into a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds.
Again, each water-based adhesive was applied to each of cotton canvas and M-EVA (cotton canvas coating amount: weight after drying about 40 g / m ² , M-EVA coating amount: weight after drying about 80 g / m ² ), The obtained cotton canvas and M-EVA were put into a microwave oven and subjected to electromagnetic wave treatment at 750 W for 30 seconds.
Subsequently, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds. Immediately removed from the microwave and crimped by hand.

<Peel strength test of laminated structure>
Each laminated structure obtained above was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), at a peeling rate of 200 mm / min and a peeling angle of 180 degrees, Adhesion was evaluated by measuring peel strength. The results are shown in Table 5.
○: Peel strength of 10 N / inch or more.
X: Peel strength is less than 10 N / inch.

  Even when aqueous emulsions (E-1) to (E-7) are used, it is possible to produce a laminated structure with good adhesion in the same manner as in Example A (evaluation of adhesion to M-EVA) described above. it can.

<Example B: Evaluation 2 of adhesion of water-based adhesive to M-EVA>
Table 6 shows Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant in each of the water-based emulsions (nonvolatile content ratio) obtained in the production examples of water-based emulsions. Add the indicated amount (non-volatile content ratio, unit: parts by weight) and prepare with water so that the non-volatile content of the formulation is 40%, and stir with a three-one motor to prepare aqueous adhesive B1 and aqueous adhesive B2. Got each.
The obtained water-based adhesive B2 was applied to 100% cotton canvas using a glass rod (application amount: weight after drying about 130 g / m ² ) and air-dried for 20 minutes. The resulting canvas was microwaved (Microelectronics company make, 9KW microwave oven, frequency 2.45GHz) It put into electromagnetic waves for 30 seconds at 3000W.
Also, water-based adhesive B1 was applied to bar coater No. 75 was applied to M-EVA (application amount: weight after drying: about 30 g / m ² ), and the obtained M-EVA was put in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 110 seconds.
Again, water-based adhesive B2 was applied to each of cotton canvas and M-EVA (cotton canvas coating amount: weight after drying about 60 g / m ² , M-EVA coating amount: weight after drying about 30 g / m ² ), The obtained cotton canvas and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 15 seconds.
Subsequently, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Immediately removed from the microwave and crimped by hand.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 6.

<Example C: Evaluation 3 of adhesion of water-based adhesive to M-EVA>
Table 7 shows Adekanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant in each emulsion (nonvolatile content ratio) obtained in the production example of the aqueous emulsion. (Non-volatile content ratio, unit: parts by weight) and the water-based adhesive C1 and the water-based adhesive C2 are prepared with water so that the nonvolatile content of the formulation is 40% and stirred with a three-one motor. Got.
The obtained water-based adhesive C2 shown in Table 7 was applied to a 100% cotton canvas using a glass rod (weight application amount after drying: about 130 g / m ² ), and air-dried for 20 minutes to obtain. The canvas was subjected to electromagnetic wave treatment in a microwave oven at 3000 W for 30 seconds.
In addition, each water-based adhesive C1 shown in Table 7 was replaced with a bar coater No. 75 was applied to M-EVA (weight application amount after drying: about 30 g / m ² ), and the obtained M-EVA was placed in a microwave oven and subjected to electromagnetic wave treatment at 5000 W for 170 seconds.
A water-based adhesive C2 was applied to each of the obtained cotton canvas and M-EVA (cotton canvas application amount: weight after drying: about 70 g / m ² , M-EVA application amount: weight after drying: about 30 g / m ² ) These cotton canvases were placed in a hot air oven at 80 ° C. for about 15 minutes, and M-EVA was placed in a hot air oven at 80 ° C. for about 10 minutes, and the coated surfaces of the aqueous adhesive were bonded together while hot.
The obtained cotton / adhesive layer / M-EVA laminated structure was again put into a hot air dryer, heat-treated at 80 ° C. for 10 minutes, taken out from the dryer, and then pressure-bonded by hand.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 7.

<Example D: Evaluation 4 of adhesion of water-based adhesive to M-EVA>
In 100 parts by weight of each aqueous emulsion (non-volatile content ratio) obtained in the production example of the aqueous emulsion, Adecanol UH-420 (manufactured by ADEKA) as a thickener, and Nopco Wet 50 (manufactured by San Nopco) as a dispersant, The amount shown in Table 8 (nonvolatile content ratio, unit: parts by weight) was added and water was prepared so that the nonvolatile content of the formulation was 40%, and the mixture was stirred with a three-one motor to obtain an aqueous adhesive D. .
The obtained water-based adhesive D in Table 8 was applied to 100% cotton canvas using a glass rod (coating amount: weight about 130 g / m ² after drying) and air-dried for 1 hour.
Also, the same water-based adhesive D applied to cotton was applied to the bar coater No. 75 was applied to M-EVA (foamed ethylene / vinyl acetate copolymer) (weight application amount after drying: about 30 g / m ² ), and the obtained M-EVA was naturally dried for 1 hour. Then, apply to cotton canvas and M-EVA using a glass rod (cotton canvas: weight after drying about 70 g / m ² , M-EVA coating amount: weight after drying about 30 g / m ² ), put in a microwave oven, Electromagnetic wave treatment was performed at 750 W for 30 seconds.
Subsequently, the coated surfaces of the cotton canvas and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The cotton / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 750 W for 110 seconds. After removing from the dryer, it was crimped by hand. Thereby, a laminated structure composed of cotton / adhesive layer / M-EVA was obtained.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 8.

<Example F: Evaluation 5 of adhesion and heat resistance of water-based adhesive to M-EVA>
As shown in Table 9-1, terpene phenol as the adhesive resin 1 was added to the aqueous emulsions (E-36) to (E-38) (nonvolatile content ratio, unit: parts by weight) obtained in the production examples of the aqueous emulsion. Aqueous urethane emulsion (Tamanol E-200NT, manufactured by Arakawa Chemical Co., Ltd.) and adhesive urethane 2 as an aqueous urethane emulsion (Disco Pearl U-54, manufactured by SBU) are blended so that the nonvolatile content ratio is 100: 100: 100. Furthermore, Adecanol UH-756VF (manufactured by ADEKA) is added as a thickener, Nopco Wet 50 (manufactured by San Nopco) is added as a dispersant, and Desmodur N3300 (manufactured by SBU) is added as a crosslinking agent. After preparing with water so that the non-volatile content would be 40%, the mixture was stirred with a three-one motor to obtain aqueous adhesives F1 to F10.

The obtained water-based adhesive (F10) in Table 9-1 was applied to 100% cotton canvas using a glass rod (coating amount: about 130 g / m ² weight after drying), and after natural drying for 20 minutes, The electromagnetic wave treatment was performed at 3000 W for 30 seconds.
Further, each of the water-based adhesives (F1) to (F9) was transferred to a bar coater No. 75 was applied to M-EVA (ethylene / vinyl acetate copolymer foam) (coating amount: weight after drying: about 30 g / m ² ), and the obtained M-EVA was irradiated with an electric wave at 3000 W for 110 seconds. Processed. Thereafter, the water-based adhesive (F10) was applied to cotton canvas and M-EVA using a glass rod (cotton canvas coating amount: about 70 g / m ² after drying ^, M-EVA coating amount: about 70 g / weight after drying) m ² ), and M-EVA was subjected to electromagnetic wave treatment at 3000 W for 15 seconds.
Subsequently, the coated surfaces of the cotton canvas and the M-EVA aqueous adhesive were bonded together and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Then, it crimped | bonded by hand. Thereby, a laminated structure composed of cotton / adhesive layer / M-EVA was obtained.

Each of the obtained laminated structures was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Shimadzu Corporation, Autograph), at a peeling rate of 50 mm / min and a peeling angle of 180 degrees, the adhesion of the laminated structure. Was evaluated by measuring the peel strength. The results are shown in Table 9-2.
○: Peel strength of 70 N / inch or more.
X: Peel strength is less than 70 N / inch.

Each of the obtained laminated structures was allowed to stand at room temperature for 24 hours, and then, using a tensile tester (manufactured by Toyo Seiki, Strograph T), a set temperature in the tank of 60 ° C., a peeling speed of 50 mm / min, and a peeling angle of 180 degrees Thus, the heat resistance of the laminated structure was evaluated by measuring the peel strength. The results are shown in Table 9-2.
○: Peel strength of 15 N / inch or more.
X: Peel strength is less than 15 N / inch.

<Example H: Evaluation 7 for Adhesion of Water-based Adhesive to M-EVA / Synthetic Leather>
Table 10 shows Adecanol UH-756VF (manufactured by ADEKA) as a thickener and Nopco Wet 50 (manufactured by San Nopco) as a dispersant in each emulsion (nonvolatile content ratio) obtained in the production example of an aqueous emulsion. (Non-volatile content ratio, unit: parts by weight), and prepared with water so that the non-volatile content of the formulation is 40%, and stirred with a three-one motor, the aqueous adhesive H1 and the aqueous adhesive H2 Obtained.
The obtained water-based adhesive H-1 in Table 10 was used as a bar coater No. 75 was applied to M-EVA (weight application amount after drying: about 30 g / m ² ), and the obtained M-EVA was placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 110 seconds.
Aqueous adhesives H-1 and H-2 were applied to each of the obtained M-EVA and synthetic leather (the amount of H-2 applied to the synthetic leather: weight after drying: about 30 g / m ² , to M-EVA) H-1 coating amount: weight about 30 g / m ² after drying, and the obtained synthetic leather and M-EVA were placed in a microwave oven and subjected to electromagnetic wave treatment at 3000 W for 15 seconds.
Subsequently, the coated surfaces of the synthetic leather and the aqueous adhesive of M-EVA were bonded together and pressure-bonded.
The synthetic leather / adhesive layer / M-EVA laminated structure thus obtained was again placed in a microwave oven and subjected to electromagnetic wave treatment at 3900 W for 120 seconds. Immediately removed from the microwave and crimped by hand.
The obtained laminated structure was allowed to stand at room temperature for 24 hours, and the adhesion of the laminated structure was evaluated by the same method and evaluation criteria as described above. The results are shown in Table 10.

  According to the method for producing a laminated structure of the present invention, a laminated structure having excellent adhesiveness can be produced.

Claims (4)

A manufacturing method of a laminated structure in which a first base material, an adhesive layer, and a second base material are laminated in this order,
(A) applying a water-based adhesive to the surface of the first base material, subjecting the first base material coated with the water-based adhesive to an electromagnetic wave with an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz;
(B) applying a water-based adhesive to the surface of the second substrate and drying the second substrate coated with the water-based adhesive;
(C) A method of manufacturing a laminated structure including a step of bonding a surface of the first base material to which the aqueous adhesive has been applied and a surface of the second base material to which the aqueous base material has been applied, which has been dried. .   The manufacturing method of the laminated structure of Claim 1 which processes with respect to the base material of both the said 1st base material and a 2nd base material with an electromagnetic wave with a frequency band of 2.45 +/- 0.02 GHz.   Prior to the bonding step, an aqueous adhesive is again applied to the surface of at least one of the adhesive layers applied to the first base material and the second base material, and the obtained base material is dried. The manufacturing method of the laminated structure of Claim 1 or 2 including the process to do. The laminated structure obtained by bonding the first base material and the second base material is further processed with an electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz. The manufacturing method of the laminated structure of description.