JP2013151144A - Laminated structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated structure of a nylon resin, an adhesive layer, and a cotton-containing fibers having excellent adhesion properties.SOLUTION: A laminated structure is accumulated with: a first base material that comprises a polyolefin; an adhesive layer including a copolymer that has one or more kinds of the structural unit derived from a C2-20 α-olefin; and a second base material that comprises the cotton-containing fibers in this order. In addition, the adhesive layer is desirable to be formed with the aqueous adhesive including the surfactant shown by formula (I). In the formula, X represents a hydrogen atom or -SOM (M is a hydrogen atom, NH, or an alkali metal). n represents an integer between 1 and 3, inclusive. m represents an integer between 1 and 100, inclusive.

Description

  The present invention relates to a laminated structure comprising polyolefin / adhesive layer / cotton-containing fibers.

  In general, in a laminated structure obtained by bonding substrates together with an adhesive, various studies have been made on the types and combinations of the substrate and the adhesive layer (Non-Patent Document 1).

Japan Adhesive Edition "Adhesion Handbook (4th edition)" published by Nikkan Kogyo Shimbun, December 28, 2007, page 98

  In the conventional laminated structure, in particular, the adhesion of the adhesive layer located between the polyolefin and the cotton-containing fiber to the polyolefin and the cotton-containing fiber may not always be satisfactory.

The present invention includes the following inventions.
[1] A first substrate made of polyolefin, an adhesive layer containing a polymer having one or more structural units derived from α-olefins having 2 to 20 carbon atoms, and a second substrate made of cotton-containing fibers A laminated structure laminated in this order.
[2] The laminated structure according to [1], wherein the adhesive layer is a layer further containing a surfactant represented by the following formula (I).
(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.)
[3] The surfactant is a surfactant including two or more of a surfactant in which X is a hydrogen atom and a surfactant in which X is —SO ₃ M. The laminated structure described.
[4] The stacked structure according to [2] or [3], wherein —SO ₃ M in the surfactant is SO ₃ NH ₄ .
[5] The laminated structure according to any one of [1] to [4], wherein the adhesive layer is a layer further containing a basic compound (C).
[6] The laminated structure according to any one of [1] to [5], wherein the adhesive layer further includes a pressure-sensitive adhesive resin.
[7] The adhesive layer according to any one of [1] to [6], wherein the adhesive layer is a layer obtained from an adhesive containing a dispersoid having a particle size (number basis) of 0.01 to 1.0 μm. Laminated structure.

  According to the present invention, there is provided a laminated structure of polyolefin / adhesive layer / cotton-containing fiber, in which the adhesive layer located between the polyolefin and the cotton-containing fiber is firmly bonded to both the polyolefin and the cotton-containing fiber. Can do.

The laminated structure of the present invention includes a first base material made of polyolefin, an adhesive layer containing a polymer having one or more types of structural units derived from α-olefins having 2 to 20 carbon atoms, and a second base made of cotton-containing fibers. Are laminated in this order.
In this laminated structure, the adhesive layer is a layer obtained by an adhesive, particularly an aqueous adhesive, and is a layer formed by evaporation of water and a solvent when contained in the adhesive.

<First base material>
The first substrate is made of polyolefin.
Here, the polyolefin is a thermoplastic resin obtained by polymerizing an olefin, and examples thereof include homopolymers and copolymers having a structural unit 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 and the like. In addition, what is mentioned later is mentioned about the polymer which has a structural unit derived from a C2-C20 alpha olefin.

  In particular, polyethylene has various properties such as high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, and ultra-high-molecular-weight polyethylene depending on the difference in molecular weight. The polyethylene as the adherend includes any of these.

  Polypropylene is a thermoplastic resin obtained by polymerizing propylene, and there are polypropylenes having different isotactic (isotactic), syndiotactic, and atactic stereoregularity due to the difference in stereoregularity. Polypropylene as an attachment includes any of these.

Examples of the form of the polyolefin as the first substrate of the laminated structure of the present invention include various forms such as a woven fabric, a knitted fabric, a nonwoven fabric, a knitted fabric, a felt, a film, and a block shape. Examples thereof include cotton-containing fibers used for films and sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing, shoes, and the like.
Among these, polyolefins used as a constituent material for covering, insole, outer bottom, etc. in footwear including men's shoes and women's shoes such as sports shoes, town shoes, and business shoes, and industrial work shoes, etc. Can be mentioned.
The size, thickness, shape, and the like of the first base material can be appropriately adjusted depending on the purpose of use of the laminated structure.
The surface facing the adhesive layer of the first substrate may be smooth or may have irregularities.

<Second base material>
A 2nd base material consists of a cotton containing fiber. Examples of the cotton-containing fiber include 100% cotton fiber, cotton, and a blended fiber of other natural fiber and / or chemical fiber. 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.

Examples of the form of the cotton-containing fiber as the second substrate of the laminated structure of the present invention include various forms such as woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape. Examples thereof include cotton-containing fibers used for films and sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing, shoes, and the like.
Among them, containing cotton, which is used as a constituent material for cover, insole, outer bottom, etc. in footwear including men's shoes and women's shoes such as sports shoes, town shoes, business shoes, and industrial work shoes, etc. Fiber.
The size, thickness, shape, and the like of the second substrate can be appropriately adjusted according to the purpose of use of the laminated structure.
The surface facing the adhesive layer of the second substrate may be smooth or may have irregularities.

<Adhesive layer>
An adhesion layer contains the polymer which has 1 or more types of structural units derived from a C2-C20 alpha olefin. This adhesive layer is an adhesive layer that is sandwiched between substrates made of various materials, in particular, between laminated structures of polyolefin and cotton-containing fibers.

<Manufacturing method of laminated structure>
In order to produce the laminated structure of the present invention, first, an adhesive is applied to either one of the first base material or the second base material, preferably both.
Before applying the adhesive, a primer treatment may be applied to the surface of the first base material and / or the second base material in order to enhance the adhesion with the adhesive layer. 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. In particular, when using a substrate that can absorb water, such as cotton-containing fibers, as the primer treatment, an adhesive may be applied and dried. Application | coating and drying of an adhesive agent here can be performed by the method mentioned later. When the primer treatment is performed, only one type of adhesive may be used, or two or more types may be used. The primer treatment may be performed twice or more. Different adhesives may be used for the first and second substrates, but it is preferable to use the same adhesive.

Application is a known film formation method, for example, applying an adhesive to the surface of one or both of polyolefin and cotton-containing fibers, and allowing to stand near room temperature as necessary, followed by drying or heat treatment for drying and baking The method attached to is mentioned.
In place of application, depending on the composition of the adhesive, it may be formed into a film by extrusion, or may be applied to various substrate surfaces and dried to form the obtained film. The substrate may be sandwiched between the second substrate and the second substrate, and may be pressed (or heated) and bonded.
Examples of the application method include gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, spatula coating, and the like.

Drying may be natural drying, non-thermal drying such as air drying, or a normal hot-air circulating oven, infrared or far-infrared heater, electromagnetic wave (for example, electromagnetic wave having a frequency band of 2.45 ± 0.02 GHz) irradiation device or electronic It can be performed by heat drying using a range or the like. The heating temperature and the heating time can be appropriately adjusted according to the characteristics of the substrate, the composition of the adhesive used in the present invention, and the like. For example, as heating 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.
Application and drying of the adhesive may be performed only once, or may be performed twice or more. At that time, the coating method and the drying method may be combined with each other, or may be combined with different methods. Moreover, you may combine the frequency band from which electromagnetic waves differ.

When laminating the first and second substrates, 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 addition, after the first and second substrates are bonded, the obtained laminated structure is subjected to the above-described non-thermal drying or heat drying (for example, electromagnetic wave irradiation), and further, a pressure load is applied. May be.

  The thickness of the adhesive layer formed using the adhesive can be appropriately adjusted depending on the form of the first base material and the second base material that are adherends. For example, about 0.01-300 micrometers is mentioned, Preferably it is about 0.01-200 micrometers, More preferably, it is about 0.2-200 micrometers.

  The adhesive layer in such a laminated structure is obtained by using an adhesive, particularly an aqueous adhesive, as described above. This adhesive is a structural unit derived from an α-olefin having 2 to 20 carbon atoms. Includes one or more polymers.

<Polymer>
Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, vinylcyclohexane and the like. Preferably, ethylene, propylene, 1-butene, etc. are mentioned.

  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 an α-olefin 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.

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 adhesive to the adherend can be further improved.

  Among them, the polymer having a structural unit 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 an α-olefin having 2 to 20 carbon atoms. A structure derived from one or more monomers selected from the group consisting of different α-olefins having 2 to 20 carbon atoms, α, β-unsaturated carboxylic acid esters, α, β-unsaturated carboxylic acid anhydrides, and vinyl acetate. More preferably, the copolymer has a structural unit derived from ethylene, an α-olefin having 3 to 20 carbon atoms, an α, β-unsaturated carboxylic acid ester, and 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. And alpha, a copolymer having a structural unit derived from one or more monomers selected from the group consisting of β- unsaturated carboxylic acid.

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

<Other resins>
The adhesive may contain other resins other than the polymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms.
Examples of other resins include polyolefin resins other than the above-described polymers, acrylic resins (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetra Examples thereof include polymers and copolymers such as fluoroethylene (PTFE), acrylonitrile butadiene styrene resin (ABS resin), 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, indene resins and 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 polymers, terpene phenols, β-pinene polymers, aromatic-modified terpene polymers, α-pinene polymers, terpene-based hydrogenated resins, etc .; petroleum fractions having 5 carbon atoms Petroleum resins obtained by polymerizing styrene, 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 polyols described later Polyurethane obtained by reacting a compound and, if necessary, another compound For example, lettan 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 its molecule is called an ionomer structure and has a surface-active ability in itself. Therefore, there exists a tendency which is easy to disperse | distribute in water, and there exists a tendency which improves the water resistance of the aqueous emulsion obtained by emulsion-polymerizing a monomer further to the polyurethane aqueous emulsion.

As the hydrophilic group, anionic groups such as a sulfonyl group and a 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 or a commercially available water-soluble urethane resin may be used as it is.
For example, a polyurethane dispersion (or polyurethane aqueous solution) in which a polyurethane resin is dispersed or dissolved in water can be mentioned. 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 adhesive used in the present invention contains other resins, the content thereof is preferably 1 to 99% by weight, more preferably 3 to 99% by weight, based on the total amount of the adhesive. Preferably it is 5-90 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>
It is preferable that the adhesive further contains a surfactant that generally acts as an emulsifier. Such surfactants include cationic, anionic, amphoteric and nonionic surfactants. Of these, anionic or nonionic surfactants are preferred. Particularly preferred are those having the structure of formula (I). 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).
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 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, more preferably 0.1 to 100 parts by weight of the resin constituting the adhesive. 1 to 10 parts by weight.
When the 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) are used. The total content of the surfactant other than the surfactant is usually 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin constituting the adhesive. Part, 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 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, organic amine compounds having a boiling point of 200 ° C. or less can be easily dispersed by ordinary drying, and maintain / improve the water resistance and alkali resistance of the coating film when the coating film is formed using an adhesive. This 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 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 adhesive. Yes, more preferably 2 to 10 parts by weight.

<solvent>
The adhesive used in the present invention preferably does not contain a solvent, but in some cases, in addition to water, for example, an aromatic hydrocarbon such as toluene and xylene; an aliphatic hydrocarbon 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 Glycol solvents, methyl cellosolve, cellosolve, butyl cellosolve, dioxane, cellsolve solvents such as MTBE (methyl tertiary butyl ether), butyl carbitol, diethylene glycol monomethyl ether, triethyleneglycol Glycol solvents such as dimethyl 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 ether An organic solvent such as a glycol ester solvent such as acetate; You may use these individually or in combination of 2 or more types.
When the adhesive used in the present invention contains a solvent, the content thereof is usually 0.01 to 30 parts by weight, preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the resin constituting the adhesive. Parts, more preferably 0.01 to 10 parts by weight.

<Other ingredients>
The 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 needed, within a range that does not impair the intended properties of the adhesive. Stabilizers such as antioxidants, heat stabilizers, light stabilizers; thixotropic agents, thickeners, dispersants, antifoaming agents, viscosity modifiers, weathering agents, pigments, pigment dispersants, antistatic agents, lubricants Additives such as nucleating agents, flame retardants, oil agents, dyes, curing agents, cross-linking agents; transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, titanic acid Potassium fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate, clay, kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, Aluminum, magnesium oxide, alumina, inorganic, such as celite, may contain optional components such as organic fillers.

(water)
As water contained in the 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 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, still more preferably 45% by weight or more, and preferably 85% by weight or more based on the total amount of the adhesive. % By weight or less, more preferably 80% by weight or less, still more preferably 70% by 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 an adhesive agent, and 0.1-10 weight part is more preferable. The curing agent may be added after being dissolved in an organic solvent.

<Method for producing adhesive>
As a method for producing an adhesive, a method known in the art, for example, a post-emulsification method (for example, a forced emulsification method, a self-emulsification method, a phase inversion emulsification method, etc.) after polymerizing a resin and dispersing the resin in an aqueous medium ) And the like.
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 rotation speed as the dispersion / stirring of the 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 adhesive agent.
Further, in the production process of the adhesive, it is preferable to use the surfactant within a desired range. However, when the surfactant is used in an excessive amount, it is arbitrarily added to the excess interface from the obtained adhesive. The active agent may be separated and removed. Separation and removal of the surfactant is, for example, a centrifuge, a filtration filter having an average pore size smaller than the average particle size of the adhesive (preferably having an average pore size of 0.05 to 0.5 μm). Examples thereof include a method using a microfiltration membrane) or an ultrafiltration membrane.
Further, the obtained adhesive is preferably cooled. Thereby, the adhesive agent 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 adhesive can be obtained without agglomeration of resin or the like during the cooling process.

The particle size of the dispersoid contained in the 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. Good static stability.
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 plural types of dispersoids are contained in the adhesive (for example, a polymer having a structural unit derived from an α-olefin and a polyurethane resin), it is preferable that the particle diameters 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%.

In the laminated structure of the present invention, the polymer is
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, an α, β-unsaturated carboxylic acid ester, α, β- A copolymer having a structural unit derived from one or more monomers selected from the group consisting of an unsaturated carboxylic acid anhydride and vinyl acetate,
One or more kinds 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,
A 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,
Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-1-butene An α-olefin copolymer such as a copolymer or a modified product thereof; or a mixture of two or more of these,
Ethylene-propylene copolymer, propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-hexene copolymer, ethylene-propylene-1-butene An α-olefin copolymer such as a copolymer or a maleic anhydride modified product thereof; or a mixture of two or more of these,
a copolymer of α-olefin and vinyl acetate or a modified product thereof; or a mixture of two or more of these,
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 a copolymer of α-olefin, (meth) acrylate and maleic anhydride It is preferably at least one selected from the group consisting of a polymer or a modified product thereof; or a mixture of two or more thereof.
In the laminated structure of the present invention, the polymer preferably has a melting point of 60 to 110 ° C.
In the laminated structure of the present invention, the adhesive layer preferably further contains a polyurethane resin or a water-insoluble polyurethane resin.
In the laminated structure of the present invention, the adhesive layer is further selected from the group consisting of terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, and terpene hydrogenated resins. It is preferable to contain a terpene resin.
In the laminated structure of the present invention, the adhesive layer 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 hydrogenated resin. It preferably contains a terpene resin selected from the group.
In the laminated structure of the present invention, the adhesive layer preferably further contains a polyurethane resin and terpene phenol or a water-insoluble polyurethane resin and terpene phenol.
In the laminated structure of the present invention, the adhesive layer preferably further contains an isocyanate.
In the laminated structure of the present invention, the adhesive layer is further selected from the group consisting of diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI) and oligomers or polymers thereof. It is preferable to contain an isocyanate.
In the laminated structure of the present invention, the adhesive layer is 0.1 to 50 parts by weight, 0.1 to 20 parts by weight, or 0.1 to 10 parts by weight with respect to 100 parts by weight of the total resin constituting the aqueous emulsion. It is preferable to include a surfactant.
In the laminated structure of the present invention, the adhesive layer has a mass ratio of the surfactant represented by the formula (A) and the surfactant represented by the formula (B) from 1 to 99:99 to 1,5. -95: 95-5, 10-90: 90-10, 30: 70-90: 10, 40: 60-90: 10 or 50: 50-90: 10 are preferable.
In the laminated structure of the present invention, after polymerization of a thermoplastic resin, the resin is dispersed in an aqueous medium and then adhered by an adhesive obtained by an emulsification method, a forced emulsification method, a self-emulsification method or a phase inversion emulsification method. It is preferable that an increase is formed.

  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)
The measurement was performed according to JIS-K-7210.

(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) obtained by modification 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) obtained by modification 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, a thermometer, a dropping funnel and a reflux condenser, and the pressure was reduced, and then 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%.

  <Manufacture example 10 of aqueous | water-based emulsion> It replaces with 100 parts of polymers (B-1-2), 67 parts of polymers (B-4-2), adhesive resin (terpene phenol, Tamanol 803L, Arakawa Chemical Co., Ltd.) 33 An aqueous emulsion (E-10) was produced in the same manner as in <Preparation Example 1 of Aqueous Emulsion> except that the parts were used. 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 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 and 3 in the weight ratios shown in Tables 2 and 3, an aqueous emulsion (E-47) substantially in the same manner as <Production Example 1 of 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 and 5.
○: Aggregation, precipitation, and phase separation were not observed, and the condition was good.
X: Aggregation, precipitation, and phase separation occurred.

<Polypropylene laminate>
A polypropylene (PP) plate (thickness 3 mm: hereinafter referred to as a PP plate) is washed with IPA, and the aqueous emulsions (E-1) to (E-7) are coated thereon with a thickness of 10 μm after drying. It applied so that it might become. This was dried at 80 ° C. for 5 minutes with a hot air dryer, and further heated and dried in an oven at 120 ° C. for 30 minutes to obtain a film.
Based on JIS-K5400 (cross-cut peeling tape method test), the obtained film was cut with a grid-like cut with a gap interval of 1 mm, and then a cellophane tape was stuck on the coating film. Next, one to two minutes after applying the cellophane tape, the tape was peeled off at a right angle to evaluate the adhesion. The evaluation criteria were as follows. The results are shown in Table 4 as Test Examples 1 to 7.
○: The area of peeling is less than 40% of the square area.
X: The area of peeling is 40% or more of the square area.

<Polyethylene laminate>
The aqueous emulsion obtained above was applied to a high-density polyethylene (HDPE) base material (manufactured by Shin-Kobe Electric Machinery Co., Ltd., EL-N-AN, 2 mm thickness) so that the film thickness after drying was about 10 μm. A heat treatment was carried out at 30 ° C. or 120 ° C. for 30 minutes to obtain a laminated structure having a layer derived from an aqueous emulsion as a coating film on the surface of the HDPE substrate.
Each of the obtained laminated structures was allowed to stand at room temperature for 24 hours, and then a cut of 100 squares with a width of 1 mm was made in the coating film, and the number of cells where the coating film remained completely was counted by cellophane tape peeling. Adhesiveness was evaluated by the amount of the coating film remaining after peeling the cellophane tape three times. The results are shown in Table 3. In Table 6, a larger number (closer to 100) means better adhesion.

  Table 7 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 content ratio) obtained in the production example of an aqueous emulsion. The indicated amount (nonvolatile content ratio) was added and stirred with a three-one motor to obtain an aqueous adhesive shown in Table 7.

  In addition, all of Examples 15 to 41 of the aqueous adhesive obtained above were in a good state with no aggregation, precipitation, or phase separation observed in the appearance after standing for 5 days. Moreover, the adhesiveness with respect to various base materials, such as polyolefin, especially polyethylene and a polypropylene, was also favorable.

  According to the laminated structure of the present invention, a strong laminated structure of polyolefin, particularly polyethylene and polypropylene, an adhesive layer, and cotton-containing fibers can be obtained.

Claims (7)

  A first base material made of polyolefin, an adhesive layer containing a polymer having one or more structural units derived from α-olefins having 2 to 20 carbon atoms, and a second base material made of cotton-containing fibers are laminated in this order. Laminated structure. The laminated structure according to claim 1, wherein the adhesive layer is a layer further containing a surfactant represented by the following formula (I).
(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.) The laminated structure according to claim 2, wherein the surfactant is a surfactant containing two or more types of surfactants in which X is a hydrogen atom, surfactants in which X is —SO ₃ M, and the like. . Layered structure according to -SO ₃ M is, claim 2 or 3 is _SO 3 NH ₄ in the surfactant.   The laminated structure according to any one of claims 1 to 4, wherein the adhesive layer is a layer further containing a basic compound (C).   The laminated structure according to claim 1, wherein the adhesive layer is a layer further containing an adhesive resin.   The laminated structure according to any one of claims 1 to 6, wherein the adhesive layer is a layer obtained from an adhesive containing a dispersoid having a particle size (number basis) of 0.01 to 1.0 µm.