JP2000280415A - Laminated structure - Google Patents

Abstract

(57) Abstract: By applying and drying an emulsion composition in which resin particles containing an olefin polymer (A) and an acrylic polymer (B) in the same particle are dispersed in water. The resulting laminated structure. The laminated structure according to the present invention has excellent adhesion to both a non-polar substrate such as polyethylene and polypropylene and a polar substrate such as nylon, polystyrene, polyacryl, and polyethylene terephthalate, and has further strength. Olefin polymer (A) with excellent transparency and low-temperature adhesion
And a layer containing the acrylic polymer (B),
Laminated structure by laminating various plastic films, lamination of various plastic films with aluminum foil, paper, non-woven fabric, wood, plywood, laminated wood, etc., and olefin polymer on various substrates A laminated structure having a layer containing (A) and the acrylic polymer (B) is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminated structure comprising a layer containing an olefin polymer (A) and an acrylic polymer (B). The laminated structure according to the present invention comprises, for example, applying and drying an emulsion composition in which resin particles containing an olefin polymer (A) and an acrylic polymer (B) in the same particle are dispersed in water. Obtained by

[0002]

2. Description of the Related Art At present, a laminated structure in which a resin is applied to a base material such as various kinds of plastics, plastic films, vapor-deposited films, aluminum foil, paper, nonwoven fabric, wood, etc. A laminated structure, which is a laminated product laminated by the above, is widely used. Plastics include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer, ethylene
Examples thereof include polyolefins such as vinyl alcohol copolymers, and cellophane, polyamide (nylon), polyester, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polystyrene, and polyacrylonitrile copolymer. Furthermore, these plastic films are mentioned. As vapor deposition films, aluminum, gold, silver, copper, nickel, zinc, titanium, cobalt,
Examples thereof include a film obtained by evaporating a metal such as indium and chromium, and a film obtained by evaporating aluminum oxide and silicon oxide. Usually, a solvent-based resin is used as a resin or an adhesive applied on these base materials. However, in recent years, a laminated structure made of an aqueous resin due to a problem of environmental load and a problem such as a residual solvent of a product. Is required. However, few of them are water-based and have good adhesiveness and adhesiveness to various substrates, and their performances are insufficient.

For example, an emulsion composition of an olefin polymer has excellent adhesion to a substrate of a polyolefin such as polyethylene or polypropylene.
There has been a problem that adhesion to polar substrates such as polystyrene, polyacryl, and polyethylene terephthalate is poor, and film forming properties at low temperatures are poor. In addition, the emulsion composition of an acrylic polymer, contrary to olefins, has excellent adhesion to polar substrates and excellent film forming properties at low temperatures, but has the problem of poor adhesion of polyolefins to substrates. I was holding it. The technologies disclosed at present include the following.

[Japanese Patent Application Laid-Open No. 57-40545]
No. 7-40545 discloses a production method in which an acrylic monomer is polymerized under a water-soluble initiator in the presence of an aqueous emulsion of an ethylene-vinyl acetate polymer containing 5 to 30% by weight of ethylene. The emulsion composition obtained by this production method has a low ethylene content and a high vinyl acetate content.

[Japanese Patent Publication No. 63-64446]
No. 64446 discloses that in a suspension containing olefin polymer particles, a vinyl monomer and a specific initiator, a vinyl monomer is impregnated in the olefin polymer particles, and then heated to carry out polymerization. A method for producing olefin polymer particles to be completed is disclosed. This polymerization is carried out in a solvent, the particles are taken out after the polymerization, and the particles themselves are used as a product. It is also disclosed that the average particle size (average particle diameter) of the olefin polymer particles is preferably about 1 to 8 mm.

[0006]

The problem to be solved by the present invention is to adhere to both polar and non-polar substrates.
An object of the present invention is to provide a laminated structure including a layer containing an olefin polymer (A) and an acrylic polymer (B).

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that an olefin polymer (A) which firmly adheres both a polar substrate and a non-polar substrate. ) And a layer containing the acrylic polymer (B), containing a specific olefin polymer and a specific acrylic polymer in the same particle, applying the emulsion composition in which the particle is dispersed in water, and drying. The present inventors have found out what can be obtained by doing so, and have completed the present invention. That is, the present invention
It is specified by the items described below.

[1] It comprises a layer containing an olefin polymer (A) and an acrylic polymer (B).
Laminated structure. [2] Based on the total weight of the olefin polymer (A) and the acrylic polymer (B), 95 to 10% by weight of the olefin polymer (A) and 5 to 5% of the acrylic polymer (B).
The laminated structure according to [1], which is 90% by weight. [3] Any one of [1] to [2], wherein the “olefin-based polymer (A)” includes a (co) polymer of an olefin-based monomer (a-1). 3. The laminated structure described in 1. above.

[4] "Olefin polymer (A)"
Is a composition including at least one selected from the group consisting of an ethylene / butene copolymer, an ethylene / propylene copolymer, and an ethylene / butene / propylene copolymer, [1] to The laminated structure according to any one of [3]. [5] "Olefin polymer (A)" is ethylene
Comprising a vinyl acetate copolymer,
The laminated structure according to any one of [1] to [4].

[6] "Olefin polymer (A)"
Is a composition comprising a copolymer of an olefin monomer (a-1) and a monomer (a-2) other than the olefin monomer (1) to (5). A laminated structure according to any one of the above. [7] The ratio of the olefin monomer (a-1) and the monomer (a-2) other than the olefin monomer is other than the olefin monomer (a-1) and the olefin monomer. Of the olefin monomer (a-1) based on the total weight of the monomer (a-2), and 99.9 to 35.0% by weight of the monomer (a-2) other than the olefin monomer. ) 0.1 to 65.0% by weight
The laminated structure according to [6].

[8] The monomer (a-2) other than the olefinic monomer contains at least a part of a monomer having no carboxyl group, [6] or [7]. ] The laminated structure as described in []. [9] “A monomer other than the olefin monomer (a-
2)] is a layered structure according to [6] or [7], wherein the layered structure contains only a monomer containing no carboxyl group. [10] “A monomer other than the olefin monomer (a-
2) is “vinyl acetate”, wherein the laminated structure according to [8] or [9].

[11] The laminated structure according to any one of [1] to [10], wherein the acrylic polymer (B) contains a polymer of the acrylic monomer (b). . [12] The laminated structure according to [11], wherein the “acrylic monomer (b)” contains at least a part of a monomer having a water solubility of 0.0 to 0.5%. . [13] The laminated structure according to [11] or [12], wherein the “acrylic monomer (b)” at least partially contains a monomer having no carboxyl group.

[14] "Acrylic monomer (b)"
Has a carboxyl group-free monomer only, the laminated structure according to [11] or [12]. [15] “Acrylic monomer (b)” is styrene,
And / or the laminated structure according to any one of [11] to [14], which contains at least a portion of 2-ethylhexyl acrylate.

[16] A layer containing the olefin polymer (A) and the acrylic polymer (B) is formed as a step 1
An olefin polymer (A) and an acryl polymer obtained by polymerizing an acrylic monomer (b) in an olefin emulsion in which resin particles containing the olefin polymer (A) are dispersed in water. A step of producing an emulsion composition in which resin particles containing the polymer (B) in the same particle are dispersed in water; and a step of applying and drying the emulsion composition obtained in the step 1 as a step 2. The laminated structure according to any one of [1] to [15], which is obtained by a manufacturing method including the above.

[17] The weight average particle diameter of the resin particles is
The laminated structure according to [16], which has a thickness of 10 nm to 500 μm. [18] The laminated structure according to [16] or [17], wherein an initiator having water solubility of 0 to 10% is used when polymerizing the acrylic monomer (b). . A)
And layers other than the layer containing the acrylic polymer (B) are plastic, plastic film, vapor-deposited film,
The laminated structure according to any one of [1] to [18], which is at least one selected from paper, nonwoven fabric, and wood.

[20] The laminated structure according to [19], wherein one of the layers in contact with the layer containing the olefin polymer (A) and the acrylic polymer (B) is a polyolefin layer. Is a polyolefin film, [20]
3. The laminated structure described in 1. above.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an olefin monomer (a-1), that is, an olefin polymer (A) is used.
The olefin monomer (a-1) to be used for the polymerization of is not particularly limited. In the present invention, specific examples of the olefin-based monomer (a-1) include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4
-Methyl-1-pentene, 3-methyl-1-pentene, 1-
Α-olefins such as heptene, 1-hexene, 1-decene and 1-dodecene; conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene and 1,5-hexadiene, and non-conjugated dienes; One or more types of body can be selected.

In the present invention, the monomer (a-2) other than the olefin monomer, that is, the monomer other than the olefin monomer used for the polymerization of the olefin polymer (A) is an olefin monomer. It is not particularly limited as long as it is a monomer copolymerizable with the monomer. In the present invention, specific examples of the monomer (a-2) other than the olefin-based monomer include, for example, vinyl acetate, vinyl alcohol, and the like. Can be selected.

The ratio of the olefin monomer (a-1) and the monomer (a-2) other than the olefin monomer is determined by the ratio of the olefin monomer (a-1) to the monomer other than the olefin monomer. Preferably, based on the total weight of the monomer (a-2), the olefin monomer (a-1) is 99.9 to 35.0% by weight /
Monomers (a-2) other than olefinic monomers 0.1 to 6
5.0% by weight, and more preferably 99.9 to 50.0% by weight of olefin-based monomer (a-1) /0.1 of monomer (a-2) other than olefin-based monomer. To 50.0% by weight, more preferably an olefin-based monomer (a
-1) 99.9 to 70.0% by weight / 0.1 to 30.0% by weight of monomer (a-2) other than olefinic monomer. The olefin monomer (a-1) is 35.0% by weight.
If it is less than the characteristic as an olefin is not expressed,
For example, there is a case where a problem that adhesion to a non-polar base material is reduced occurs.

In the present invention, embodiments of the olefin polymer (A) include the following. An olefin polymer (A) obtained by polymerizing the olefin monomer (a-1). An olefin polymer (A) obtained by polymerizing an olefin monomer (a-1) and a monomer (a-2) other than the olefin monomer.

In the present invention, specific examples of the olefin polymer (A) include low-density polyethylene, high-density polyethylene, polypropylene, poly 1-butene, poly 3-methyl-1-butene, and poly 4-methyl-1. -Pentene, poly-3-methyl-1-pentene, or ethylene / propylene copolymer, ethylene / 1-butene copolymer, propylene / 1-butene copolymer, propylene / 1
-Ethylene, propylene, 1-butene, 3-methyl-1-butene, 4- represented by butene-ethylene copolymer
Methyl-1-pentene, 3-methyl-1-pentene, 1
A homopolymer of α-olefin such as heptene, 1-hexene, 1-decene, 1-dodecene, or a random or block copolymer thereof, or an ethylene / butadiene copolymer or ethylene / ethylidene norbornene copolymer Copolymers of α-olefins represented by coalescence with conjugated dienes or non-conjugated isodienes, or ethylene
Propylene / butadiene terpolymer, ethylene / propylene / dicyclopentadiene terpolymer, ethylene / propylene / ethylidene norbornene terpolymer,
Copolymer of two or more types of α-olefins represented by ethylene / propylene / 1,5-hexadiene terpolymer and conjugated diene or non-conjugated diene, or ethylene / vinyl acetate copolymer And a copolymer of an olefin resin such as an ethylene / vinyl alcohol copolymer and another thermoplastic monomer.

In particular, in the ethylene / vinyl acetate copolymer, those having a repeating unit derived from a vinyl acetate monomer in a proportion of 50% by weight or less are preferred from the viewpoint of water resistance, and more preferably 30% by weight or less. Are more preferred. In the present invention, the acrylic monomer (b), that is, the acrylic monomer (b) used for the polymerization of the acrylic polymer (B)
Is not particularly limited. In the present invention, specific examples of the acrylic monomer (b) include, for example, (meth) acrylic esters, particularly alkyl esters having 1 to 12 carbon atoms, but, for example, methyl acrylate, acrylic acid Ethyl, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-methacrylic acid Ethylhexyl, lauryl methacrylate, etc .; as an aromatic monomer, for example, styrene, α-methylstyrene, etc., as a polar group-containing monomer,
Hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate having a hydroxyl group; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and maleic acid having a carboxyl group; Examples of the monomer having a polar group include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, glycidyl methacrylate, and the like, and one or more of these can be selected.

It is preferable that at least one of the acrylic monomers (b) has a water solubility of 0.0 to 0.5%. Aqueous solubility refers to acrylic monomer (b) at 20 ° C
Is a ratio that dissolves in water, and when a monomer having water solubility of more than 0.5% is used for all the acrylic monomers (b),
This is because it becomes difficult to generate the acrylic polymer (B) in the particles of the olefin polymer (A). When the total amount of the acrylic monomer (b) is 100% by weight, the acrylic monomer (b) having a water solubility of 0.0 to 0.5% is preferably 20% by weight or more. , More preferably 30% by weight or more, still more preferably 40% by weight.
That is all.

Specific examples of the acrylic monomer (b) having a water solubility of 0.0 to 0.5% include, for example, styrene, 2-ethylhexyl (meth) acrylate, (meth)
Examples thereof include n-butyl acrylate, i-butyl (meth) acrylate, and t-butyl (meth) acrylate.

When a monomer having a carboxyl group is used as the acrylic monomer (b), the amount used is 5% when the total amount of the acrylic monomer (b) is 100% by weight. % By weight or less, more preferably 3% by weight or less.
%, Most preferably not used. When the amount of the monomer having a carboxyl group exceeds 5% by weight, it may be difficult to form the acrylic polymer (B) in the particles of the olefin polymer (A).

The weight ratio of the olefin polymer (A) to the acrylic polymer (B) is based on the total weight of the olefin polymer (A) and the acrylic polymer (B). A) 95 to 10% by weight, acrylic polymer (B) 5 to 90% by weight is preferable, and olefin polymer (A) 95 to 30% by weight, and acrylic polymer (B) 5 to 70% are more preferable. %, Most preferably 95 to 40% by weight of the olefin polymer (A) and 5 to 60% by weight of the acrylic polymer (B). If the amount of the olefin-based polymer (A) is less than 5% by weight, the characteristics of the olefin are not exhibited, and for example, there is a problem that the adhesion to a non-polar substrate is reduced. Conversely, an olefin polymer (A)
Is 90% by weight or more, the characteristics of acrylic are not exhibited,
For example, there is a problem that adhesion to a polar substrate is reduced.

In the present invention, the resin particles comprise the olefin polymer (A) and the acrylic polymer (B) in the same particle.
And its form is not particularly limited, and examples thereof include, for example, “adhesive (1990, Vol. 34, No. 1, 1)
7)), a core / shell structure, a composite structure, a localized structure, a bar-shaped structure, a weed-like structure, a raspberry-like structure, a multi-particle composite structure, and an IPN structure.

In the present invention, the weight average particle diameter of the resin particles is preferably 10 nm to 500 μm, more preferably 10 nm to 500 μm.
nm to 100 μm, more preferably 10 nm to 10 μm
m, most preferably from 10 nm to 2 μm. When the particle diameter exceeds 500 μm, particle separation during long-term storage usually becomes remarkable, and further, low-temperature film-forming properties and water resistance are likely to be reduced.

The emulsion composition according to the present invention is produced by polymerizing an acrylic monomer (b) in the presence of an emulsion in which particles of an olefin polymer (A) are dispersed in water. Olefin polymer (A)
Acrylic polymer (B) is generated in the particles of (1).

The olefin-based emulsion in which the particles of the olefin-based polymer (A) are dispersed in water is obtained by dispersing the olefin-based polymer (A) in water using an emulsifier or a dispersant. For example, Japanese Patent Publication No. 7-0089
No.33, No.5-099975, No.4-030
970, JP-B-42-000275, JP-B-42-0
No. 23085, JP-B-45-029909, JP-A-5-209
No. 1-062890. Specific examples of commercially available olefin-based emulsions include, for example, Chemipearl A100 and V10 manufactured by Mitsui Chemicals, Inc.
0, V200, V300, W100, W200 and the like.

The initiator used in the polymerization of the acrylic polymer (B) is not particularly limited. As specific examples of the initiator used at the time of polymerization of the acrylic polymer (B), for example, all initiators generally used for emulsion polymerization can be used. Representative examples include hydrogen peroxide; persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, and t-butylperoxy-. 2-
Organic peroxides such as ethylhexanoate, t-butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; or metal ions such as iron ions and sodium sulfoxylate, formaldehyde; Redox initiators in combination with reducing agents such as sodium pyrosulfite, sodium bisulfite, L-ascorbic acid, and Rongalite, and the like, and one or more of these can be used. Specific examples of the initiator preferably used include those having a water solubility of 0 to 10%, more preferably 0 to 5%, and most preferably 0 to 3%. Generally, using initiators with water solubility greater than 10%,
It becomes difficult to generate the acrylic polymer (B) in the particles of the olefin polymer (A). The amount of the initiator used is practically 0.1 to 5% by weight based on the total amount of the monomers.

If necessary, mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan;
It is also possible to use allyl compounds such as allylsulfonic acid, methallylsulfonic acid and their soda salts as molecular weight regulators. When polymerizing the acrylic monomer (b) in the presence of the olefin-based emulsion, a surfactant used in ordinary emulsion polymerization can be used to improve the stability of the particles. Specific examples of such surfactants include, for example, anionic surfactants, nonionic surfactants, cationic surfactants, and other reactive surfactants, and one or more of these surfactants. Can be used in combination.

Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene / oxypropylene block copolymer, tert-octyl. Phenoxyethyl polyethoxyethanol, nonylphenoxyethyl polyethoxyethanol and the like can be mentioned.

Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, and sodium dioctylsulfosuccinate. , Sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, tert-octylphenoxyethoxy polyethoxyethyl sodium sulfate And the like.

Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and the like. The use amount of the surfactant is not particularly limited, but if the use amount is large, particles composed only of the acrylic polymer (B) are generated. Therefore, the acrylic polymer (A) is contained in the particles of the olefin polymer (A). B) is difficult to generate. The amount of the surfactant used is usually 0.02 to 5% by weight based on the total weight of the acrylic monomer (b).

The various monomers described above collectively include
Or dividedly, or continuously added dropwise, in the presence of the above-mentioned initiator at 0 to 100 ° C, practically 30 to 100 ° C.
Polymerized at a temperature of 90 ° C. The emulsion composition used for producing the laminated structure of the present invention includes various additives such as a curing agent, a cross-linking agent, a film-forming aid, an antifoaming agent, an anti-cissing agent, a leveling agent, and a tackifier. , Hardness imparting agents, preservatives, thickeners, antifreezing agents, dispersants, etc., and various pigments such as inorganic pigments and organic pigments can also be added. These additives can be contained in the layer containing the olefin polymer (A) and the acrylic polymer (B).

Specific examples of layers other than the layer containing the olefin polymer (A) and the acrylic polymer (B) constituting the laminated structure of the present invention include various plastics,
Plastic film, vapor deposition film, aluminum foil, paper,
Non-woven fabrics, woods, etc. are mentioned. Examples of plastics are polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer, polyolefin such as ethylene-vinyl alcohol copolymer, cellophane, polyamide (nylon), polyester, polyvinyl chloride, and the like. Polyvinylidene chloride, polyvinyl alcohol, polycarbonate,
Polystyrene, polyacrylonitrile copolymer, etc., and plastic films made of these plastics, and aluminum, gold,
Metals such as silver, copper, nickel, zinc, titanium, cobalt, indium, chromium, and the like, and vapor-deposited films on which aluminum oxide and silicon oxide are deposited, as well as wood such as aluminum foil, paper, non-woven fabric, plywood and particle board. One or two or more of these can be selected.

[0038]

The laminated structure according to the present invention has excellent adhesion to both non-polar substrates such as polyethylene and polypropylene and polar substrates such as nylon, polystyrene, polyacryl and polyethylene terephthalate. Furthermore, since it has a layer containing an olefin polymer (A) and an acrylic polymer (B), which is excellent in strength, transparency, and low-temperature adhesion, a laminated structure formed by laminating various kinds of plastic films. , Laminated structure of various plastic films and aluminum foil, paper, non-woven fabric, wood, plywood, laminated wood, etc., and olefin polymer (A) and acrylic polymer (B) on various substrates Is obtained.

[0039]

Next, the present invention will be described specifically with reference to examples.
You. Hereinafter, all parts and percentages are based on weight. [Example 1] Production of olefin-based emulsion As an olefin-based polymer, ethylene / 1-butene copolymer was used.
Combined (ethylene content 93 mol%, MFR = 15 g /
10 minutes, density 0.89 g / cm^Three) 100 parts, basic substance
Maleic anhydride graph acting as dispersant depending on quality
Polyethylene (maleic acid content 3.3% by weight, weight average
Equivalent molecular weight 2700, density 0.94 g / cm ^Three) 10 copies,
And, 5 parts of oleic acid is put into a pressure kneader,
Melt and knead at 140 ° C for 30 minutes. Next, anhydrous maleic
Acid-grafted polyethylene and all carboxylic acids of oleic acid
Potassium hydroxide (basic substance) necessary for neutralization
20 parts of the dissolved alkaline water were added to a pump connected to a kneader.
Press in for 5 minutes using a pump. The pressure inside the kneader is 3k
g / cm^TwoIt became. After continuing kneading for 30 minutes,
The contents were taken out after cooling to 60 ° C. The contents are
It was a white solid. Pour 10 parts of white solid into 10 parts of water
After stirring with a turbine blade stirrer, 100 mesh
It was filtered through a wire mesh. No residue was found. Got
Olefin emulsion has a solid content of 50%, pH 10
The weight average particle diameter by light scattering measurement is 0.80 μm.
there were. Polymerization of acrylic monomer (b) 140 parts of obtained olefin emulsion, deionized
Charge 152 parts of water into a reaction vessel and reach 80 ° C under a nitrogen stream.
The temperature rose. Separately, 15 parts of styrene, acrylic acid
15 parts of 2-ethylhexyl, benzoyl peroxide
0.3 parts of dodecylbenzenesulfur in 12 parts of deionized water
Emulsified mixture emulsified with 0.12 parts of sodium phonate
And the emulsified mixture is dropped into the reaction vessel in 3 hours.
Then, the mixture was further maintained at the same temperature for 4 hours to complete the polymerization.
I let you. The obtained emulsion has a nonvolatile content of 30% and a pH of 1
0, the weight average particle diameter by light scattering measurement is 0.83 μm
Met.

Example 2 A reaction vessel was charged with 100 parts of the olefin-based emulsion obtained in Example 1 and 165 parts of deionized water, and heated to 80 ° C. under a nitrogen stream. Separately, 25 parts of styrene, 25 parts of 2-ethylhexyl acrylate, and 0.5 part of benzoyl peroxide were added to 20 parts of deionized water in sodium dodecylbenzenesulfonate.
The emulsified mixture was emulsified using 2 parts, and the emulsified mixture was dropped into the reaction vessel in 3 hours, and then kept at the same temperature for 4 hours to complete the polymerization. The obtained emulsion had a nonvolatile content of 30% and a pH of 10, and had a weight average particle size of 0.87 μm as measured by light scattering.

Comparative Example 1 The olefin emulsion produced in Example 1 was directly used for evaluation.

Comparative Example 2 197 parts of deionized water and 0.1 part of sodium dodecylbenzenesulfonate were charged into a reaction vessel and heated to 80 ° C. under a nitrogen stream. After the temperature was raised, 1 part of potassium persulfate was poured into the reaction vessel. Separately, 50 parts of styrene and 50 parts of 2-ethylhexyl acrylate were added to 40 parts of sodium dodecylbenzenesulfonate in 40 parts of deionized water.
The emulsified mixture was emulsified using 3 parts, and the emulsified mixture was dropped into the reaction vessel in 3 hours, and then kept at the same temperature for 4 hours to complete the polymerization. The obtained emulsion had a nonvolatile content of 30% and was adjusted to pH 10 with aqueous ammonia. Weight average particle size by light scattering measurement is 0.11
μm. The obtained emulsion composition was evaluated by the following method. The results are shown in the table.

[Evaluation Example 1] A polypropylene (PP) plate,
And a film thickness of 20 on a polyacryl (MMA) plate after drying.
The emulsion composition is applied to a thickness of
For 30 minutes. After standing at room temperature for one day and night, JIS K
The adhesion was tested according to the method of 5400 8.5.2. Table 1 shows the evaluation results.

[Evaluation Example 2] An emulsion composition was applied on a 25 μm-thick polyethylene terephthalate (PET) film to a dry thickness of 10 μm.
Dry at 10 ° C. for 1 minute. Furthermore, a film thickness of 50 μm is applied on the coating surface.
m LDPE (low density polyethylene) film,
Under conditions of 100 ° C., 50 kg / cm ² and 50 cm / min, the PET film and the LDPE film were bonded. The bonding strength of the laminated film is 50m
It was measured at m / min. Table 2 shows the evaluation results.

[Table 1] Results of Evaluation Example 1 {Emulsion base material type}種 Composition type PP board MMA board ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 100/100 100/100 Example 2 90/100 100/100 ─────────────────────────── Comparative Example 1 100/100 0/100 ────────────── ─────────────── Comparative Example 2 0/100 100/100 ━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━

[Table 2] Results of Evaluation Example 2 {Emulsion PET / LDPE composition type [g / 25 mm]} ━━━━━━━━━━━━━ Example 1 220 ──────────────────── Example 2 250 ───────── ─────────── Comparative Example 1 5 比較 Comparative Example 2 2 ━━━━━━━━━━━ ━━━━━━━━━

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Keiichi Taki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. term (reference) 4F100 AH02 AK01B AK01C AK03A AK03B AK03J AK04A AK04J AK07A AK07J AK09A AK09J AK12A AK12J AK25A AK25J AK64A AK65A AK68A AK70 AK80A AL01A AL04 AL05A AP00B AP00C AT00B AT00C BA02 BA03 BA06 BA07 BA10B BA10C BA13 DE01A DG10B DG10C DG15B DG15C EH46 EH66B EH66C JB09A JK01 JK06 JM01A JN01 YY00A 4J002 BB03W BB05W BB06W BB12W BB14W BB15W BB17W BC04X BC09X BE03W BF03W BG04X BG05X BG06X BG07X BK00W BL01W BL02W BP02W CE00W FD090 FD140 FD090 FD090 FD090 FD090 FD140

Claims (21)

[Claims] 1. A laminated structure comprising a layer containing an olefin polymer (A) and an acrylic polymer (B). 2. 95 to 10% by weight of the olefin polymer (A) and the acrylic polymer (B) based on the total weight of the olefin polymer (A) and the acrylic polymer (B).
The laminated structure according to claim 1, which is 5 to 90% by weight. 3. The olefin polymer (A) according to claim 1, wherein the olefin polymer (A) includes a (co) polymer of the olefin monomer (a-1). 3. The laminated structure described in 1. above. 4. The olefin polymer (A) is at least one selected from the group consisting of an ethylene / butene copolymer, an ethylene / propylene copolymer, and an ethylene / butene / propylene copolymer. The laminated structure according to any one of claims 1 to 3, wherein the laminated structure comprises: 5. The laminated structure according to claim 1, wherein the “olefin-based polymer (A)” includes an ethylene-vinyl acetate copolymer. 6. An olefin polymer (A) comprising a copolymer of an olefin monomer (a-1) and a monomer (a-2) other than the olefin monomer. The laminated structure according to any one of claims 1 to 5, wherein the laminated structure is formed. 7. The ratio of the olefin monomer (a-1) to the monomer (a-2) other than the olefin monomer is such that the olefin monomer (a-1) and the olefin monomer 99.9-35.0% by weight of the olefin-based monomer (a-1), based on the total weight of the monomer (a-2) other than the -2) The laminated structure according to claim 6, wherein the content is 0.1 to 65.0% by weight. 8. A monomer other than the olefin-based monomer (a
The laminated structure according to claim 6 or 7, wherein (2)) contains at least a part of a monomer containing no carboxyl group. 9. A monomer other than the olefin monomer (a)
The laminated structure according to claim 6 or 7, wherein the compound (2) contains only a monomer not containing a carboxyl group. 10. The laminated structure according to claim 8, wherein the “monomer (a-2) other than the olefin-based monomer” is “vinyl acetate”. 11. The laminated structure according to claim 1, wherein the acrylic polymer (B) comprises a polymer of an acrylic monomer (b). 12. The laminate according to claim 11, wherein the “acrylic monomer (b)” contains at least a part of a monomer having a water solubility of 0.0 to 0.5%. Structure. 13. The laminated structure according to claim 11, wherein the “acrylic monomer (b)” contains at least a part of a monomer having no carboxyl group. 14. The laminated structure according to claim 11, wherein the “acrylic monomer (b)” contains only a monomer having no carboxyl group. 15. The acrylic monomer (b) contains at least a part of styrene and / or 2-ethylhexyl acrylate.
5. The laminated structure according to any one of 4. 16. An olefin emulsion in which a layer containing the olefin polymer (A) and the acrylic polymer (B) is used as a step 1 in which resin particles containing the olefin polymer (A) are dispersed in water. Emulsion in which resin particles containing an olefin polymer (A) and an acrylic polymer (B) in the same particles obtained by polymerizing an acrylic monomer (b) are dispersed in water 16. The method according to any one of claims 1 to 15, wherein the method comprises a step of producing a composition, and a step of applying and drying the emulsion composition obtained in the step 1 as a step 2. A laminated structure according to any one of the above. 17. The resin particles having a weight average particle diameter of 10 n
The laminated structure according to claim 16, wherein the thickness is from m to 500 μm. 18. The laminated structure according to claim 16, wherein an initiator having a water solubility of 0 to 10% is used when polymerizing the acrylic monomer (b). . 19. The layer other than the layer containing the olefin polymer (A) and the acrylic polymer (B) is at least one selected from plastic, plastic film, vapor-deposited film, paper, nonwoven fabric, and wood. The laminated structure according to any one of claims 1 to 18. 20. The laminated structure according to claim 19, wherein one of the layers in contact with the layer containing the olefin polymer (A) and the acrylic polymer (B) is a polyolefin layer. 21. The laminated structure according to claim 20, wherein the polyolefin layer is a polyolefin film.