JPH1077455A - Adhesive composition for dry laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for dry laminate which is water soluble, does not give any bad effect to environment, has a performance comparable to a solvent type urethane, is excellent in adhesion between plastic films, plastic film and aluminum foil, and plastic film and metal vapor deposition film, moreover, is resistant to hot water, and cheap. SOLUTION: This adhesive composition comprises an aqueous resin dispersed solution (A) and a hydrazine derivative (B) having at least two hydrazine groups in a molecule, and the aqueous resin dispersed solution (A) is obtd. by the emulsion polymerization of a monomer mixture comprising 0.1-8wt.% unsaturated monomer contg. a carbonyl group, 50-85wt.% 4-18C alkyl ester of acrylic acid, 0.1-3wt.% unsaturated monomer having phosphate group, and 15-49.8wt.% other copolymerizable unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition for dry lamination, and more particularly to a plastic film, a plastic film and an aluminum foil, or
The present invention relates to an adhesive composition for dry lamination that gives excellent adhesion when used for laminating a plastic film and a metallized film, and has an excellent hot water resistance so that the obtained laminate can withstand hot water.

[0002]

2. Description of the Related Art Conventionally, as an adhesive composition for dry lamination, a solvent type adhesive made of polyurethane having ethyl acetate or the like as a main solvent has been used. Such a solvent-type adhesive has excellent adhesiveness, but has a problem in that the solvent is released into the atmosphere during coating, adversely affects the environment such as odor, and also saves resources.

[0003] In recent years, solvent-free polyurethanes and aqueous polyurethanes have been developed to address the above problems. However, the above-mentioned solventless adhesive requires not only a special laminator, but also has a shortage of hot water resistance and is expensive in price, and the above-mentioned aqueous adhesive is not suitable in terms of adhesive performance. It is enough. In recent years, metal-deposited films have become widespread mainly for the purpose of improving the preservability of foods, and it is desired to improve the adhesive strength between a plastic film and a metal-deposited film.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has as its object that there is no fear of adversely affecting the environment because it is water-based, and it is comparable to solvent-type polyurethane. To provide an adhesive composition for dry lamination having excellent performance, excellent adhesiveness between plastic films, between plastic film and aluminum foil, or between plastic film and metal-deposited film, and which is hot water resistant and inexpensive. is there.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned crosslinkable composition comprising an aqueous dispersion of an acrylic resin containing a certain amount of carbonyl groups and phosphate groups and a hydrazine derivative has the above-mentioned properties. It was found that the object of the invention could be achieved.

The present invention has been completed on the basis of the above findings, and the gist of the present invention is to provide an aqueous resin dispersion (A) and a hydrazine derivative (B) having at least two hydrazino groups in the molecule. And the resin aqueous dispersion (A)
Is a carbonyl group-containing unsaturated monomer (a) 0.1 to 8% by weight, an acrylic acid alkyl ester having 4 to 18 carbon atoms (b) 50 to 85% by weight, an unsaturated monomer having a phosphate group Emulsion polymerization of a monomer mixture consisting of 0.1 to 3% by weight of the compound (c) and 15 to 49.8% by weight of another unsaturated monomer copolymerizable with these unsaturated monomers (d) The adhesive composition for dry lamination, which is an aqueous resin dispersion obtained by the above method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The adhesive composition for dry lamination of the present invention contains an aqueous resin dispersion (A) and a hydrazine derivative (B) having at least two hydrazino groups in a molecule. Then, in the preparation of the resin aqueous dispersion (A) in the present invention,
The following components (a) to (d): an unsaturated monomer having a carbonyl group (a), an alkyl ester of acrylic acid having 4 to 18 carbon atoms (b), and an unsaturated monomer having a phosphate group (C) and other unsaturated monomers (d) copolymerizable with these unsaturated monomers are used.

The carbonyl group-containing unsaturated monomer as the component (a) is a polymerizable polymer containing at least one carbonyl group (excluding a carbonyl group based on a carboxyl group and a carboxylic ester group) in the molecule. Is an unsaturated monomer having a polymerizable double bond containing at least one carbonyl group based on an ald group or a keto group in a molecule. .

Specific examples of the above component (a) include, for example, acrolein, diacetone acrylamide, formylstyrene, vinyl alkyl ketone (preferably 4 to
Vinyl alkyl ketones having 7 carbon atoms, such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, etc.), diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-
Hydroxypropyl acrylate acetyl acetate,
Examples thereof include butanediol-1,4-acrylate acetyl acetate and acryl (or methacryl) oxyalkylpropanal represented by the following general formula (1).

[0010]

Embedded image

In the above general formula (1), R ¹ is H or CH
₃ , R ² is H or an alkyl group having 1 to 3 carbon atoms, R ³ is an alkyl group having 1 to 3 carbon atoms, R
⁴ represents an alkyl group having 1 to 4 carbon atoms.

Among the above components (a), acrolein, diacetone acrylamide and vinyl methyl ketone are preferred. The component (a) may be used in combination of two or more.

The above component (a) is used in an amount of usually 0.1 to 8% by weight, preferably 0 to 8% by weight, based on the total unsaturated monomers used for preparing the aqueous resin dispersion (A). .3-5
% By weight. When the use ratio of the component (a) is less than 0.1% by weight, the adhesive strength tends to be inferior. Conversely, when the amount exceeds 8% by weight, the hardness of the adhesive film becomes too high and the shrinkage stress is too low. Since relaxation cannot be performed, the adhesive strength after lamination tends to decrease.

Specific examples of the above-mentioned component (b), an alkyl ester of acrylic acid having 4 to 18 carbon atoms (b), include n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate and n-butyl acrylate. Octyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, palmityl acrylate, stearyl acrylate, and the like are included, but in particular, it is easy to adjust the adhesive film strength,
N-butyl acrylate or 2-ethylhexyl acrylate is preferably used because it has good copolymerizability.

The above-mentioned component (b) has the function of imparting surface tackiness to the adhesive composition of the present invention and also maintaining the flexibility of the obtained laminated material. The amount of the component (b) used is usually 50 to 85% by weight, preferably 6% by weight, based on the total unsaturated monomers used for preparing the resin aqueous dispersion (A).
0 to 80% by weight. When the use ratio of the component (b) is less than 50% by weight, the above functions cannot be sufficiently obtained, and
If the amount is more than 10% by weight, the adhesive strength after lamination tends to decrease as a result of the decrease in the film cohesion of the adhesive composition of the present invention.

Specific examples of the unsaturated monomer (c) having a phosphate group as the component (c) include acid phosphoxyethyl (meth) acrylate and acid phosphoxypropyl (meth) acrylate Acid phosphoxy polyoxyethylene glycol mono (meth) acrylate, acid phosphoxy polyoxypropylene glycol mono (meth) acrylate, N-acid phosphoxyethyl acrylamide, N-acid phosphoxypropyl acrylamide, and the like. .

The component (c) has the effect of improving the adhesive strength after lamination of the metal-deposited film and the plastic film. Component (c) is used in an amount of usually 0.1 to 3% by weight, preferably 0.4 to 3% by weight, based on the total amount of the unsaturated monomers used for preparing the aqueous resin dispersion (A).
2% by weight. Component (c) is used in an amount of 0.1% by weight.
If it is less than 3, the above function cannot be obtained sufficiently.
If the amount is more than 10% by weight, further improvement of the function is not recognized, and there is a problem that the adhesive layer is whitened when the laminate is immersed in hot water.

Specific examples of the unsaturated monomer (d) which can be copolymerized with the unsaturated monomer, which is the component (d), include methyl acrylate, ethyl acrylate, and acrylic acid. Lower alkyl esters of acrylic acid such as n-propyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lower alkyl esters of methacrylic acid such as butyl methacrylate, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, acetic acid Vinyl, vinyl propionate, ethylene, vinyl chloride, vinylidene chloride and the like.

Further, specific examples of the above component (d) include unsaturated monomers having an amide group such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, acrylic acid,
Examples include carboxyl group-containing unsaturated monomers such as methacrylic acid, itaconic acid, and maleic acid, and derivatives thereof.

When the adhesive composition for dry lamination of the present invention contains a water-dispersible isocyanate according to a preferred embodiment described later, the component (d) includes glycidyl acrylate as a component for crosslinking with an isocyanate group-containing compound. And unsaturated monomers having an epoxy group such as glycidyl methacrylate, and unsaturated monomers having a hydroxyl group such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.

The component (d) has functions of adjusting the strength of the adhesive composition of the present invention and stabilizing the production of the aqueous resin dispersion (A). Component (d) is used in an amount of usually 15 to 49.8% by weight, preferably 25 to 40% by weight, as a percentage of the total unsaturated monomers used in the preparation of the aqueous resin dispersion (A). is there.

In the preparation of the aqueous resin dispersion (A),
From the viewpoints of further increasing the adhesive strength after lamination, improving the stability of the aqueous resin dispersion against mechanical stress, and improving the physical properties of the film when a crosslinking agent is used, a part of the component (d) is used. As, it is preferable to use the aforementioned carboxyl group-containing unsaturated monomer, the amount of which is used,
The proportion in the total unsaturated monomers used for preparing the resin aqueous dispersion (A) is usually 0.2 to 5% by weight, preferably 0.3 to 3% by weight. When the amount of the carboxyl group-containing unsaturated monomer is less than 0.2% by weight, the above-mentioned effect of sufficiently improving the performance is not recognized. Conversely, when the amount exceeds 5% by weight, the laminated material is heated. There are problems such as whitening of the adhesive layer when immersed in water.

Emulsion polymerization for obtaining the resin aqueous dispersion (A) can be carried out according to a conventional method. That is, in water containing a dispersant, emulsifier, protective colloid, etc.,
The monomer mixture comprising the above components (a) to (d) is emulsion-polymerized at a temperature of, for example, 80 to 95 ° C. in the presence of a polymerization initiator. The method of supplying the monomer may be a batch charging method, a sequential addition method of the monomer, or a method of adding the monomer after forming the aqueous emulsion.

Examples of the emulsifier include anionic surfactants such as higher alcohol sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkylphenol ether sulfates, and various nonionic surfactants. Anionic surfactants can be used. Further, a reactive emulsifier having a polymerizable double bond in the molecule may be used. The amount of the emulsifier to be used is generally 0.2 to 10% by weight based on all unsaturated monomers.

As the above protective colloid, (1) 3-
5 to 80% by weight of a monoolefinically unsaturated carboxylic acid unit having 5 carbon atoms, (2) an alkyl ester unit having 1 to 8 carbon atoms of acrylic acid or methacrylic acid, a styrene unit, a (meth) acrylonitrile unit, 20 to 95% by weight of at least one unit selected from the group of saturated carboxylic acid vinyl ester units, (3) monoolefinically unsaturated carboxylic acid amide unit, N-alkyl of the carboxylic acid amide, N-alkyl of the carboxylic acid amide At least 1 unit selected from the group of roll derivatives, 0 to 30% by weight,
(4) a copolymer containing 0 to 50% of a monomer unit containing at least one carbonyl group in the molecule, or
A neutralized product of the same copolymer can be used.

In particular, when the copolymer protective colloid containing the monomer unit of the above (4) is used, the protective colloid is integrated with the resin molecule by crosslinking, and is formed by the adhesive composition of the present invention. The adhesive strength and hot water resistance of the adhesive layer are enhanced.

Examples of the polymerization initiator include persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, peroxide catalysts such as benzoyl peroxide and di-t-butyl peroxide, and azobisisobutyro. An azo catalyst such as nitrile or azobisisobutyric acid nitrile is used. Further, a redox initiator using a reducing agent may be used.

In the present invention, the hydrazine derivative (B) containing at least two hydrazino groups in the molecule used for preparing the adhesive composition is usually 2 to 10
Dihydrazide, which is a dehydration condensate of a dicarboxylic acid having 4 to 6 carbon atoms with hydrazine, an aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms, and the like are used.

Specific examples of the above dicarboxylic acid dihydrazide include oxalic acid dihydrazide, malonic acid dihydrazide,
Succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and the like. Specific examples of the above aliphatic water-soluble dihydrazine include ethylene-1, 2-dihydrazine, propylene-1,3-dihydrazine, butylene-
1,4-dihydrazine and the like can be mentioned.

As the hydrazine derivative (B), a polymer having a hydrazino group represented by the following general formula (2) can also be used. Such a polymer having a hydrazino group is disclosed in, for example, JP-A-55-653.
No. 5 discloses this in detail.

[0031]

Embedded image

In the above general formula (2), X is a hydrogen atom or a carboxyl group, Y is a hydrogen atom or a methyl group, and A is acrylamide, methacrylamide, acrylate, methacrylate or maleic anhydride. And B is a monomer unit of acrylamide, methacrylamide, acrylate, methacrylate or maleic anhydride. Further, k, m and n are numbers satisfying the following equations.

[0033]

1 mol% ≦ k ≦ 100 mol% 0 mol% ≦ (m + n) ≦ 95 mol% (k + m + n) = 100 mol%

The amount of the hydrazine derivative used in the present invention is selected from the range of usually 0.1 to 5 mol, preferably 0.3 to 2 mol, as the ratio of the hydrazino group to 1 mol of the carbonyl group in the component (A). Is done.

The adhesive composition of the present invention containing the resin aqueous dispersion (A) and the hydrazine derivative (B) exhibits extremely excellent adhesive properties as an adhesive composition for dry lamination, When used in applications where hot water treatment is used, in addition to the above components (A) and (B), (C)
If one or more compounds selected from the group consisting of an epoxy group-containing compound containing at least two epoxy groups in a molecule, a water-dispersible isocyanate compound, a polyoxazoline compound and a carbodiimide compound are contained, It is preferable because the hot water resistance is further improved.

Examples of the above epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and glycerin polyglycol. Polyglycidyl ether of polyhydric alcohols such as glycidyl ether, pentaerythritol polyglycidyl ether, sorbitan polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether of bisphenol A, alicyclic epoxy resin, nitrogen-containing epoxy resin, polybutadiene epoxy resin And urethane-modified epoxy resins.

The water-dispersible isocyanate compound is not particularly limited, but is generally derived from a nonionic group (for example, polyoxyalkylene group) or an anionic group (for example, carboxylic acid, sulfonic acid or phosphonic acid). An isocyanate compound containing a hydrophilic group is used. And the number of functional groups of the isocyanate group may be two or three or more. Specific examples of such an isocyanate compound include a reaction product of an excess polyisocyanate compound and a polyol compound, a reaction product of a polyisocyanate compound and a polyamine compound,
Allophanate compounds obtained by reacting hydrogen in urethane bonds with isocyanate groups, and burette compounds obtained by reacting hydrogen in urea bonds with isocyanate groups are exemplified. For example, the product “Basonat FDS 3425” (product name) manufactured by BASF is
It is an example of a suitable water-dispersible isocyanate compound. In particular, a water-dispersible isocyanate compound having three or more isocyanate groups is preferable.

As the above-mentioned polyoxazoline-based compound, a compound having at least two oxazoline rings in the molecule and being compatible with the above-mentioned component (A) is generally used. Specific examples of such polyoxazoline-based compounds include “Epocross K-1010E”, “Epocross K-1020E”, and “Epocross K-10” manufactured by Nippon Shokubai Co., Ltd.
50E "," Epocross CX-K-2010E ",
"Epocross CX-K2020E", "Epocross
CX-K2030E "(all are trade names).

The carbodiimide compound described above includes
Specifically, the product “X” manufactured by Union Carbide Co., Ltd.
L-29SE "(trade name).

The amount of each component (C) used is usually 0.5 to 100 parts by weight of the component (A) as a solid content ratio.
A range of 10 parts by weight is suitable.

Further, other resin components can be added to the adhesive composition of the present invention as long as the physical properties are not impaired. Examples of the resin component include a water-soluble resin such as a cellulose resin, an acrylic resin, shellac, casein, and a polyester resin, and an alkali-soluble resin, and an aqueous resin dispersion such as an acrylic resin emulsion and a urethane resin emulsion. Further, in the adhesive composition of the present invention, various types of dispersants, defoamers, thickeners, wetting agents, solvents, plasticizers, antifreeze agents, etc. Can be added.

The aqueous resin dispersion (A) in the present invention comprises:
It is common to neutralize with a neutralizing agent after producing by emulsion polymerization. Here, a volatile basic compound such as ammonia or triethylamine can be used as the neutralizing agent. And when using a laminate container for food applications, since volatile basic compounds migrate to the contents through the sealant base material and emit an odor, it is not preferable,
It is preferable to use an inorganic alkali compound or a nonvolatile amine as the neutralizing agent. Examples of the inorganic alkali compound include sodium hydroxide, potassium hydroxide and the like,
Examples of the non-volatile amine include diethanolamine, triethanolamine, diethylenetriamine, diazabicyclooctene and the like.

The ammonia component present in the aqueous resin dispersion (A) according to the present invention includes, in addition to ammonia as a neutralizing agent, an anionic surfactant used in emulsion polymerization, ammonium persulfate and the like. Some are derived from agents. Therefore, it is necessary to consider the above points when designing the emulsion polymerization depending on the use of the adhesive composition of the present invention.

[0044]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist of the present invention. In the following, “parts” and “%” indicate parts by weight and% by weight, respectively.

The evaluation was performed in the following manner. That is, using the adhesive composition for dry lamination obtained in each of Examples and Comparative Examples, a laminate of a film was prepared by the following method, and a dry lamination strength test, a seal strength test, and a water boiler were performed. The test was performed.

(1) Production of film laminate: The adhesive composition for dry lamination was diluted with water until the solid content concentration became 30%, and a gravure reverse method was performed using a dry laminator (manufactured by Modern Machinery). And coated on a stretched polypropylene film (hereinafter abbreviated as OPP film) and a nylon film (hereinafter abbreviated as Ny film) so that the amount of the adhesive applied is 3 g / m ² (in terms of solid content). After drying with OPP film, unstretched polypropylene film (hereinafter referred to as CPP)
Film-abbreviated film), aluminum-deposited unstretched polypropylene film (hereinafter abbreviated as VM-CPP film), CPP film and VM-
CPP film line speed 100 mm / min, laminated at a nip pressure 1.6 kg / cm ^2, to obtain a film laminate by performing post-processing for 2 days under an atmosphere temperature of 40 ° C.. Other manufacturing conditions are as shown in Table 1 below.
Details of each film used are as shown in Table 2 below.

[0047]

[Table 1] <Drying temperature> First stage heater: 60 ° C Second stage heater: 70 ° C Third stage heater: 80 ° C

[0048]

<Table 2><Film> OPP film: “P-21” manufactured by Toyobo Co., Ltd.
61 ", thickness 30 μm Ny film: trade name“ Emblem ”manufactured by Unitika Ltd., thickness 15 μm CPP film: trade name“ P-11 ”manufactured by Toyobo Co., Ltd.
21 ”, 30 μm thick VM-CPP film:“ ML ”manufactured by Toyo Cellophane Co., Ltd.
Film CP-WA ”, thickness 25μm

(2) Dry lamination strength test: The film laminate prepared by the above method was subjected to a width of 15 mm and a length of 15 mm.
The film was cut into 0 mm, and using an Instron tensile tester (manufactured by Instron), the peel strength at the time of T-peeling of both laminated films at a head speed of 300 mm / min was measured. / 15 mm).

(3) Seal strength test: A test piece having the same size as that for measuring the laminate strength was used, and the CPP film faces or the VM-CPP films were put together.
The sample was pressed at a pressure of ² kg / cm ² for 1 second with a heat sealer (manufactured by Toyo Seiki Co., Ltd.) heated to 160 ° C. to obtain a sample having a seal width of 15 mm × 20 mm. Then, using an Instron tensile tester, a head speed of 300 m
When a tensile test was performed on the test piece at m / min, the strength at which the seal surface was peeled was measured, and the value (Kg / 15 m
m).

(4) Water boiling test: Ny film / CP
The P film laminate was formed into a bag, water was poured into the bag, and the mouth was sealed. Then, the bag was immersed in hot water of 90 ° C. for 30 minutes, and the suitability for water boiling was evaluated from the change in appearance. Evaluation is shown in Table 3 below.
The following three steps were performed.

[0052]

A: No change is observed in appearance. B: Streak-like or pinhole-like laminar floating is observed. C: Lami floating is observed on the entire surface.

Example 1 A temperature controller, an irrigating stirrer, a reflux cooler, a supply vessel,
Water 250 in a reactor equipped with a thermometer and nitrogen inlet
And 5 parts of a 30% aqueous solution of sodium salt of p-nonylphenol sulfate (anionic emulsifier) reacted with 20 mol of ethylene oxide.

Separately, a feed (I) shown in Table 4 below was prepared, and an initiator solution prepared by dissolving 6 parts of sodium persulfate in 100 parts of water was prepared as the feed (II).

[0055]

[Table 4]

After the inside of the reactor previously supplied with the anionic emulsifier solution was purged with nitrogen, 10% of the above-mentioned feed (I) was added into the reactor, and the mixture was heated to 85 ° C. Next, 10% of the feed (II) was injected into the reactor, and the feed (I) and the remainder of the feed (II) were gradually and uniformly mixed in parallel over 4 hours. Supplied. After the completion of the supply, the mixture was emulsion-polymerized while maintaining the temperature at 90 ° C. for 1.5 hours, cooled, and then adjusted to pH 8 with triethanolamine to obtain a copolymer aqueous dispersion. The solids content of the aqueous copolymer dispersion was about 49%. Next, 12 parts of adipic dihydrazide were added to the obtained aqueous resin dispersion,
The mixture was stirred and mixed for 1 hour to obtain an adhesive composition for dry lamination.

Table 7 shows the evaluation results of the obtained adhesive composition. Table 6 shows the types and amounts of the monomer composition, the type of the neutralizing agent, and the amount of the hydrazine derivative.
The symbol “TEA” for the type of neutralizer is triethanolamine,
The symbol “ADH” of the hydrazine derivative type indicates adipic hydrazide, and “SDH” indicates sebacic hydrazide (the same applies hereinafter). Further, “phosphate group-containing monomer 1” indicates acid phosphoxyethyl acrylate, and “phosphate group 2” indicates N-acid phosphoxyethyl acrylamide (the same applies hereinafter).

Examples 2 to 4 and Comparative Examples 1 to 7 Table 6 (Examples 2 to 4) shows the monomer composition, the kind of the neutralizing agent, the kind of the hydrazine derivative and the amount used in the emulsion polymerization.
4) and Table 12 and Table 14 (Comparative Examples 1 to 7), respectively, and the dry laminate adhesive composition was prepared according to the method described in Example 1 except for the above. Table 7 also shows the evaluation results of the adhesive compositions of Examples 2 to 4. Comparative Example 1
Tables 13 and 15 show the evaluation results of the adhesive compositions of Nos. 7 to 7.

Examples 5 to 11 The monomer composition, the kind of the neutralizing agent, the kind of the hydrazine derivative and the amount of the hydrazine derivative used in the emulsion polymerization were added to 100 parts of the compositions prepared as shown in Tables 8 and 10, respectively. The additives shown in Tables 8 and 10 were blended, and an adhesive composition for dry lamination was prepared according to the method described in Example 1. The meanings of the symbols indicating the types of the additives in each table are as shown in Table 5 below. Tables 9 and 11 show the evaluation results of the obtained adhesive composition.

[0060]

[Table 5] a: glycerin triglycidyl ether b: propylene glycol diglycidyl ether c: water-dispersible isocyanate (trade name “Basonat FDS 3425” manufactured by BASF) d: polyoxazoline compound (trade name “Nippon Shokubai Co., Ltd.”) Epocross K-1010E ") e: carbodiimide compound (trade name" XL-29SE "manufactured by Union Carbide)

[0061]

[Table 6] ──────────────────────────────────── Example 1 2 3 4 <single amount Body composition (parts)> Acrolein 1.5-1.5-Diacetone acrylamide-5.0-5.0 N-butyl acrylate 70.0-70.0-2-Ethylhexyl acrylate-65.0-65.0 Methyl methacrylate 26.8 10.0 26.0 10.0 Styrene-17.8-15.0 Acrylamide 1.5 2.0-1.0 Acrylic acid--1.5 1.0 Phosphate group-containing monomer 1 0.2 0.2--Phosphate group-containing monomer 2--1.0 3.0 <Neutralizer> Type TEA TEA TEA TEA <Hydrazine derivative> Type ADH SDH ADH SDH amount _{(parts) 1.2 3.4 1.2 3.4 -NHNH 2 /} CO ( molar ratio) 0.5 1.0 0.5 1.0 <additives> type - - - - amount added (parts) - - - - ──────── ──────────────── ────────────

[0062]

[Table 7] ──────────────────────────────────── Example 1 2 3 4 <Lamination strength (G / 15 mm)> OPP / CPP 220 240 230 260 Ny / CPP 610 600 570 610 OPP / VM-CPP 130 140 150 170 Ny / VM-CPP 150 140 160 180 <Seal strength (Kg / 15 mm)> OPP / CPP 1.4 1.6 1.7 1.8 Ny / CPP 4.0 4.1 4.1 4.2 OPP / VM-CPP 1.1 1.2 1.2 1.4 Ny / VM-CPP 3.1 3.4 3.3 3.2 <Water boil suitability> B B B B ──────────── ────────────────────────

[0063]

[Table 8] ──────────────────────────────────── Example 5 6 7 8 <single amount Body composition (parts)> Acrolein 1.5-1.5-Diacetone acrylamide-5.0-5.0 N-butyl acrylate 70.0-70.0-2-Ethylhexyl acrylate-65.0-65.0 Methyl methacrylate 26.8 10.0 26.0 10.0 Styrene-17.8-15.0 Acrylamide 1.5 2.0-1.0 Acrylic acid--1.5 1.0 Phosphate group-containing monomer 1 0.2 0.2--Phosphate group-containing monomer 2--1.0 3.0 <Neutralizer> Type TEA TEA TEA TEA <Hydrazine derivative> Type ADH SDH ADH SDH amount _{(parts) 1.2 3.4 1.2 3.4 -NHNH 2 /} CO ( molar ratio) 0.5 1.0 0.5 1.0 <additives> type a b c d amount (parts) 1.5 1.5 5.0 10.0 ──────── ─────────────── ────────────

[0064]

[Table 9] ──────────────────────────────────── Example 5 6 7 8 <Lamination strength (G / 15mm)> OPP / CPP 330 300 360 360 Ny / CPP 620 610 600 640 OPP / VM-CPP 150 170 180 180 Ny / VM-CPP 170 190 200 190 <Seal strength (Kg / 15mm)> OPP / CPP 2.0 1.9 2.0 2.0 Ny / CPP 4.4 4.3 4.5 4.1 OPP / VM-CPP 1.5 1.3 1.4 1.4 Ny / VM-CPP 3.8 3.7 3.7 3.6 <Water boiling suitability> A A A A ──────────── ────────────────────────

[0065]

[Table 10] Example 9 10 11 <Monomer Composition (parts)> Acrolein 1.5-1.5 Diacetone acrylamide-5.0-N-butyl acrylate 70.0-70.0 2-Ethylhexyl acrylate-65.0-Methyl methacrylate 26.8 10.0 26.0 Styrene-17.8-Acrylamide 1.5 2.0-Acrylic acid--1.5 Phosphoric acid group-containing monomer 1 0.2 0.2-Phosphate group-containing monomer 2--1.0 <Neutralizer> Type TEA NaOH Triethylamine <Hydrazine derivative> Type ADH SDH ADH Addition amount (parts) 1.2 3.4 1.2 -NHNH ₂ / CO (molar ratio) 0.5 1.0 0.5 <Additives> Type ebc Addition amount (parts) 1.5 1.5 5.0 ───────────────────────── ───────────

[0066]

[Table 11] ──────────────────────────────────── Example 9 10 11 <Laminate strength ( g / 15 mm)> OPP / CPP 330 300 360 Ny / CPP 620 610 600 OPP / VM-CPP 150 170 180 Ny / VM-CPP 170 190 200 <Seal strength (Kg / 15 mm)> OPP / CPP 2.2 2.1 2.1 Ny / CPP 4.6 4.3 4.3 OPP / VM-CPP 1.6 1.4 1.3 Ny / VM-CPP 3.8 3.6 3.6 <Water boiling suitability> A A A ────────────────────── ──────────────

[0067]

[Table 12] Comparative Example 1 2 3 4 <single amount Body composition (parts)> Acrolein-1.5 1.5-Diacetone acrylamide---10.0 N-butyl acrylate 70.0 70.0 70.0-2-Ethylhexyl acrylate---65.0 Methyl methacrylate 27.0 27.0 23.0 4.0 Styrene---18.0 Acrylamide 1.5 1.5 1.5 2.0 Acrylic acid----Phosphate group-containing monomer 1 1.5-4.0 1.0 Phosphate group-containing monomer 2----<Neutralizer> Type TEA TEA TEA TEA <Hydrazine derivative> Type ADH ADH ADH SDH addition amount (parts) 1.2 1.2 1.2 6.8 -NHNH ₂ / CO (molar ratio) 0.5 0.5 0.5 1.0 ────────────────────────── ──────────

[0068]

[Table 13] Comparative Example 1 2 3 4 <Laminate strength (G / 15 mm)> OPP / CPP 40 230 210 60 Ny / CPP 90 610 580 90 OPP / VM-CPP 30 70 180 40 Ny / VM-CPP 50 90 180 80 <Seal strength (Kg / 15 mm)> OPP / CPP 0.6 1.7 1.6 0.8 Ny / CPP 0.7 4.1 4.4 0.9 OPP / VM-CPP 0.4 0.5 1.4 0.6 Ny / VM-CPP 0.7 1.8 3.6 0.8 <Water boil suitability> C B C B ──────────── ────────────────────────

[0069]

[Table 14] Comparative Example 5 67 <Monomer Composition (parts)> Acrolein 1.5 1.5 1.5 Diacetone acrylamide---N-butyl acrylate 44.0 87.0 70.0 2-Ethylhexyl acrylate---Methyl methacrylate 52.0 9.0 26.0 Styrene---Acrylamide 1.5 1.5 1.5 Acrylic acid--- Phosphate group-containing monomer 1-1.0 1.0 Phosphate group-containing monomer 2 1.0--<Neutralizing agent> Type TEA TEA TEA <Hydrazine derivative> Type ADH ADH-Amount added (parts) 1.2 1.2--NHNH ₂ / CO (molar ratio) 0.5 0.5 − ────────────────────────────────────

[0070]

[Table 15] Comparative Example 5 6 7 <Laminate strength ( g / 15 mm)> OPP / CPP 40 70 30 Ny / CPP 80 100 50 OPP / VM-CPP 30 60 20 Ny / VM-CPP 50 90 30 <Seal strength (Kg / 15 mm)> OPP / CPP 0.6 0.5 0.5 Ny / CPP 0.9 0.8 0.7 OPP / VM-CPP 0.5 0.4 0.4 Ny / VM-CPP 0.8 0.7 0.7 <Water boil aptitude> B B C ────────────────────── ──────────────

[0071]

According to the present invention described above, there is provided a solvent-free type having no adverse effect on the environment, and
Provided is an inexpensive dry laminating adhesive composition that has performance comparable to that of solvent-based polyurethane and is inexpensive. The adhesive composition of the present invention provides excellent adhesiveness particularly when used for laminating plastic films, plastic film and aluminum foil, or metal-deposited film, and the resulting laminate is made of hot water. It has excellent hot water resistance that can withstand even heat.

Claims (4)

[Claims] 1. A resin aqueous dispersion (A) and a hydrazine derivative (B) having at least two hydrazino groups in a molecule, wherein the resin aqueous dispersion (A) is a carbonyl group-containing unsaturated monomer. Monomer (a) 0.1 to 8% by weight, alkyl ester of acrylic acid having 4 to 18 carbon atoms (b) 5
0 to 85% by weight, unsaturated monomer having a phosphate group (c)
A monomer mixture comprising 0.1 to 3% by weight and 15 to 49.8% by weight of another unsaturated monomer (d) copolymerizable with these unsaturated monomers is obtained by emulsion polymerization. An adhesive composition for dry lamination, which is an aqueous resin dispersion. 2. A carboxyl group-containing unsaturated monomer in an amount of 0.2 to 5% by weight in the total monomer mixture as at least a part of another unsaturated monomer (d). Adhesive composition for dry lamination. 3. The adhesive composition for dry lamination according to claim 1, wherein the ratio of the hydrazino group in the component (B) is 0.1 to 5 mol per 1 mol of the carbonyl group in the component (A). . 4. In addition to the components (A) and (B), as component (C), at least two epoxy groups are present in the molecule.
The dry laminate according to any one of claims 1 to 3, which comprises one or more compounds selected from the group consisting of an epoxy group-containing compound, a water-dispersible isocyanate, a polyoxazoline-based compound and a carbodiimide-based compound. Adhesive composition.