JPH1088089A - Water-base adhesive composition and laminating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To avoid the occurrence of roll marks in right-turn gravure coating and improve the appearance of a laminate by incorporating a water-base resin and a specific acetylene glycol into a water-base adhesive. SOLUTION: This water-base adhesive compsn. contains a water-base polyurethane resin and/or a water-base acrylic resin, 0.5-8wt.% acetylene glycol represented by the formula (R<1> to R<4> are each H or a 1-10C org. group; and m and n are each 0-3), and 1-10wt.% polyoxyethylene-polyoxyalkylene copolymer. This laminating method comprises coating a flexible substrate with the compsn. by rightturn gravure coating to form an adhesive layer, smoothing the surface of the adhesive layer with a smoothing roll, drying the layer with a dryer, and sticking another flexible substrate to the surface of the layer. The acetylene glycol and the polyoxyethylene-polyoxyalkylene copolymer may be added by any method. The figure shows the concept of right-turn gravure coating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The aqueous adhesive composition of the present invention is used for laminating flexible substrates such as plastic films, metal foils, metallized films and paper.
The aqueous adhesive composition of the present invention and the laminated product produced by the laminating method using the same exhibit excellent transparency and smoothness.

[0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous adhesive composition suitable for forward gravure coating and a laminating method using the same. The normal rotation gravure coating is, as shown in FIG. 1, at the contact point between the web and the gravure roll, the gravure roll is rotated in the forward direction with respect to the flow of the web, and the adhesive is transferred and the adhesive coating is applied. With a coating method of smoothing with a smoothing roll, the normal rotation gravure coating aptitude is that when the adhesive is coated by the above method, the roll surface does not occur and the coated surface of the adhesive can be coated smoothly. Indicates aptitude.

[0003] Forward gravure coating is generally used for coating an organic solvent type adhesive. However, when a water-based adhesive is applied by forward rotation gravure coating, rolls are generated, and even if smoothing is performed with a smoothing roll, there is a problem that the appearance of the laminated product is poor due to the rolls. It was difficult to apply the water-based adhesive in the work. Usually, reverse gravure coating, reverse roll coating, and rod coating are used for the aqueous adhesive. However, in recent years, the adhesive has been made more water-based, and the necessity of applying the water-based adhesive by forward gravure coating, which has a high market penetration rate, has increased.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an aqueous adhesive composition and a water-based adhesive composition characterized in that roll appearance does not occur in forward gravure coating and the appearance of a laminated product is improved. It is an object of the present invention to provide a laminating method using the same.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have conducted research to develop an aqueous adhesive composition suitable for forward gravure coating and a laminating method using the same. As a result, the aqueous resin containing acetylene glycol, or the aqueous adhesive composition containing an acetylene glycol and an aqueous resin containing a polyoxyethylene polyalkylene copolymer, the above object, that is, good forward rotation The present inventors have found that gravure suitability can be expressed in an aqueous adhesive, and have completed the present invention.

That is, a first constitution of the present invention is an aqueous adhesive composition, which comprises an aqueous resin and a compound represented by the following general formula (1):

[0007]

Embedded image

(Where R ¹ , R ² , R ³ and R ⁴ are hydrogen or an organic group having 1 to 10 carbon atoms, m = 0 to 3, n = 0 to 0)
1 to 20% by weight of the acetylene glycol represented by 3)
It relates to an aqueous adhesive composition characterized by containing.

The first composition further comprises an aqueous resin, 0.5 to 8% by weight of an acetylene glycol represented by the general formula (1) based on the aqueous resin, and a polyoxyethylene polyalkylene. The present invention relates to an aqueous adhesive composition containing 1 to 10% by weight of a copolymer.

Further, the present invention provides an aqueous adhesive comprising an aqueous resin, a crosslinking agent, and 1 to 20% by weight of the acetylene glycol represented by the general formula (1) based on the aqueous resin. Agent composition.

Further, the present invention provides an aqueous resin, a crosslinking agent, and 0.5 to 8% of an acetylene glycol represented by the general formula (1) based on the aqueous resin, and a polyoxyethylene polyalkylene. The present invention relates to an aqueous adhesive composition containing 1 to 10% of a copolymer.

Further, the present invention relates to an aqueous adhesive composition wherein the aqueous resin is a polyurethane resin and / or an acrylic resin.

[0013] In a second aspect of the present invention, the above-mentioned aqueous adhesive composition is applied to a flexible substrate by a forward gravure coating method to form an adhesive layer, and then applied by a smoothing roll. The present invention relates to a laminating method characterized in that the surface is smoothed, and after drying with a drier, the adhesive-coated surface is bonded to another flexible substrate.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Acetylene glycol has the general formula (1)

[0015]

Embedded image

(Where R ¹ , R ² , R ³ , R ⁴ are hydrogen or an organic group having 1 to 10 carbon atoms, m = 0 to 3, n = 0 to
3).

Examples of those containing acetylene glycol include, for example, R ¹ , R ⁴ = (CH ₃ ) ₂ CHCH ₂ ,
Surfynol 104 consisting of 100% acetylene glycol with R ² , R ³ ＣＨCH ₃ , m = 0, n = 0;
R ¹ , R ⁴ = (CH ₃ ) ₂ CHCH ₂ , R ² , R ³ = CH ₃ ,
Surfynol 420 consisting of 100% acetylene glycol with m = 1 and n = 1, R ¹ , R ⁴ = (CH ₃ ) ₂ C
Surfynol 44 consisting of 100% acetylene glycol with HCH ₂ , R ² , R ³ ＣＨCH ₃ , m = 2, n = 2
0, R ¹ , R ⁴ = CH ₃ CH ₂ , R ² , R ³ = CH ₃ , m =
Surfynol 82 consisting of 100% acetylene glycol with 0 and n = 0, Surfynol 104E diluted with ethylene glycol, Surfynol 104E containing 50% Surfynol 104, Surfynol 104
Is diluted with isopropyl alcohol, and Surfynol 10
Surfynol 104PA containing Surfynol 104 containing 50%
Surfynol 104H and Surfynol 104 diluted with dipropylene glycol monomethyl ether, and Surfynol 104 DPM and Surfynol 104 containing 50% Surfynol 104 were diluted with butyl cellosolve and 50% Surfynol 104, respectively.
Surfynol 104BG, Surfynol 1
Surfynol SE-F, Surfynol TG, Surfinol GA, Surfynol CT-111, Surfynol CT-136, Surfynol CT-15 containing Surfynol 104 diluted with a surfactant
1, Surfynol DF-110D, Surfinol 5
04 (both manufactured by Air Products).
The substance containing acetylene glycol is not limited to these, and any substance having acetylene glycol represented by the general formula (1) can be used.

When acetylene glycol is used alone to impart forward gravure suitability to the aqueous adhesive, the acetylene glycol addition rate is 1 to 20%, preferably 2 to 10%, based on the aqueous resin solution.

Any known polyoxyethylene polyoxyalkylene copolymer can be used. As the polyoxyethylene polyoxyalkylene copolymer, ethylene oxide is used as an essential component, and is further copolymerized with at least one of monomers such as propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene by block or random copolymerization. And at least one of monomers such as propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc., having ethylene oxide as an essential component using an alkyl alcohol having 1 to 4 carbon atoms as an initiator.
Examples include those obtained by block or random copolymerization with a seed. Preferably, the polyoxyethylene polyalkylene copolymer contains at least 1 to 50% by weight of ethylene oxide repeating units, and has a molecular weight of 100 to 10,000, preferably 300 to 400.
0 is a polyoxyethylene polyoxyalkylene copolymer.

Examples of the polyoxyethylene polyoxyalkylene copolymer include Pluronic L-31, Pluronic L35, Pluronic L-42, Pluronic L-43, Pluronic L-44, and Pluronic L-L.
61, Pluronic L-62, Pluronic L-63,
Pluronic L-64, Pluronic P-65, Pluronic F-68, Pluronic L-72, Pluronic L-81, Pluronic P-84, Pluronic P-8
5, Pluronic L-92, Pluronic P-94, Pluronic L-101, Pluronic L-121, Pluronic L-122 (all manufactured by Asahi Denka Kogyo KK),
Epan 410, Epan 420, Epan 450, Epan 6
10, Epan 710, Epan 720, Epan 740, Epan 750 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Pionin P-1525, Pionin P2310, Pionin P-2535, Pionin P-3750, Pionin P
4015, Pionin P-0735-B, Pionin P
-1050-B, Pionin P-1525-B, Pionin P-1750-B, Pionin P-1425-B Pionin P-1440-L (all Takemoto Yushi Co., Ltd.)
Manufactured), Unilube 50MB-2, Unilube 50MB-
5, Unilube 50MB-11, Unilube 50MB-
26, Unilube 50MB-72, Unilube 50MB
-168, Unilube 25TG-55 (Nippon Oil & Fats Co., Ltd.)
Manufactured). However, as the polyoxyethylene polyoxyalkylene copolymer which is a requirement of the present invention,
It is not limited to these.

Addition of acetylene glycol and polyoxyethylene polyoxyalkylene copolymer to aqueous resin when acetylene glycol and polyoxyethylene polyoxyalkylene copolymer are used in combination to impart forward gravure suitability to the aqueous adhesive The ratio is 0.5 to 8% of acetylene glycol and 1 to 10% of polyoxyethylene polyalkylene copolymer based on the aqueous resin solution.

Any method can be used for adding the acetylene glycol and the polyoxyethylene polyoxyalkylene copolymer to the aqueous resin. For example, a method of simply mixing the aqueous resin and the acetylene glycol or the polyoxyethylene polyoxyalkylene copolymer with stirring after the synthesis of the aqueous resin, the organic solvent with the acetylene glycol or the polyoxyethylene polyoxyalkylene copolymer. A method of mixing the aqueous resin and the acetylene glycol with stirring after the aqueous resin is synthesized in a state where it is easily dissolved and dispersed in the aqueous resin, dissolving the acetylene glycol or the polyoxyethylene polyoxyalkylene copolymer in a surfactant. A method of mixing the aqueous resin and the acetylene glycol or the polyoxyethylene polyoxyalkylene copolymer with stirring after the synthesis of the aqueous resin in a state in which the acetylene glycol is easily dispersed in the aqueous resin; Or a method of adding a polyoxyethylene polyoxyalkylene copolymer, or the like, but the method of adding the acetylene glycol or the polyoxyethylene polyoxyalkylene copolymer is not limited thereto. Absent.

As the aqueous resin, any aqueous resin that can be used as an adhesive can be used.
The aqueous resin is a form dispersed in water by a known method, and includes any of a water-soluble resin, a dispersion, and an emulsion. The particle size of the aqueous resin is not particularly limited, but is preferably 500 nm or less.

Examples of the water-based resin include a polyurethane resin, an acrylic resin, a polyester resin, a polyamide resin, an epoxy resin, a polyurea resin, a polyurethane urea resin, a modified vinyl resin, a simple substance of natural rubber, and a composite resin thereof. it can. Preferably, a polyurethane resin, an acrylic resin, or a composite resin of a urethane resin and an acrylic resin and a crosslinking agent thereof are used. Any known method of emulsifying these resins can be used.

Any known crosslinking agents can be used. As the cross-linking agent, any compound or resin having a functional group that undergoes a cross-linking reaction with the resin-containing functional group can be used. Examples of the functional group of the crosslinking agent include an epoxy group, an isocyanate group, an oxazoline group, an aziridine group, a hydrazine group, a keto group, an amino group, a silyl group, a silanol group, a carboxyl group, a carbodiimide group, and a zirconium group.

Examples of the crosslinking agent having an epoxy group include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and trimethylolethanetriol. Aliphatic polyepoxy compounds such as glycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether; epoxy compounds of bisphenol A or bisphenol F type; polyglycidyl ethers such as xylylenediamine; Or a hydrophilic group-containing compound containing a repeating unit of ethylene oxide Part modified polyepoxy compound of hydrophilic self-emulsifying, and the like are. The trade names include Epicron EM85-75W, CR-75, Dick Fine EM60 (Dainippon Ink Chemical Industry Co., Ltd.)
), Epicoat DX-255 (manufactured by Mitsubishi Yuka Shell Epoxy Co., Ltd.), Aquatoto 510 (Toto Kasei Co., Ltd.)
Manufactured), Denacol EX-721, EX-EX-313,
EX-314, EX-321, EX-421, EX-5
12, EX-521, EX-810, EX-811, E
X-832, EX-851, EX-861 (manufactured by Nagase Kasei Kogyo Co., Ltd.), Epolite 400E, 200E, 4
0E (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

Examples of the crosslinking agent containing an isocyanate group include 2,4-tolylene diisocyanate,
6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 2,4'-
Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-
4,4'-biphenylene diisocyanate, 3,3'-
Dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate,
1,5-tetrahydronaphthalenediisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,
3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, 3,3'- Polyisocyanate compounds such as dimethyl-4,4'-dicyclohexylmethane diisocyanate, or isocyanurate type or burette type trifunctional polyisocyanates, or terminal isocyanate group-containing prepolymers obtained by reaction with difunctional or higher functional polyol compounds. Examples thereof include those in which an emulsifier is blended with a substantially hydrophobic polyisocyanate such as a polymer so as to be dispersed in water. Further, a self-emulsifiable polyisocyanate compound obtained by copolymerizing a hydrophilic group-containing compound containing a repeating unit of alkylene oxide with the polyisocyanate may be used. As a product name,
As the polyisocyanate compound, CR-60N (manufactured by Dainippon Ink and Chemicals, Inc.), Aquanate 100,
110, 200, 210 (Nippon Polyurethane Industry Co., Ltd.)
And DisModule 0772 (manufactured by Sumitomo Bayer Urethane Co., Ltd.).

Examples of the crosslinking agent containing an oxazoline group include Epocross K-1020, K-2020,
WS-500 (manufactured by Nippon Shokubai Chemical Co., Ltd.).

The crosslinking agent containing an aziridine group includes
For example, Chemitite PZ-33, DZ-22, MZ-1
1, HZ-22 (manufactured by Nippon Shokubai Chemical Co., Ltd.).

The crosslinking agent containing a hydrazine group includes
For example, hydrazine, ethylene-1,2-hydrazine,
Propylene-1,3-dihydrazine, butylene-1,4
-Dividrazine, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide,
And itaconic dihydrazide.

Examples of the crosslinking agent containing a silyl group or a silanol group include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) urea , 3-ureidopropyltrimethoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-
Aminosilanes such as trimethoxysilane and hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
And mercaptosilanes such as mercaptopropyl-methyldimethoxysilane. As a product name,
KBE1003, KBC1003, KBM403, KB
M503, KBM603, KBM602, KBM80
3, KBE903 (manufactured by Shin-Etsu Silicone Co., Ltd.), A-1
50, A-172, A-186, A-187, A-18
9, A-1100, A-1120, A-1160, Y-
9669 (manufactured by Nippon Unicar Co., Ltd.).

As the cross-linking agent containing a carbodiimide group, carbodilite V-02, V-0
4, V-06 (manufactured by Nisshinbo Co., Ltd.).

Examples of the crosslinking agent containing a zirconium group include zirconium acetate, zirconium carbonate, and Baycoat 20 (manufactured by Nippon Light Metal Co., Ltd.) as trade names.

Preferably, the crosslinking agent containing an epoxy group includes Epicron EM85-75W, CR-75,
Dick Fine EM60 (manufactured by Dainippon Ink and Chemicals, Inc.), Epicoat DX-255 (manufactured by Mitsubishi Yuka Shell Epoxy Co., Ltd.), Aquatoto 510 (manufactured by Toto Kasei Co., Ltd.), EX-314, EX-512 And (made by Nagase Kasei Kogyo Co., Ltd.). As a crosslinking agent containing an isocyanate group, as a polyisocyanate compound, CR-60N (manufactured by Dainippon Ink and Chemicals, Inc.), Aquanate 100, 110, 200, 2
10 (manufactured by Nippon Polyurethane Industry Co., Ltd.) and DisModule 0772 (manufactured by Sumitomo Bayer Urethane Co., Ltd.). Examples of the crosslinking agent containing an oxazoline group include WS-500 (manufactured by Nippon Shokubai Chemical Co., Ltd.). Examples of the crosslinking agent containing an aziridine group include Chemitite PZ-33 (manufactured by Nippon Shokubai Chemical Co., Ltd.). As a crosslinking agent containing a silyl group and a silanol group, KBE1003, KB
C1003, KBM403, KBM503, KBM60
3, KBM602, KBM803, KBE903 (manufactured by Shin-Etsu Silicone Co., Ltd.), A-150, A-172, A-
186, A-187, A-189, A-1100, A-
1120, A-1160, and Y-9669 (manufactured by Nippon Unicar Co., Ltd.). Examples of the crosslinking agent containing a carbodiimide group include carbodilite V-02 and V
-04 and V-06 (manufactured by Nisshinbo Co., Ltd.).

The crosslinking agent is not limited to these, and any known crosslinking agent can be used.

The acetylene glycol or the acetylene glycol and the polyoxyethylene polyalkylene copolymer are required to be contained in an aqueous resin, and may be contained in any of the resin and the crosslinking agent. However, the aqueous adhesive composition comprising the present aqueous resin has the above-mentioned resin as a main component and the above-mentioned crosslinking agent as a curing agent.
Often used in liquid type. In this case, acetylene glycol, or acetylene glycol and a polyoxyethylene polyalkylene copolymer, are added in advance to a curing agent having a small blending amount, and an adhesive is used in order to maintain the effect of developing forward gravure suitability. It is preferable that a method of mixing two liquids consisting of a main agent and a curing agent be used on site.

When the aqueous adhesive composition is used, in addition to the above components, known emulsifiers, antioxidants, stabilizers,
An adhesion promoter, a leveling agent, an antifoaming agent, a plasticizer, a tackifying resin, a coloring agent such as a pigment, a usable time extending agent, and the like can be used. As the adhesion promoter, silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like are preferably used. Rosin derivatives and the like are preferably used as the tackifying resin.

In the laminating method of the present invention, the aqueous adhesive composition is coated on a flexible substrate by forward gravure coating to form an adhesive layer, and then the adhesive layer is smoothed with a smoothing roll. After drying the adhesive layer, the adhesive-formed surface and another flexible substrate are thermocompression-bonded to obtain a laminated product.

When the aqueous adhesive composition of the present invention is applied by the laminating method of the present invention, the aqueous adhesive composition of the present invention may be diluted with a diluent. At that time, the diluted aqueous adhesive composition of the present invention contains acetylene glycol in an amount of 0.3 to 20%, preferably 0.6 to 10%,
Or 0.1 to 8% of acetylene glycol and 0.3 to 10 of polyoxyethylene polyalkylene copolymer.
%. As the diluent, any known diluent can be used, but water is preferable in order not to lose the characteristic of being aqueous. When the diluted aqueous adhesive composition of the present invention is applied, the solid content as a coating liquid is 10 to 50%, preferably 20 to 40%.

The amount of the adhesive applied in the laminating method of the present invention is 0.5 to 50 g / m ² -dry, preferably 1 to 10 g / m ² -dry.
g / m ² -dry.

As the flexible substrate used in the mining method of the present invention, for example, PVC, PET, biaxially stretched P
P, unstretched PP, PE, nylon, polyvinyl alcohol, vinylidene chloride coated OPP, polystyrene, EV
Various plastic films such as OH, polycarbonate, cellophane, etc., various metal-deposited films, silica-deposited films, metal foils and the like can be used.

As the gravure roll used for the gravure coating in the laminating method of the present invention, any known gravure roll can be used.

The smoothing roll used in the laminating method of the present invention is a cylindrical roll having a smooth surface or a cylindrical roll having a Mayer bar shape. The material of the smoothing roll is not particularly limited. In the smoothing roll of the present invention, the smoothing roll may rotate in the forward or reverse direction with respect to the flow of the web at the contact point between the web and the smoothing roll, but preferably rotates in the reverse direction.

As the dryer used in the laminating method of the present invention, any known dryer can be used. For example, a hot air dryer, an infrared irradiation dryer, a microwave irradiation dryer, or a drying device using at least two or more of these dryers can be used. The drying temperature is from 40 to 180C, preferably from 60 to 80C.
The laminated product obtained by the above laminating method is usually cultivated at room temperature, but may be heated and cultivated.

Thus, an aqueous adhesive composition comprising an aqueous resin containing 1 to 20%, preferably 2 to 10% of the acetylene glycol of the present invention, or 0.5 to 8% of acetylene glycol, and An aqueous adhesive composition comprising an aqueous resin containing 1 to 10% of a polyoxyethylene polyalkylene copolymer and a laminating method using the same are provided by an adhesive coating method for laminating various films. In the forward gravure coating, it is possible to produce a laminated product having high smoothness and transparency without generating rolls.

[0046]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

(1) Preparation Example of Resin A Dick Dry WS-304A (made by Dainippon Ink and Chemicals, Inc.), which is an adhesive made of an aqueous urethane resin having a nonvolatile content of 40% and is used for dry lamination of a plastic film. Was designated as resin A.

(2) Preparation Example of Resin B Hydran HW-311 (manufactured by Dainippon Ink and Chemicals, Inc.), which is an adhesive made of an aqueous urethane resin having a nonvolatile content of 35% and used for dry lamination of a plastic film, was used. Resin B was used.

(3) Preparation Example of Resin C Hydration L-5503A (made by Dainippon Ink and Chemicals, Inc.) which is an adhesive made of an aqueous acrylic resin having a nonvolatile content of 45% and is used for dry lamination of a plastic film. ) Was designated as resin C.

(4) Preparation Example of Resin D 115 parts by weight of styrene, 290 parts by weight of butyl acrylate, 75 parts by weight of ethyl acrylate, 10 parts by weight of N-methylolacrylamide, 7.5 parts by weight of acrylic acid, dimethylaminoethyl methacrylate 5 parts by weight was used as a monomer mixture, and this mixture was used for Aqualon HS-10 1
Using 0 parts by weight, the emulsion was emulsified in 130 parts by weight of ion-exchanged water to prepare a pre-emulsion. The reaction vessel was charged with 570 parts of ion-exchanged water, and the inside of the reaction vessel was heated to 70 ° C. while stirring while supplying nitrogen gas. After temperature rise, Dick Dry WS-305A (aqueous polyurethane adhesive composition) 6
25 parts by weight, 15 parts of the pre-emulsion were charged into a reaction vessel, and then 1 part of a 0.75% ferric chloride aqueous solution, 0.5 part of ammonium persulfate, and 0.3 part of sodium pyrosulfite were added. Pre-emulsion, 2.0 parts of ammonium persulfate dissolved in 50 parts of ion-exchanged water, 1.2 parts of sodium pyrosulfite in 5 parts of ion-exchanged water
Each of the components dissolved in 0 parts was dropped and polymerized using a dropping funnel. The dropping time was 3 hours, and the temperature in the flask was maintained at 70 ° C. during this time. After completion of the dropwise addition, the mixture was further kept at 70 ° C. for 2 hours, cooled, adjusted to a pH of about 7.5 with 10% aqueous ammonia, and a composite aqueous resin of a polyurethane resin and an acrylic resin having a nonvolatile content of 45% was synthesized. This composite aqueous resin of a polyurethane resin and an acrylic resin was designated as resin D.

(5) Preparation Example of Aqueous Adhesive Composition E 52.3 parts by weight of polypropylene glycol having an OH value of 280 and 329.1 parts of polypropylene glycol having an OH value of 56
Parts by weight, neopentyl glycol 8.8 parts by weight, dimethylolpropionic acid 35.2 parts by weight, polyoxyethylene polyoxypropylene copolymer (molecular weight about 3000,
(EO / PO = 50/50% by weight) 29.4 parts by weight and 173.3 parts by weight of isophorone diisocyanate were reacted to obtain a prepolymer solution having a terminal isocyanate group. Next, this prepolymer was diluted with 314 parts by weight of MEK and 314 parts by weight of isopropanol, and 54.7 parts by weight of isophoronediamine was added thereto with stirring to extend the chain. By adding 26.5 parts by weight of triethylamine, propionic acid in the polyurethane resin was neutralized. Next, 70.9 parts by weight of Surfynol 104 was charged and sufficiently stirred. Further, ion-exchanged water 1064
A part by weight was added dropwise, the phase inversion emulsification of the polyurethane resin was performed, and then the solvent was removed.
A water-based adhesive composition E having a terminal amine having a white appearance of 0 mPa · s was prepared. This aqueous adhesive composition contains 4% of Surfynol 104, which is acetylene glycol.

The above resin and the additive of the present invention were blended as shown in Tables 1 to 4 below to prepare an aqueous adhesive composition of the present invention.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

The abbreviations in Tables 1 to 4 represent the following. : Surfynol 104 Acetylene glycol manufactured by Air Products Co.: Pluronic L-61 Polyoxyethylene polyoxyalkylene copolymer manufactured by Asahi Denka Kogyo Co., Ltd.: Pluronic L-64 Polyoxyethylene polyoxyalkylene manufactured by Asahi Denka Kogyo Co., Ltd. Polymer: LB-60 Water-dispersed epoxy resin-based crosslinker manufactured by Dainippon Ink and Chemicals, Inc .: L-60B Water-dispersed epoxy resin-based crosslinker manufactured by Dainippon Ink and Chemicals, Inc .: CR-5L Dainippon Ink and Chemicals Industrial Co., Ltd. epoxy resin crosslinking agent

Coating and lamination were carried out using the aqueous adhesive compositions shown in Tables 1 to 4. Tables 5 to 7 show the lamination conditions and the evaluation results.

[0059]

[Table 5]

[0060]

[Table 6]

[0061]

[Table 7]

The abbreviations shown in Tables 5 to 7 indicate the following. Coating substrate (substrate on which adhesive is coated by gravure): OPP # 25 Taiko FOR 25 μm manufactured by Nimura Chemical Co., Ltd. Laminating substrate (base on which adhesive is bonded to substrate coated by gravure) Material): CPP # 30 Pyrene film CT P-1128E, 30 μm, manufactured by Toyobo Co., Ltd. Gravure roll: 150 L * 50, 150 lines, plate engraving grid type gravure with 50 μm depth: 170 L * 30, 170 lines, 30 μm plate depth Engraving plate grid type gravure smoothing (Smooth cylindrical metal roll with chrome plating on the surface) Coating amount: (g / m ² ) in dry state Line speed: (m / min) Appearance evaluation: ＝= Roll Good appearance equivalent to solvent-based adhesive: × = rolls appear and poor appearance

[0063]

The water-based adhesive composition and the laminating method of the present invention can be used for laminating in a forward gravure coating, in which a water-based adhesive does not generate a roll but has a good finished appearance equivalent to that of an organic solvent type, even though it is a water-based adhesive. Made it possible to get things.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a normal rotation gravure coating method.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 171/02 C09J 171/02 175/04 175/04

Claims (6)

[Claims] 1. An aqueous resin and, with respect to the aqueous resin, a general formula (1): (Where R ¹ , R ² , R ³ , and R ⁴ are hydrogen or carbon 1
An aqueous adhesive composition comprising 1 to 20% by weight of an acetylene glycol represented by the following formula: 2. An aqueous resin and acetylene glycol represented by the general formula (1) in an amount of 0.5 to 8 based on the aqueous resin.
An aqueous adhesive composition comprising 1% by weight and 1 to 10% by weight of a polyoxyethylene polyalkylene copolymer. 3. An aqueous adhesive composition comprising an aqueous resin, a crosslinking agent, and 1 to 20% by weight of acetylene glycol represented by the general formula (1) based on the aqueous resin. 4. An aqueous resin, a crosslinking agent, and 0.5 to 8% of an acetylene glycol represented by the general formula (1) and a polyoxyethylene polyalkylene copolymer based on the aqueous resin. An aqueous adhesive composition comprising 1 to 10%. 5. The aqueous adhesive composition according to claim 1, wherein the aqueous resin is a polyurethane resin and / or an acrylic resin. 6. An adhesive layer is formed by applying the aqueous adhesive composition according to claim 1 to a flexible substrate by a forward gravure coating method, and then the applied surface is smoothed with a smoothing roll. And laminating the adhesive-coated surface and another flexible substrate after drying with a drier.