WO2006109395A1

WO2006109395A1 - Adhesive for laminate

Info

Publication number: WO2006109395A1
Application number: PCT/JP2006/305107
Authority: WO
Inventors: Yukihiro Morikawa; Tadayuki Kawaguchi; Takanori Kobayashi; Takashi Taguchi
Original assignee: Nippon Polyurethane Industry Co., Ltd.
Priority date: 2005-03-31
Filing date: 2006-03-15
Publication date: 2006-10-19
Also published as: JP2006282768A; TW200643133A; CN101146883A; KR100918458B1; KR20070086029A; CN101146883B; JP4771276B2

Abstract

Disclosed is an adhesive for laminates which has high initial adhesion, high productivity and good workability while maintaining excellent resistance to contents. Specifically disclosed is an adhesive for laminates composed of a base material solution and an isocyanate curing agent. The base material solution contains at least a polyurethane resin, a silane coupling agent and an organic solvent, and the polyurethane resin is obtained by reacting the following components (A), (B), (C) and (D) at a mass ratio of (A)/(B)=95/5-75/25 (A) a polyester polyol containing an aromatic ring in a molecule wherein a hydroxyl group substantially forms a molecular end (B) a polyester polyol containing no aromatic ring in a molecule (C) a dimethylolalkanoic acid (D) an organic polyisocyanate

Description

Specification

Laminating adhesive

Technical field

[0001] The present invention relates to an adhesive particularly suitable for dry lamination of a film of metal or the like.

Background art

[0002] Recently, as a packaging method, composite flexible packaging due to its strength, product protection, workability at the time of packaging, transmission effect by packaging, large amount of plastic material, reduction of packaging cost by cheap supply, etc. Has developed significantly.

As an adhesive used for laminating such a film, in general, it has excellent adhesion performance, cold resistance, and heat resistance, and has a wide range of application to substrates such as various plastics and metal foils. Two-component polyurethane adhesives consisting of a main agent having an active hydrogen group such as a hydroxyl group and a curing agent having an isocyanate group have become mainstream.

However, the current two-component polyurethane laminate adhesive requires a curing acceleration process called aging because the curing reaction of the adhesive after bonding is very slow. Specifically, it is necessary to cure the adhesive by storing and aging the laminated film in a 35-60 ° C storage room for about 3-5 days. At this time, since the degree of curing of the adhesive varies depending on the aging conditions, it may affect the adhesive strength of the laminating film. If the aging is insufficient, delamination due to poor curing of the adhesive ( May cause delamination. Particularly in the case of an aliphatic polyurethane adhesive, this curing reaction takes a considerably long time. Therefore, such an aging process is an indispensable process in the dry lamination process, and there is an expense such as capital investment for the installation of a greenhouse for aging and utility for the subsequent heat insulation. It was necessary.

[0003] In order to solve these points and shorten the curing time, thereby improving the production efficiency and improving the coating and adhesion performance, Patent Document 1 describes (a) diethylene glycol-based polyester polyol polyol and ( There has been proposed an adhesive for dry laminate containing b) a carboxyl group-containing aromatic polyester polyol and (c) a polyisocyanate. This (b) force Since a ruboxyl group-containing aromatic polyester polyol is obtained by reacting a polyester polyol with a water-free aromatic polyvalent carboxylic acid, the molecular end of the polyester polyol is a carboxyl group. As a result, the laminated film packaging material manufactured using the dry laminate adhesive disclosed in Patent Document 1 is filled with food or pharmaceuticals as the contents and used for high temperature processing such as boiling and retort. Although the content performance such as adhesion performance, hot water resistance, and acid resistance could be improved, the appearance (peeling) of finoleum after high temperature treatment was rather deteriorated.

Patent Document 1: Japanese Unexamined Patent Publication No. 2000-154365

Disclosure of the invention

Problems to be solved by the invention

[0004] An object of the present invention is to provide an adhesive for laminating with excellent productivity and workability with high initial adhesiveness while maintaining excellent content resistance performance.

Means for solving the problem

[0005] The inventors of the present invention use (A) a rigid polyester polyol containing an aromatic ring in the molecule and (B) another flexible polyester polyol as a raw material for a polyurethane resin that is a main component of the main agent. In addition, the present inventors have found that the above problem can be solved by introducing a carboxyl group at a specific site in the resin, and have completed the present invention.

That is, the present invention includes the following (1) to (3).

(1) A polyurethane resin obtained by reacting at least the following (A), (B), (C) and (D) at a mass ratio (A) Z (B) = 95Z5 to 75Z25, A laminating adhesive comprising: a main agent solution containing a silane coupling agent and an organic solvent; and an isocyanate curing agent.

(A) Polyesterol having an aromatic ring in the molecule and having substantially a hydroxyl group at the molecular end

(B) A polyester polyol that does not contain an aromatic ring in the molecule

(C) Dimethylolalkanoic acid

(D) Organic polyisocyanate

[0007] (2) The laminating adhesive according to (1), wherein both (A) and (B) are viscous liquids at room temperature. [0008] (3) The adhesive for laminating according to (1) or (2), wherein (C) is dimethylolbutanoic acid. The invention's effect

[0009] Laminate films such as plastic films and metal foils produced using the laminating adhesive of the present invention have excellent peel resistance and adhesion such as initial peel adhesive strength and normal peel adhesive strength. The performance is also excellent. In addition, it was confirmed that there was no abnormality such as delamination in the appearance of the laminate film after boiling or retort treatment, and that it maintained practical adhesive strength. As a result, in film production, tunneling can prevent the film from shifting, and the productivity and workability are also improved.

Therefore, according to the present invention, the productivity and workability of the laminate film are greatly improved, and the cost can be reduced and the delivery time can be shortened.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] Hereinafter, the present invention will be described in detail.

The laminating adhesive of the present invention comprises at least a main agent solution and an isocyanate curing agent.

The main agent solution in the present invention contains a polyurethane resin, a silane coupling agent, and an organic solvent.

The polyurethane resin in the main agent solution comprises (A) a polyester polyol having an aromatic ring in the molecule and a molecular end substantially having a hydroxyl group, and (B) a polyester polyol having no aromatic ring in the molecule, polyester polyol ( It is obtained by reacting C) dimethylolalkanoic acid with (D) organic polyisocyanate.

Further, (A) Mass ratio of polyester polyol having an aromatic ring in the molecule and a molecular terminal substantially having a hydroxyl group and (B) polyester polyol not having an aromatic ring in the molecule (A) / (B) Is from 95/5 to 75/25.

[0011] (A) Polyester polyol contains an aromatic ring in the molecule, but the molecular terminal is substantially a hydroxyl group (that is, a carboxyl group does not substantially exist at the molecular terminal, ). Specifically, the acid value of the polyester polyol is preferably 1 mgK0H / g or less.

Specific examples of (A) polyester polyols include terephthalic acid and isophthalanol. A polyester polyol obtained by a dehydration condensation reaction of an aromatic dicarboxylic acid such as an acid, its acid ester, an acid anhydride, and the like with a polyol, or the aromatic dicarboxylic acid, its acid ester, an acid anhydride, etc., and a succinic acid, Polyester obtained by dehydration condensation reaction of non-aromatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, acid esters, acid anhydrides, etc. Examples thereof include a polyol, or a mixture of a polyester polyol obtained by a dehydration condensation reaction of the aromatic dicarboxylic acid, its acid ester, acid anhydride and the like with a polyol, and another polyester polyol. Examples of such polyester polyols (other than this) include polyester polyols obtained by dehydration condensation reaction of non-aromatic dicarboxylic acids, their acid esters, acid anhydrides and the like with polyols, and ε Rataton-based polyester polyols obtained by ring-opening polymerization of cyclic ester (ie, latatane) monomers such as prolatatatone, alkyl-substituted ε-force prolatatone, δ-valerolataton, alkyl-substituted δ-valerolataton, and the like.

Of these, polyester polyols obtained by a dehydration condensation reaction of the aromatic dicarboxylic acid, its acid ester, acid anhydride, etc. with non-aromatic dicarboxylic acid, their acid ester, acid anhydride, etc. and polyol are preferred. .

Examples of the polyol include ethylene glycol, 1,3-propylene glycol, 1,2_propylene glycol, 1,4-butylene glycol, 1,5_pentandaricone, 1,6-hexane glycol, 3_Methyl_1,5_Pentandalycol, 2_Butyl_2—Ethyl_1,3_Propanediol, Neopentylglycol, 1,8_Octaneglycol, 1,9-Nonanediol, Diethylene glycol, Cyclohexane 1, 1,4-dio mononole, cyclohexane _ 1, 4_ dimethanol, dimer acid dinore, trimethylololepropane, glycerin, hexanetriol, or glycols such as ethylene oxide or propylene oxide adducts thereof And triol.

Any of these may be used alone or in admixture of two or more.

It should be noted that because of availability (inexpensive and generally industrially produced, etc.), the aromatic ring has an acid component (specifically, the aromatic dicarboxylic acid, its acid ester, and acid anhydrate). Etc.), preferably introduced from. [0012] (B) The polyester polyol does not contain an aromatic ring in the molecule, and specifically includes, for example, dicarboxylic acids other than the above-mentioned aromatics, their acid esters, acid anhydrides and the like (aromatics Polyester polyol obtained by a dehydration condensation reaction with a polyol (other than the above), and a rataton-based polyester polyol obtained by ring-opening polymerization of the cyclic ester (ie, rataton) monomer.

These can be used alone or in admixture of two or more.

Of these, polyester polyols obtained by a dehydration condensation reaction of the above-mentioned non-aromatic dicarboxylic acids, their acid esters, acid anhydrides and the like with polyols (other than aromatic) are preferred.

[0013] All of these (A) and (B) polyester polyols are preferably viscous liquids at room temperature.

The molecular weights of these (A) and (B) polyester polyols are preferably 200 to 20,000 S, particularly those having a molecular weight of 400 to 10,000. If the molecular weight is too large, the introduction amount of urethane groups or the like is decreased, and the toughness of the polyurethane resin is not preferable because the strength and cohesive force are decreased. If the molecular weight is too small, the polyurethane resin tends to be brittle, which is preferable.

[0014] Examples of (C) dimethylolalkanoic acid include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolhexanoic acid, dimethylolheptanoic acid, dimethyloloctanoic acid, dimethylolnonanoic acid, and dimethylolnonanoic acid. Methyloldecanoic acid is mentioned.

These can be used alone or in admixture of two or more.

Of these, dimethylol butanoic acid is preferred.

[0015] Examples of the organic polyisocyanate (D) include organic polyisocyanate compounds containing modified organic polyisocyanate in addition to organic polyisocyanate monomers. For example, 2,4_tolylene diisocyanate, 2,6_tolylene diisocyanate, xylene_1,4-diisocyanate, xylene-1,3-diisocyanate, 4,1-diphenole methane diisocyanate, 2, 4 ^; —Diphenylmethane diisocyanate, 4, 1-diphenyl ether diisocyanate, 2—2-diphenyl ether di-isocyanate, 2 , 2 '-diphenylpropane-1,4,4'-diisocyanate, 3,3 '-dimethyldiphenylmethane 4,4,1 diisocyanate, 4,1 diphenylpropanediisocyanate, m-phenylene diisocyanate, p —Phenylene diisocyanate, naphthylene-1,4—Diisocyanate, naphthylene-1,5, diisocyanate, 3, 3 ^; —Dimethoxydiphenyl-1,4, A ′ —Diisocyanate and other aromatic diisocyanates, tetramethylene dissociates Aliphatic diisocyanates such as cyanate, hexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane Fats such as isocyanate and tetramethyl xylene diisocyanate Diisocyanates such as polyisocyanate diisocyanates, and polymer forms such as biuret, dimer, trimer, dimer 'trimer, and uretonimine modified forms of the above diisocyanates, and bifunctional or higher functional polyols, and the above diisocynates or their polymeric forms. And organic polyisocyanate modified products such as adducts of polyisocyanate obtained by the reaction with.

These can be used alone or in admixture of two or more.

Of these, aliphatic diisocyanates and / or alicyclic diisocyanates are preferred, and alicyclic diisocyanates are preferred.

The polyurethane resin in the main agent solution comprises (A) a polyester polyol having an aromatic ring in the molecule and a molecular end substantially having a hydroxyl group, and (B) a polyester polyol having no aromatic ring in the molecule, polyester polyol ( C) Dimethylolalkanoic acid and (D) organic polyisocyanate at (8) / (8) = 95 5 to 75/25 (mass ratio), preferably equivalent of isocyanate group equivalent of Z hydroxyl group = 0. Each component can be mixed and reacted uniformly at 50 / 1.00 to 0.98 / 1.00, 100 ° C or less.

The number average molecular weight of the resulting polyurethane tree is f 3,000 to 60,000, in particular 10,000 to 40,000.

As the reaction apparatus, any apparatus may be used as long as the above reaction can be achieved. Examples thereof include a mixing and kneading apparatus such as a reaction kettle or kneader equipped with a stirring apparatus, a uniaxial or multiaxial extrusion reactor, and the like.

Used as a catalyst in the production of polyurethane-polyurea as a catalyst to accelerate the reaction. A metal catalyst such as dibutyltin dilaurate or a tertiary amine catalyst such as triethylamine can be used.

[0017] As the silane coupling agent in the base resin solution, for example, _I - methacryloxy propyl Le trimethoxysilane, and Byurushiran compounds such Bulle triethoxysilane, beta - (3, epoxysilane compounds such Tokishishiran and, _I - § Examples include minopropyltriethoxysilane, compounds, and mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane.

These can be used alone or in admixture of two or more.

Of these, γ-glycidoxypropyltrimethoxysilane is preferred, with epoxysilane compounds being preferred.

The compounding amount of the silane coupling agent is 0.05 to 10.00 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin, from the viewpoints of the base material film covering area of the coupling agent and the coating efficiency and adhesive performance. Further, it is preferably 0.1 to 5.00 parts by mass.

[0018] Examples of the organic solvent in the main agent solution include inert organic solvents commonly used in the polyurethane industry, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester-based homogeneous 1J such as ethyl acetate and butyl acetate, Ketone solvents such as methyl ethyl ketone and cyclohexanone, glycol ether ester solvents such as ethylene glycol eno retinoate acetate, propylene glycol eno methenoate acetate, ethyl _ 3 _ ethoxypropionate, tetrahydrofuran, Examples include ether solvents such as dioxane, and polar solvents such as dimethylenolenolemamide, dimethylacetamide, N_methylpyrrolidone, and furfural. These can be used alone or in admixture of two or more.

[0019] As the isocyanate curing agent in the present invention, the compound described above as (D) organic polyisocyanate can be used. Specifically, Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd., Organic polyisocyanate modified products such as Coronate 3041, Coronate HL, and Coronate HX are preferred. The compounding amount of the isocyanate curing agent is preferably from! To 30 parts by mass, particularly from 3 to 15 parts by mass in terms of solids per 100 parts by mass of the solid content of the polyurethane resin.

In the present invention, a catalyst, a foam stabilizer and the like can be used in combination. These can be blended in the isocyanate curing agent, but are preferably blended in the main agent solution. As the catalyst, specifically, for example, dibutyltin dilaurate, di O lipped rutin dill Ureto, tin catalysts such as stannous O transfected benzoate, triethylene di § Min, ^{Toryechiruamin, N, N, N r,} N r - tetra methyl propylene diene § ^{Min, N, N, N r,} N r - tetrakis (2-hydroxypropyl Honoré) Echirenjiamin, N- methylmorpholine, 1, 2-Jimechiruimida tetrazole, 1, 5-Jiaza one bicyclo (4, 3, 0) Nonene 1, 5, 8—Diazabicyclo (5, 4, 0) —undecene 1 (DBU), borane salts of these amine catalysts, DBU phenol salts, D BU octylates, DBU carbonates, etc. Amine salt catalysts, magnesium naphthenate, lead naphthenate, potassium acetate and other carboxylates, triethylphosphine, tribenzylphosphine and other trialkylphosphines, Alkoxides such as potassium methylate, zinc-based organometallic catalysts.

The blending amount of the catalyst is preferably 0.001 to 5.00% by mass, particularly 0.01 to 2.00% by mass with respect to the solid content of the polyurethane resin.

[0021] Examples of the foam stabilizer include at least one reaction with a polyglycol ether containing a necessary number of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, preferably ethylene oxide. The strength obtained by condensing with an organic compound containing a reactive hydrogen atom. Such organic compounds containing at least one reactive hydrogen atom include alcohols, phenols, thiols, primary or secondary amines, carboxylic acids or sulfonic acids, and nonionic surfactants that are amides thereof. Examples include 1J and polyalkylene oxide derivatives of phenolic compounds having one or more alkyl group substituents.

There may also be mentioned pull nick type surfactants, which are 1, 2 _, such as butylene oxide, butylene oxide, phenylethylene oxide, cyclohexene oxide, propylene oxide, or mixtures thereof. The alkylene oxide or substituted alkylene oxide is polymerized in the presence of an alkali catalyst to give the corresponding water-insoluble polyalkylene group. It is a nonionic surfactant obtained by producing recall and condensing with the required number of moles of ethylene oxide under the same conditions.

Furthermore, it is necessary for alcohols obtained by reducing aldehydes produced by catalytic reaction of polyolefins such as tripropylene, tetrapropylene, pentapropylene, ditributylene, triisobutylene, propyleneisobutylene and tributene with carbon monoxide and hydrogen. Examples thereof include nonionic surfactants obtained by reacting ethylene oxide in the number of moles.

Furthermore, organic polysiloxane can also be mentioned as an example of a preferable foam stabilizer. The blending amount of the foam stabilizer is preferably 3% by mass or less based on the solid content of the polyurethane resin.

[0022] Films used for laminating in the present invention include metal foils such as Al and Cu, stretched polypropylene, unstretched polypropylene (hereinafter abbreviated as CPP), polyester (hereinafter abbreviated as PET), and nylon. (Hereinafter abbreviated as NY), linear low density polyethylene (hereinafter abbreviated as LLDPE), low density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer, polyvinyl alcohol, ethylene vinyl alcohol copolymer, Examples thereof include plastic films such as polystyrene, polycarbonate, polyvinylidene chloride, and polyvinyl chloride, paper, and films obtained by polymer coating on these.

These films are preferably subjected to an appropriate surface treatment such as a corona discharge treatment before lamination in order to improve the adhesive force.

In addition, since polymer coated films may cause problems such as bubble generation and reduced adhesive strength, it is necessary to consider the type of coated polymer, coating amount, surface characteristics, etc. in advance.

[0023] The adhesive for laminating of the present invention can be used in a known laminating method such as dry lamination, hot-melt lamination, and ethanol extrusion lamination. The laminated film can complete the curing reaction by aging at room temperature (preferably 40 to 50 ° C) for a certain time (preferably within 48 hours).

According to the present invention, it is possible to manufacture a film in which three or more films are laminated only by a film in which two films are laminated. Example

Next, the power to explain the embodiments of the present invention in detail The present invention is not construed as being limited to these embodiments. Unless otherwise specified,% in Synthesis Examples, Examples and Comparative Examples means “% by mass”.

[Synthesis of polyester polyol having an aromatic ring in the molecule and a molecular terminal substantially having a hydroxyl group]

'

A reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler was charged with 25 g of ethylene glycol and 400 g of talented pentinoreglinole. After melting at 120 ° C, 269 g of didipic acid and isophthalic acid were added. 306 g of acid was charged and esterification was performed at 220 ° C under normal pressure. After flowing out the prescribed water, add 0.03 g of tetrabutyl titanate, gradually reduce the pressure from normal pressure to 2.7 kPa abs (absolute pressure) over 5 hours, and conduct transesterification at 220 ° C for 5 hours. A polyester polyol having an acid value of 0.4 mgK0H / g, a hydroxyl value of 56. lmgK0H / g, a number average molecular weight of 2,000, and a room temperature viscous liquid was obtained.

This polyester polyol is referred to as A_1.

[Synthesis of a polyester polyol containing no aromatic ring in the molecule]

Synthesis example 2

In the same reactor as in Synthesis Example 1, 148 g of ethylene glycol and 148 g of diethylene glycol were charged, dissolved at 120 ° C, 61 lg of adipic acid was charged, and esterification was performed at 220 ° C under normal pressure. After flowing out the prescribed water, add 0.03 g of tetrabutyl titanate, gradually reduce the pressure from normal pressure to 2.7 kPa abs (absolute pressure) by applying 5 hours, and then perform ester exchange reaction at 220 ° C for 5 hours. Thus, a polyester polyol having an acid value of 0.3 mgKOH / g, a hydroxyl value of 56. lmgKOH / g, a number average molecular weight of 2,000, and a room temperature viscous liquid was obtained.

This polyester polyol is referred to as A-2.

[0027] Examples 1 to 7 and comparative examples:! To 4

[Synthesis of polyurethane resin]

Polyester polyol monole A-1, A-2, and dimethylolbutanoic acid were dissolved in ethyl acetate, and a catalyst (dioctyltin dilaurate) was added thereto. In addition to this, isophorone Diisocyanate was added and reacted to produce a polyurethane resin solution having a nonvolatile content of 80% by mass.

(Preparation of main agent solution)

To the obtained polyurethane resin solution, ethyl acetate, a silane coupling agent (KBM _403 manufactured by Shin-Etsu Chemical Co., Ltd., —glycidoxypropyltrimethoxysilane) and an antifoaming agent (BITK Chemy's BYK manufactured by Japan) ) To prepare a main agent solution of an adhesive for laminating having a nonvolatile content of 60% by mass.

[Preparation of adhesive for laminating]

Using the prepared main agent solution and isocyanate curing agent (Nihon Polyurethane Industry Co., Ltd. Coronet HX, hexamethylene diisocyanate trimer, isocyanate group content 21 · 3%, solid content 100%) A laminate film was produced by the following method and its performance was tested.

These results are summarized in Table 1.

[Manufacture of laminate film]

Under the conditions shown below, the adhesives of Examples 1 to 7 or Comparative Examples 1 to 4 were applied to the first plastic film and dried, and then the second plastic film or metal foil was applied to the first plastic film with a nip roll. Bonding and aging were performed to produce a two-layer laminate film. In addition, using this two-layer laminate film, the adhesive was further applied and dried, and then the third plastic film was bonded with a nip roll and aged to produce a three-layer laminated film. .

Adhesive solid content: 30% (diluted with ethyl acetate)

Laminate film composition: 15 μΝΥ / 60 μ LLDPE

12 μPET / 7 μ Al / 70 μ CPP

Adhesive application amount: 3.5 g / m ² (after drying)

Drying conditions: 80 ° C x 5 seconds

Aging condition: 40 ° C x 30 hours

[Performance test of laminate film]

The laminate film was evaluated under the following conditions. The results are summarized in Table 1. Initial peel adhesion strength: T-type peel test immediately after bonding at 25 ° C

(Compliant with JIS K 6854)

§ I tension speed: 300mm / min

Normal peel adhesion strength: T-type peel test after 30 hours at 40 ° C after bonding

(Compliant with JIS K 6854)

§ I tension speed: 300mm / min

Content resistance (retort treatment): 4 laminated films of PET / A1ZCPP

Heat seal immediately after aging treatment at 0 ° CX for 30 hours to create a bouch and fill with a mixture of vinegar / edible oil / tomato ketchup = 1/1/1 (mass ratio), then steam retort at 135 ° C for 30 minutes After the treatment, the peel adhesion strength between A1 / CPP was measured.

Content resistance (boiled): NY / LLDPE strength laminate film at 40 ° C X

Heat seal immediately after aging treatment for 30 hours to make a pouch, and after filling with water / edible oil = 1/9 (mass ratio), boil at 100 ° C for 30 minutes, NY / LLDPE The peel adhesion strength between them was measured.

[table 1]

Example

1 2 3 4 5 6 7 Raw material for polyurethane resin production (g),)

Polyester polyol A-1 ₎ 506.2 475.2 475.2 475.2 475.2 455.5 402.4

A- 2 30.6 61.1 61.1 61.1 61.1 80.4 133.6 Major dimethylolbutanoic acid 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Isophorone disocyanate 56.8 56.8 56.8 56.8 56.8 56.8 56.8

Silane force 'sopling agent (g) 2.99 2.99 2.93 2.99 2.99 2.99 2.99

Ethyl acetate (g) 398.7 398.7 398.7 398.7 398.7 398.7 398.7 Solution

Catalyst (g) 0.12 0.12 0.12 0.12 0.12 Antifoam (g) 0.02 0.02 0.02 0.02 0.02 Isocyanate curing agent (g) 55.6 55.6 55.6 55.6 55.6 55.6 55.6 Polyester polyol quality MJ: J

A- 1 / A- 2 94/6 89/11 89/11 89/11 89/11 85/15 75/25 Main agent solution / Isocyanate hardener (mass ratio) 18/1 18/1 18/1 18 / 1 18/1 18/1 18/1 Performance of laminated film

Initial peel adhesion ¾Jt (N / 1 5mm)

Between A 1 / CPP 0.65 0.75 0.75 0.75 0.75 0.9 1.25

NY / LLDP E 0.6 0.7 0.7 0.7 0.7 0.85 1.1 Normal peel adhesion (N / 1 5mm)

Between A 1 / CPP 12.3 12.2 12.2 12.2 12.2 11.6 8.4

NY / LLDP E material ¾1 Material broken material Broken material Broken material Broken material 7 Content resistance (N / 1 5mm)

1 35 ° C retort 10 9.8 9.8 9.8 9.8 7.8 5 Appearance immediately after retorting Peel Peel Peel Peel Peel Peel Peel Peel None None None None None None None

10 (TC boiled material broken material broken material broken material broken material broken 6 Note 1) Polyester polyol A— 1

: Adipic acid / isofuric acid / ethylene glycol / neopentyl glycol = 269/306/25/400

2) Polyester polyol A-2

: Adipic acid Z ethylene glycol Diethylene glycol = 6 1 1/148/24

3) Material breakage: Material job breakage

Note 1) Polyester polyol A— 1

Adipic acid / isophthalic acid / ethylene glycol / neopentyl glycol

= 269/306/25/400

2) Polyester polyol A— 2

: Adipic acid / ethylene glycol / diethylene glycol = 61 1/148/241

3) Material failure: Material failure

For example, if the film configuration for retort is PETZA1 / CPP, from the standpoint of not causing problems such as the occurrence of broken bags when dropped and the occurrence of peeling during long-term storage, The adhesive strength must be at least 5.0 N / I 5 mm.

Further, even when the film configuration for the boil is, for example, NY / LLDP, at least the same adhesive strength is required from the same viewpoint as for the retort. [0033] Comparative Example 5

An adhesive for laminating was produced by the following steps, and appearance evaluation immediately after the retort treatment was performed by the same methods as in Examples:! -7 and Comparative Examples 1-4.

[Manufacture of Polyester Polio Nore XA]

An esterification reaction was carried out at 180 to 220 ° C. under nitrogen flow using 548.5 g of isophthalanolic acid and 839.2 g of diethyleneglycolole. Next, after distilling a predetermined amount of water, 482.5 g of adipic acid was added and an esterification reaction was carried out at 180 to 220 ° C. to obtain a polyester polyol XA having a number average molecular weight of about 2,000. The whole amount was dissolved in 400. Og of ethyl acetate to obtain a solution having a solid content of 80%.

[Production of polyester polyol XB]

The esterification reaction was carried out at 180 to 220 ° C. under a nitrogen stream using 529.4 g of isophthalenolic acid, 128.8 g of ethylene glycol and 302.4 g of talented pentinoregulinole. Next, after distilling out a predetermined amount of water, 214.8 g of sebacic acid was added, and esterification was performed at 180 to 220 ° C. to obtain a polyester polyol XB having a number average molecular weight of about 3,000. . The whole amount was dissolved in 428.6 g of ethyl acetate to obtain a solution having a solid content of 70%.

[Manufacture of polyurethane resin solution XC]

Polyesterenore Poly-Nore XA 160. 74 g, Polyester Nole Poly-Nore XB459. 26 g in a nitrogen atmosphere, uniformly mixed at 50 ° C, then mixed with isophorone diisocyanate 49. 83 g at 77-80 ° C 3 A time urethane reaction was carried out. Thereafter, Stanotato (tin-based urethanization catalyst: produced by Yoshitomi Fine Chemical Co., Ltd.) was added in an amount of 0.1 g, and the urethanization reaction was continued for another 3 hours. After completion of the urethanization reaction, the mixture was cooled to 70 ° C., and 330.07 g of ethyl acetate was added to obtain a polyurethane resin solution XC having a solid content of 50%. The number average molecular weight of the obtained polyurethane resin was about 10,000.

[0037] [Production of Polyester Polio Nore XD]

Isophthalanolic acid 324. 88 g, ethylene greenole 106. 16 g, talented entinogregrinole 10 2. 61 g, 1, 6-hexanediole 151. 34 g, oxalic acid # & 0. The esterification reaction was performed at ~ 220 ° C. After distilling a predetermined amount of water, 95.24 g of adipic acid was prepared and subjected to esterification reaction at 220-230 ^° C. Gradually reduce pressure 220-2 After reacting at 30 ° C. for 60 minutes, esterification was carried out at 220 to 230 ° C.:! To 2 Torr for 4 hours to obtain a polyester polyol X having a number average molecular weight of about 5,500. Add 0.96 g of trimellitic anhydride to this, 140-150. After reacting with C, polyester polyol XD containing a carboxyl group was obtained which had a dissolution angle of 600.96 g of oxalate ethinole and made a solution with a solid content of 50%. In the obtained polyester polyol XD, about 2 mol% of the terminal hydroxyl groups were reacted with trimellitic anhydride.

[0038] [Production of isocyanate curing agent XE]

Takenate A—10 (Trimethylolpropane adduct of xylylene diisocyanate: Takeda Pharmaceutical Co., Ltd.) and 50 g of Takenate A—40 (Trimethylolpropane adduct of isophorone diisocyanate: Takeda Pharmaceutical Co., Ltd.) ) 50 g was uniformly mixed at 50 ° C under a nitrogen atmosphere to obtain isocyanate curing agent XE.

[Preparation of adhesive for lamination and production of laminate film]

Performed using 100 g of polyurethane resin solution XC, 100 g of polyester polyol XD, 23.5 g of isocyanate curing agent XE, and 0.5 g of silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) Example:! To 7 and Comparative Example:! To 4 A laminate film was produced in the same manner.

[0040] [Appearance evaluation immediately after retort processing]

Using the laminate film, the retort treatment was performed in the same manner as in Examples:! To 7 and Comparative Examples:! To 4, and the appearance immediately after the treatment was confirmed. As a result, peeling was confirmed.

Industrial applicability

[0041] The laminate film produced using the laminating adhesive of the present invention can be widely used for food packaging, refill container packaging and the like.

Claims

The scope of the claims

[1] A polyurethane resin obtained by reacting at least the following (A), (B), (C) and (D) at a mass ratio (A) / (B) = 95/5 to 75/25, A laminating adhesive characterized by comprising a main agent solution containing a silane coupling agent and an organic solvent and an isocyanate curing agent.

(B) A polyester polyol that does not contain an aromatic ring in the molecule

(C) Dimethylolalkanoic acid

(D) Organic polyisocyanate

[2] The laminating adhesive according to claim 1, wherein both (A) and (B) are viscous liquids at room temperature.

[3] The laminating adhesive according to claim 1 or 2, wherein (C) is dimethylolbutanoic acid.