JP2003113359A - Laminate adhesive and usage thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate adhesive having adequate adhesiveness even after high temperature sterilization treatment such as the hot-water spray sterilization treatment, the hot-water rotary sterilization treatment or the steam sterilization treatment and not impairing the odor and taste of the inherent properties of the packing product and to provide a usage of the laminate adhesive. SOLUTION: This laminate adhesive comprises a curing agent containing a polyisocyanate and a main agent containing a polyol, wherein a silane coupling agent is contained in at least the curing agent. The silane coupling agent is mixed with at least the curing agent, preferably both of the curing agent and the main agent. Further preferably, an epoxysilane is mixed with the curing agent, and also an aminosilane and an oxyacid of phosphorus or a derivative thereof are mixed with the main agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminating adhesive, and more particularly to a laminating adhesive useful for producing packaging materials used in various industrial fields such as foods, beverages, pharmaceuticals and quasi drugs. An adhesive and a method of using the laminating adhesive.

[0002]

2. Description of the Related Art Up to now, as a packaging material used in various industrial fields such as foods, beverages, pharmaceuticals and quasi-drugs, for example, plastic film, metal foil such as aluminum, metal vapor deposition film, silica vapor deposition film. A composite film obtained by laminating the above with an adhesive is widely used.

As a laminating adhesive used in the production of such a packaging material, a so-called two-component type urethane is used in which a curing agent containing polyisocyanate and a main agent containing polyol such as polyester polyol are used in combination. Adhesives are widely used because of their excellent adhesive performance.

Such a two-component type urethane adhesive is disclosed, for example, in Japanese Patent Publication No. 58-11912.
In order to improve the adhesive strength between the plastic film and the metal foil, it has been proposed to mix a silane coupling agent with the urethane adhesive, and in fact, it is widely practiced to mix the silane coupling agent with the main agent. There is.

[0005]

However, in recent years, due to the importance of hygiene control, a packaged product produced by using such a composite film is treated with a high temperature such as a hot water spray type, a hot water rotary type or a steam type. Sterilization is being widely carried out, and after such high temperature sterilization, there is a problem that the plastic film of the composite film and the metal foil are separated.

Therefore, in order to prevent such peeling,
Although it is considered to increase the amount of silane coupling agent, increasing the amount of silane coupling agent causes a problem that the original taste of the contents of the packaged product is reduced. .

The present invention has been made in view of the above problems, and an object thereof is a hot water spray type,
An adhesive for lamination, which has good adhesive performance even after high-temperature sterilization treatment such as hot water rotation type or steam type, and does not impair the odor originally possessed by the contents of the packaging product, and , Providing a method of using the laminating adhesive.

[0008]

In order to achieve the above object, the adhesive for lamination of the present invention comprises a curing agent containing polyisocyanate and a main agent containing polyol, and at least the curing agent contains a silane cup. It is characterized by containing a ring agent.

Further, in the laminating adhesive of the present invention,
Furthermore, it is preferable that the main component contains a silane coupling agent.

Further, in the laminating adhesive of the present invention,
The silane coupling agent is preferably epoxysilane.

Further, in the laminating adhesive of the present invention,
Furthermore, it is preferable that the main component contains aminosilane.

Further, in the laminating adhesive of the present invention,
Furthermore, it is preferable that the main component contains an oxygen acid of phosphorus or a derivative thereof.

And, the laminating adhesive of the present invention is
It can be suitably used for applications in which hot water treatment at 100 ° C. or higher is performed.

Further, in the present invention, as a laminating adhesive, a curing agent containing a polyisocyanate and a silane coupling agent and a main agent containing a polyol are prepared, and the curing agent and the main agent are mixed to prepare a coating agent. It also includes a method of using the laminating adhesive, which is characterized in that it is applied to a body.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive for lamination of the present invention is
It is prepared as a so-called two-component type urethane adhesive having a curing agent and a main component.

Further, in the present invention, the curing agent contains a polyisocyanate and a silane coupling agent.

The polyisocyanate is not particularly limited, and examples thereof include polyisocyanates having 2 to 4 functional groups.

More specifically, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate,
1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, etc. Aliphatic diisocyanates such as 1,3-cyclopentane diisocyanate, 1,4
-Cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-
3,5,5-Trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4- or 1,3-bis (isocyanato Alicyclic diisocyanates such as methyl) cyclohexane, for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,
4'- or 2,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4'-
Aromatic diisocyanates such as toluidine diisocyanate, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, for example 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω-diisocyanate-1,4-diethylbenzene, Aroaliphatic diisocyanates such as 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene or mixtures thereof, as well as, for example, triphenylmethane-4,4 ′, 4 ″ -tri Isocyanate, 1,3,5-triisocyanatobenzene,
Triisocyanates such as 2,4,6-triisocyanatotoluene, polyisocyanate monomers such as tetraisocyanates such as 4,4′-diphenyldimethylmethane-2,2′-5,5′-tetraisocyanate, And derived from the above polyisocyanate monomer, for example, dimer, trimer, biuret,
Allophanate, polyisocyanate having 2,4,6-oxadiazinetrione ring obtained from carbon dioxide gas and polyisocyanate monomer, or, for example, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol , 1,6-hexane glycol, 3-methyl-1,5
-Adducts with low molecular weight polyols having a molecular weight of less than 200 such as pentanediol, 3,3'-dimethylolheptane, cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol and sorbitol. Or, for example, polyisocyanate derivatives such as the above-mentioned polyester polyols, polyether polyols, polyester amide polyols, acrylic polyols, polyhydroxyalkanes, natural oil polyols and the like having a molecular weight of 200 to 200,000 can be mentioned.

These polyisocyanates may be used alone or in combination of two or more, and preferably hexamethylene diisocyanate and 3-isocyanatomethyl-3,5.
5-trimethylcyclohexyl isocyanate, 4,
4'-methylenebis (cyclohexylisocyanate), 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,3- or 1,4-xylylenediisocyanate or a mixture thereof, and polyisocyanate derivatives thereof are Can be mentioned.

The silane coupling agent is represented by the structural formula R
-Si≡ (X) ₃ or R-Si≡ (R ′) (X)
₂ (wherein R represents an organic group having a vinyl group, an epoxy group, an amino group, an imino group, an isocyanate group or a mercapto group, R ′ represents a lower alkyl group, and X represents a methoxy group, an ethoxy group or a chloro atom. ), Any of them may be used, for example, chlorosilane such as vinyltrichlorosilane, for example, N-
β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
Aminosilanes such as β- (aminoethyl) -γ-propylmethyldimethoxysilane, n- (dimethoxymethylsilylpropyl) ethylenediamine, n- (triethoxysilylpropyl) ethylenediamine, N-phenyl-γ-aminopropyltrimethoxysilane, for example, , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, di (γ
-Glycidoxypropyl) dimethoxysilane and other epoxysilanes, for example vinyltriethoxysilane and other vinylsilanes, such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane and other isocyanatesilanes. These silane coupling agents may be used alone or in combination of two or more kinds.

By adding a silane coupling agent to the curing agent, the hot water resistance can be improved without reducing the odor of the contents of the packaged product laminated with the laminating adhesive of the present invention. It is possible to secure good adhesion performance after high temperature sterilization.

In the present invention, the curing agent preferably contains epoxysilane. By blending epoxy silane with the curing agent, it is possible to further improve the adhesive performance.

The amount of the silane coupling agent in the curing agent is, for example, 0.1 to 25.0 parts by weight, preferably 100 parts by weight of polyisocyanate.
It is 0.5 to 20.0 parts by weight. The silane coupling agent is 0.1% by weight, depending on the polyisocyanate composition.
If the amount is less than the above, peeling may occur between films laminated by the laminating adhesive of the present invention during sterilization treatment, and if it is more than 25.0% by weight, the storage stability of the curing agent may increase. More often it drops.

The curing agent can be obtained, for example, by mixing the above polyisocyanate with the above silane coupling agent and diluting it with an organic solvent.

The organic solvent is not particularly limited as long as it is inactive with respect to polyisocyanate and polyol, for example, ester solvents such as ethyl acetate and butyl acetate, such as methyl ethyl ketone and methyl isobutyl ketone. Examples thereof include ketone solvents such as aromatic solvents such as toluene and xylene.
The blending amount of the organic solvent is appropriately selected depending on its purpose and use.

Further, for example, when the above-mentioned polyisocyanate is blended with the main agent described later, the blending viscosity thereof is from room temperature to 100 ° C. and about 100 to 10,000 mPa · s.
In the case of s, preferably about 100 to 5000 mPa · s, the silane coupling agent may be blended with the above-mentioned polyisocyanate without diluting with an organic solvent and used as it is as a curing agent.

In the present invention, the main component contains a polyol. The polyol is not particularly limited,
The number of functional groups is 2 to 6, preferably 2 to 4, and the number average molecular weight is 200 to 200,000, preferably 300 to 1000.
And polyols having an acid value of 0 to 280, preferably 0 to 100, and more preferably 0 to 50 mgKOH / g.

More specifically, for example, polyester polyol, polyether polyol, polyester amide polyol, acrylic polyol, polyhydroxyalkane, natural oil polyol, polyurethane polyol,
Alternatively, a mixture thereof or the like can be used.

Examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid and sebacic acid, dialkyl esters thereof or a mixture thereof, and, for example, ethylene glycol, propylene glycol, diethylene glycol, Butylene glycol, neopentyl glycol, 1,6-hexane glycol, 3-methyl-1,
Polyester polyol obtained by esterification reaction with glycols such as 5-pentanediol, 3,3′-dimethylolheptane, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol or a mixture thereof, or polycaprolactone, Examples thereof include polyester polyols such as polyvalerolactone and poly (β-methyl-γ-valerolactone).

The polyester polyols obtained by esterification also include those that have been acid-modified with a polybasic acid such as trimellitic anhydride or an anhydride thereof.

As the polyether polyol, for example, oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran, and low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane and glycerin are used as an initiator. Examples thereof include polyether polyols obtained by polymerization.

As the polyester amide polyol,
For example, in the esterification reaction of the polyester polyol described above, for example, a polyester amide polyol obtained by using a low molecular weight polyamine such as ethylenediamine, propylenediamine, or hexamethylenediamine as a raw material in combination is exemplified.

As the acrylic polyol, for example, 1
A polymerizable monomer having one or more hydroxyl groups in the molecule, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate or the like, or a corresponding methacrylic acid derivative thereof, for example, acrylic acid, Examples thereof include acrylic polyols obtained by copolymerizing methacrylic acid or its ester.

Examples of polyhydroxyalkanes include liquid rubbers obtained by copolymerizing butadiene or butadiene with acrylamide.

Examples of natural oil polyols include castor oil and coconut oil.

As the polyurethane polyol, a polyol having a urethane bond in one molecule, for example, a polyester polyol or a polyether polyol having a number average molecular weight of 200 to 5,000 and the above-mentioned polyisocyanate are prepared by using an isocyanate group for a hydroxyl group. Equivalent ratio (NCO / OH) of less than 1, preferably 0.8
The thing obtained by making it react below is mentioned.

Further, in addition to the above-mentioned polyols, the molecular weight is from 62 to 62 for the purpose of adjusting the average molecular weight of the polyol.
200 low molecular weight polyols may be included. Such low molecular weight polyols include, for example, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol,
Hexylene glycol, neopentyl glycol, glycols usually used in the production of polyester polyols such as cyclohexanedimethanol, glycerin,
Examples include trifunctional or higher functional polyols such as trimethylolpropane and pentaerythritol.

These polyols may be used alone or in combination of two or more, and preferably, polyester polyol, polyether polyol and polyurethane polyol are mentioned.

Further, in the present invention, in addition to the silane coupling agent added to the curing agent, a silane coupling agent can be added to the main component as long as the taste is not affected. By adding a silane coupling agent to the main agent (that is, both the curing agent and the main agent), the hot water resistance can be further improved, and good adhesive performance after high temperature sterilization treatment can be secured. be able to.

Examples of the silane coupling agent to be added to the main agent include those similar to the above-mentioned silane coupling agent to be added to the curing agent, and these may be used alone or in combination of two or more kinds. .

In the present invention, the main component may be blended with epoxysilane or aminosilane as in the case of the curing agent. Further, both epoxysilane and aminosilane may be blended. (That is, in the present invention, for example, epoxy silane and / or amino silane can be blended with the main agent.) By blending epoxy silane with the main agent, the adhesive performance can be improved. Further, in the case of adding an oxygen acid of phosphorus or a derivative thereof, which will be described later, to the main component, the addition of aminosilane can improve the adhesive performance.

In the main agent, the amount of the silane coupling agent blended is, for example, 0.1 to 2.0 parts by weight, preferably 0.1 to 1.
5 parts by weight. The silane coupling agent depends on the polyol composition, but if it is less than 0.1 parts by weight, peeling may occur between the films laminated by the laminating adhesive of the present invention during sterilization treatment, On the other hand, if the amount is more than 2.0 parts by weight, the odor and taste of the contents may be impaired more often.

Further, in the present invention, it is preferable to further mix an oxygen acid of phosphorus or a derivative thereof with the main component. By adding phosphorus oxyacid or its derivative to the main component, the acid resistance can be improved.

In the oxygen acid of phosphorus or its derivative,
As the oxygen acid of phosphorus, for example, hypophosphorous acid, phosphorous acid, orthophosphoric acid, phosphoric acid such as hypophosphoric acid, for example, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid,
Examples thereof include condensed phosphoric acids such as ultraphosphoric acid.

Examples of the oxygen acid derivative of phosphorus include phosphates such as sodium and potassium or condensed phosphates such as monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate and ortholine. Acid mono-2-ethylhexyl, monophenyl orthophosphate, monomethyl phosphite,
Monoesters such as monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, and monophenyl phosphite, for example, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, Trimethyl orthophosphate, triethyl orthophosphate, tripropyl orthophosphate, tributyl orthophosphate, tri-2-ethylhexyl orthophosphate, triphenyl orthophosphate, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, Di-2-ethylhexyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, tri-2-ethylhexyl phosphite, triphenyl phosphite, etc. Di-, triesters, or Mono obtainable from phosphoric acid with alcohols, di-, and the like triesters.

These oxygen acids of phosphoric acid or their derivatives may be used alone or in combination of two or more kinds. Preferably,
Those having at least one free oxygen acid are preferable, for example, orthophosphoric acid and polyphosphoric acid are preferable.

The oxygen acid of phosphoric acid or the derivative thereof is mixed in an amount of 0.0 to 100 parts by weight of the polyol.
1 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight. If it is less than 0.01% by weight, a sufficient acid resistance effect may not be obtained, and if it is more than 1.0% by weight, the adhesive performance may be deteriorated.

In addition, when the oxygen acid of phosphoric acid or its derivative is added to the main component and the aminosilane is added, aminosilane is added to the oxygen acid of phosphoric acid or its derivative in an amount of, for example, 2 to 5 parts by weight. It is preferable to mix 10 times.

The main agent can be obtained, for example, by diluting the above-mentioned polyol, if necessary, a silane coupling agent, and / or an oxygen acid of phosphorus or its derivative with an organic solvent. As an organic solvent,
The same organic solvent as described above can be used.

Further, for example, when the above-mentioned polyol is compounded with the above-mentioned curing agent, the compounding viscosity thereof at room temperature to 100 ° C. is about 100 to 10,000 mPa · s, preferably about 100 to 5000 mPa · s. In such a case, the silane coupling agent and / or the oxygen acid of phosphorus or its derivative can be blended with the above-mentioned polyol, if necessary, without being diluted with an organic solvent, and the mixture can be used as it is as a main component.

The silane coupling agent should be prepared in an amount of 0.1 to 5.0% by weight, more preferably 0.5 to 3.0% by weight, based on the whole laminating adhesive. Is preferred. When the silane coupling agent is less than 0.1% by weight, depending on the adhesive composition, it may cause peeling between films laminated by the laminating adhesive of the present invention during sterilization or the like. On the other hand, if it is more than 5.0% by weight, the odor and taste of the contents may be impaired more often.

Further, the laminating adhesive of the present invention includes
Known additives such as epoxy resins, catalysts, carboxylic acids or their anhydrides, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, antifungal agents, thickeners, plasticizers, pigments, fillers, etc. You may mix | blend in the range which does not impair the performance of the adhesive agent for lamination of invention.

These additives are hardeners and / or
Alternatively, it may be blended with any of the main ingredients, and it is usually blended with the main ingredient, although it is appropriately determined depending on its purpose and use.

The laminating adhesive of the present invention comprises
It is used as a two-pack type urethane adhesive by combining the above-mentioned curing agent and main agent. That is, the adhesive for lamination of the present invention is prepared in advance by separately preparing a curing agent and a main agent, and at the time of use,
The curing agent and the main agent are blended and used by being applied to an adherend. The mixing ratio of the curing agent and the main agent is
Equivalent ratio (NCO / OH) of isocyanate groups in the curing agent to active hydrogen groups (hydroxyl groups and amino groups) in the main agent
Therefore, the ratio is preferably 0.4 to 10, and more preferably 0.5 to 2.0.

When used as such a two-component type urethane adhesive, the curing agent and the main agent are prepared separately, so that the pot life is long, but at the time of use, the curing agent and the main agent are required respectively. It is possible to effectively use it as an adhesive that is fast-curing and has excellent adhesive performance by blending only the minimum amount.

More specifically, the laminating adhesive of the present invention is mainly used as an adhesive when a composite film is produced by laminating, and includes, for example, a curing agent and a main agent diluted with an organic solvent. When used, after mixing the curing agent and the main agent, this mixture is applied to the surface of each film by a solvent type laminator, the solvent is volatilized, the adhesive surfaces are pasted together, and then at room temperature or under heating. It may be cured and cured in. In addition,
The coating amount is preferably about 2.0 to 5.0 g / m ² after volatilization of the solvent.

Further, for example, when using a curing agent and a main agent which are not diluted with an organic solvent, after mixing the curing agent and the main agent, the mixture is applied to the surface of each film by a solventless laminator, The adhesive surfaces may be stuck together, and then cured and cured at room temperature or under heating. The coating amount is preferably about 1.0 to 3.0 g / m ² .

The film to be laminated is a plastic film such as polyethylene terephthalate, nylon, polyethylene, polypropylene, polyvinyl chloride, a metal foil such as aluminum, a metal vapor deposition film, or a silica vapor deposition film. Examples thereof include films, metal films such as stainless steel, iron, copper and lead. The thickness is preferably 5 to 200 μm in the case of a plastic film, for example.

The composite film produced by using the adhesive for laminating of the present invention is subjected to hot water treatment at 100 ° C. or higher, for example, hot water spray type, hot water rotary type or steam type. Even when subjected to high temperature sterilization treatment such as, the occurrence of peeling between each layer is small, and without impairing the odor of the contents, the adhesive for lamination of the present invention has interlayer adhesion, moist heat resistance, It has excellent suitability for high temperature sterilization and can be suitably used as a laminating adhesive for producing packaging materials in various industrial fields such as foods, beverages, pharmaceuticals and quasi drugs.

[0060]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
All "parts" and "%" in Examples and Comparative Examples are based on weight unless otherwise specified.

Production Example 1 (Production of Polyisocyanate A) 50 g of Takenate A-10 (a trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Takeda Chemical Co., Ltd.) and Takenate A-40 (3-isocyanatomethyl-3) Trimethylolpropane adduct of 5,5,5-trimethylcyclohexyl isocyanate, manufactured by Mitsui Takeda Chemical Co., Ltd.) 50 g under a nitrogen atmosphere at 50 ° C.
Was evenly mixed to obtain polyisocyanate A having an isocyanate group content of about 11%.

Production Example 2 (Production of Polyisocyanate B) A trimer of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate having an isocyanate group content of 17.3% (Vestanato T1890 / 10).
0, manufactured by Huls) was dissolved in 25 g of ethyl acetate to obtain polyisocyanate B as a solution having a solid content of 75%.

Production Example 3 (Production of Polyol A) 529.4 g of isophthalic acid, 12 of ethylene glycol
8.8 g and neopentyl glycol 302.4 g were subjected to an esterification reaction at 180 to 220 ° C under a nitrogen stream.
After distilling a predetermined amount of water, 214.8 g of sebacic acid was added,
Furthermore, the esterification reaction is performed at 180 to 220 ° C.,
A polyester polyol having a number average molecular weight of about 3000 was obtained. The total amount was dissolved in 428.6 g of ethyl acetate to obtain a solution having a solid content of 70%.

Then, this polyester polyol 47
33.70 g of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate was added to 3.60 g under a nitrogen atmosphere, and a urethanization reaction was carried out at 77 to 80 ° C. for 3 hours. Then, 0.25 g of tin octylate was added, and the urethane reaction was carried out for another 3 hours.
After cooling to 0 ° C., 223.39 g of ethyl acetate was added to obtain Polyol A as a solution having a solid content of 50%. The number average molecular weight of the obtained Polyol A, the polyurethane polyol, was about 10,000.

Production Example 4 (Production of Polyol B) Isophthalic acid 324.88 g, ethylene glycol 10
6.16 g, neopentyl glycol 102.61 g,
An esterification reaction of 151.34 g of 1,6-hexanediol and 0.20 g of zinc acetate was performed at 180 to 220 ° C under a nitrogen stream. After distilling a predetermined amount of water, adipic acid 9
5.24 g was added, and the esterification reaction was further performed at 180 to 220 ° C. After that, the pressure in the system is gradually reduced to 2
A condensation reaction was carried out at 20 to 230 ° C. for 4 hours to obtain a polyester polyol having a number average molecular weight of about 5,500. The total amount was dissolved in 600.00 g of ethyl acetate to obtain a solid content of 50.
% Polyol solution B was obtained.

Production Example 5 (Production of Polyol C) In Production Example 2, after obtaining a polyester polyol having a number average molecular weight of about 5,500, 9.60 g of trimellitic anhydride was added to this polyester polyol to prepare 140 to 15
After reacting (acid-denaturing) at 0 ° C., ethyl acetate 609.6
0 g was added to prepare polyol C as a solution having a solid content of 50%.
Got The number average molecular weight of the polyester polyol in the obtained polyol C was about 5,500.

Preparation of curing agent The following curing agents were prepared respectively.

Curing agent A-0: Polyisocyanate A was used as it was as curing agent A-0.

Hardener A-1: Polyisocyanate A10
Part and a silane coupling agent A (γ-glycidoxypropyltrimethoxysilane, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., the same applies hereinafter) to prepare a curing agent A-1.

Hardener A-2: Polyisocyanate A10
Part and 2.0 parts of silane coupling agent A were mixed to prepare curing agent A-2.

Curing agent B-0: Polyisocyanate B was used as it is as curing agent B-0.

Hardener B-1: Polyisocyanate B10
Part and silane coupling agent A 1.0 part were mixed to prepare a curing agent B-1.

Preparation of Base Agent The following main ingredients were prepared, respectively.

Main ingredient A-0: The ingredient A-0 was obtained by using the polyol A as it was.

Main agent A-1: Main agent A-1 was prepared by mixing 100 parts of polyol A and 1.0 part of silane coupling agent A.

Main agent A-2: 100 parts of polyol A, phosphorus oxyacid (85% orthophosphoric acid, manufactured by Wako Pure Chemical Industries, Ltd.,
The same applies hereinafter) 0.2 part and silane coupling agent B (N-
The main agent A-2 was prepared by blending 0.4 part of β (aminoethyl) -γ-aminopropyltrimethoxysilane, KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd., and the same below.

Main Agent B-0: The one in which the polyol B was used as it was was the main agent B-0.

Base Agent B-1: Base Agent B-1 was prepared by blending 100 parts of polyol B and 1.0 part of silane coupling agent A.

Main agent B-2: 100 parts of polyol B, 0.2 parts of oxygen acid of phosphorus and silane coupling agent B0.4
The main component B-2 was prepared by blending 1 part.

Main agent C-0: Main agent C-0 was prepared by blending 50 parts of polyol A and 50 parts of polyol C.

Main agent C-1: Main agent C-1 was prepared by blending 50 parts of polyol A, 50 parts of polyol C and 1.0 part of silane coupling agent A.

Main agent C-2: Main agent C-2 was prepared by blending 50 parts of polyol A, 50 parts of polyol C and 0.2 part of oxygen acid of phosphorus.

Main agent C-3: 50 parts of polyol A, 50 parts of polyol C, 0.2 part of phosphorus oxyacid and 0.4 part of silane coupling agent B were added to prepare the main agent C-.
3 was prepared.

Main agent C-4: Main agent C-4 was prepared by mixing 50 parts of polyol A, 50 parts of polyol C and 0.4 part of silane coupling agent B.

Main agent C-5: 50 parts of polyol A, 50 parts of polyol C, 0.2 part of phosphorus oxyacid, 1.0 part of silane coupling agent and B0.4 of silane coupling agent.
The main agent C-5 was prepared by blending parts.

Main agent C-6: Main agent C-6 was prepared by mixing 50 parts of polyol A, 50 parts of polyol C and 2.0 parts of silane coupling agent A.

Preparation and Evaluation of Examples and Comparative Examples The curing agent and base resin prepared as described above are shown in Table 1.
The adhesives for laminating of Examples 1 to 12 and Comparative Examples 1 to 5 were prepared in combination with each other. Then, the curing agent and the main agent of the adhesive for laminating of each of these Examples and Comparative Examples were blended, and using them, after producing a composite film by the method described later, for each composite film, a hot water resistance test and A taste test was performed. The results are shown in Table 2.

Preparation of composite film Polyethylene terephthalate film (thickness 12 μm)
/ Nylon film (thickness 25 μm) / Aluminum foil (thickness 7 μm) / Unstretched polypropylene film (thickness 70 μm: single-sided corona treatment) 4 layers composite film using the laminating adhesive of each example and each comparative example Was manufactured.

That is, the laminating adhesives (containing the curing agent and the main component) of each of the examples and comparative examples shown in Table 1 were first prepared at room temperature using a laminator.
It was applied to a polyethylene terephthalate film, the solvent was volatilized, and the applied surface was attached to a nylon film. Then, on the other surface of the nylon film of the two-layer composite film, in the same manner as above, the laminating adhesive of each Example and each Comparative Example was applied, and the solvent was volatilized,
The coated surface was attached to an aluminum foil. Then, the other side of the aluminum foil of the three-layer composite film was coated with the adhesive for laminating of Examples and Comparative Examples in the same manner as above, and the solvent was volatilized, and then the coated surface was unstretched polypropylene. It was attached to the corona-treated surface of the film. Then, the 4-layer composite film was cured at 50 ° C. for 3 days to cure the laminating adhesive.

Hot water resistance test (steam-type rotary retort test) Using each of the composite films prepared as described above, a bag of 9 × 14 cm was prepared and filled with distilled water as a content. This bag is 210 x 520 x 105
After being placed on a mm tray and subjected to steam sterilization at 130 ° C. for 30 minutes at 8 revolutions per minute under a pressure of 0.30 MPa,
The peeling state (delamination) between the layers in the corner portion of the bag was observed. The test was conducted with 5 bags each for one type of sample.

Taste Test Using each of the composite films produced as described above, a bag having a size of 13 × 17 cm was prepared and filled with distilled water as a content. This bag at 135 ℃ for 20 minutes,
After hot water sterilization under a pressure of 0.35 MPa, a sensory comparison test of distilled water before and after sterilization was performed.

[0092]

[Table 1]

[0093]

[Table 2]

INDUSTRIAL APPLICABILITY The adhesive for lamination and the method of using the same of the present invention are excellent even after high temperature sterilization such as hot water spraying, hot water rotating or steaming, in which hot water treatment at 100 ° C. or higher is performed. It has adhesive properties, does not impair the odor originally possessed by the contents of packaged products, has excellent interlaminar adhesion, resistance to moist heat and suitability for high temperature sterilization, and is suitable for foods, beverages, pharmaceuticals and quasi-drugs. It can be suitably used as an adhesive for lamination and a method of using the same for producing packaging materials in various industrial fields such as products.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yukio Igarashi             Osaka Prefecture, Osaka City Yodogawa-ku, 13-85, 2-3             Mitsui Takeda Chemical Co., Ltd. F term (reference) 4J040 EF101 EF111 EF131 EF181                       EF201 EF281 EF291 EF301                       HA286 HD30 HD32 KA17                       KA23 LA08 MA10 NA02 NA05                       NA08

Claims (7)

[Claims] 1. An adhesive for laminating, comprising a curing agent containing polyisocyanate and a main component containing polyol, wherein at least the curing agent contains a silane coupling agent. 2. The laminating adhesive according to claim 1, further comprising a silane coupling agent in the main component. 3. The adhesive for lamination according to claim 1, wherein the silane coupling agent is epoxysilane. 4. The laminating adhesive according to claim 1, wherein the main component further contains aminosilane. 5. The adhesive for lamination according to claim 1, wherein the main component further contains an oxygen acid of phosphorus or a derivative thereof. 6. The laminating adhesive according to claim 1, which is used for a hot water treatment at 100 ° C. or higher. 7. A curing agent containing a polyisocyanate and a silane coupling agent as an adhesive for laminating,
A method of using an adhesive for lamination, characterized in that a main agent containing a polyol is prepared, the curing agent and the main agent are mixed, and the mixture is applied to an adherend.