JP6631283B2 - Adhesive composition and laminate - Google Patents

Description

The present invention relates to an adhesive composition and a laminate. More specifically, the present invention relates to an adhesive composition and a laminate which exhibit high adhesive strength between various sheet-like members and can maintain high adhesive strength even when exposed to a high temperature and high humidity environment.

Conventionally, for example, as a material for food packaging, medical product packaging, cosmetic packaging, or a solar cell panel material, a multilayer laminate in which a plastic film such as polyethylene, polypropylene, nylon, or polyester, a metal-deposited film, or a metal foil such as an aluminum foil is laminated. Although widely used, these multilayer laminates generally tend to require high adhesion between various sheet-like members and resistance under high temperature and high humidity environments.

In food packaging materials, foods are sterilized in a state of being filled with various contents such as various kinds of sauces, soy sauce, vinegar, animal fats and oils, various spices, and alcohol-containing substances. Therefore, severe performance such as water resistance, oil resistance, acid resistance, and adhesive performance after sterilization at high temperatures such as 100 ° C. (boil), 120 ° C. (retort), and 135 ° C. (high retort) is required.

On the other hand, since the backsheet for solar cells is mainly used outdoors and needs to maintain its performance for about 20 years, its material and structure are required to have durability and weather resistance. For example, an acceleration test is performed in a high-temperature and high-humidity atmosphere at 85 ° C. and a relative humidity of 85% to evaluate.

As an adhesive used for joining these multilayer laminates, polyester resins or polyester polyurethane resins as shown in Patent Documents 1 and 2 are preferably used, but they are not suitable for a long time under a high temperature and high humidity environment. If it is removed, there is a problem that the molecular weight is reduced due to the hydrolysis reaction, the adhesion is reduced, the appearance is poor due to delamination, and the output of the solar cell is deteriorated.
As a resin system in which the hydrolysis reaction is suppressed, an acrylic adhesive as shown in Patent Document 3 is known, but an acrylic adhesive is generally used for bonding to a plastic film described above as compared with a polyester resin. There were issues such as insufficient power.

  As a method for improving the adhesive force between sheet-like members, a method of adding a rosin ester-based tackifier as disclosed in Patent Document 4 is known. There is a problem that heat resistance is low due to the presence of many low molecular weight residual components that are not incorporated into the system, and that the adhesive strength is reduced after an accelerated test under high temperature and high humidity.

JP-A-10-218978 JP-A-6-116542 JP 2009-246360 A JP 2015-120819 A

  An object of the present invention is to provide an adhesive composition and a laminate that exhibit high adhesive strength between various sheet-like members and can maintain high adhesive strength even when exposed to a high-temperature and high-humidity environment.

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have reached the present invention.
That is, the present invention
An adhesive composition comprising a polyol component (A), a polyisocyanate component (B), a compound (C) having a hydroxyl group and a steroid skeleton,
The polyol component (A) contains at least one selected from the group consisting of an acrylic polyol (A1), a polyether polyol (A2), a polyester polyol (A3), and a polyurethane polyol (A4);
The present invention relates to an adhesive composition comprising the compound (C) in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the polyol component (A).

The present invention also relates to the adhesive composition, wherein the compound (C) has one hydroxyl group in one molecule.

Further, the present invention provides an isocyanate group in the polyisocyanate component (B), a hydroxyl group in the polyol component (A), and an equivalent ratio of the hydroxyl group in the compound (C) (isocyanato group / hydroxyl group) of 0.6 to 5; 0.0.

Further, the present invention relates to a laminate in which at least two sheet-like substrates are laminated with the adhesive composition.

According to the present invention, it has become possible to provide an adhesive composition and a laminate that exhibit high adhesive strength between various sheet-like members and can maintain high adhesive strength even when exposed to a high-temperature and high-humidity environment.

Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist.

The present invention is an adhesive composition containing a polyol component (A), a polyisocyanate component (B), and a compound (C) having a hydroxyl group and a steroid skeleton.
Examples of the use form of the adhesive composition of the present invention include a three-component curing type in which a polyol component (A), a polyisocyanate component (B), a compound having a hydroxyl group and a steroid skeleton (C) are mixed at the time of use,
A two-part curing type in which a polyisocyanate component (B), a polyol component (A) which has been mixed in advance, and a compound (C) having a hydroxyl group and a steroid skeleton are mixed at the time of use,
One component curing type in which three components of a polyol component (A), a polyisocyanate component (B), and a compound (C) having a hydroxyl group and a steroid skeleton are mixed in advance, but from the viewpoint of pot life, a three component curing type A mold and a two-pack curing type are preferred.
Further, a plurality of types of the polyol component (A), the polyisocyanate component (B), and the compound (C) having a hydroxyl group and a steroid skeleton may be used.

Further, examples of the use form of the adhesive composition of the present invention include a solvent-type adhesive used in a state of being dissolved in a solvent described later and a solvent-free adhesive using no solvent.

<< polyol component (A) >>
As the polyol component (A) of the present invention, if it contains at least one selected from the group consisting of acrylic polyol (A1), polyether polyol (A2), polyester polyol (A3) and polyurethane polyol (A4), Although it can be used without limitation, it includes at least one selected from the group consisting of acrylic polyol (A1), polyester polyol (A3), and polyurethane polyol (A4) from the viewpoint of adhesive strength, durability, and workability. Preferably.

<Acrylic polyol (A1)>
The acrylic polyol (A1) is not limited to the following examples, but includes, for example, a copolymer of a hydroxyl group-containing mono (meth) acrylate monomer and a hydroxyl group-free mono (meth) acrylate monomer.

Hydroxyl group-containing mono (meth) acrylate monomer refers to a monomer containing one (meth) acryloyl group and one or more hydroxyl groups in one molecule, and is obtained by reacting (meth) acrylic acid with a dihydric or higher alcohol. The resulting mono (meth) acrylate monomer, ε-caprolactone-modified (meth) acrylate monomer and the like can be mentioned.

Examples of the hydroxyl group-containing mono (meth) acrylate monomer obtained from a dihydric alcohol include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (poly) ethylene glycol (meth) acrylate, and the like.
Examples of the hydroxyl group-containing mono (meth) acrylate monomer obtained from a trivalent or higher alcohol include 2,3-dihydroxypropyl (meth) acrylate.

As the mono (meth) acrylate monomer containing no hydroxyl group, a conventionally known radically polymerizable monomer can be appropriately selected and used. Preferred examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) A) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (Meth) acrylate, stearyl (meth) acrylate and the like.

In addition to the mono (meth) acrylate monomer, for example, a monomer having an ethylenically unsaturated bond having a carboxyl group, a monomer having an ethylenically unsaturated bond having an epoxy group, and an ethylenically unsaturated bond having an amino group may be used. Monomers having a monomer having an ethylenically unsaturated bond having a functional group such as a monomer having an ethylenically unsaturated bond having an isocyanato group,
(Meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, and vinyl acetate, vinyl crotonate, styrene, acrylonitrile, and the like can also be used.

  The proportion of the hydroxyl group-containing mono (meth) acrylate monomer is more preferably in the range of 1.0 to 50% by mass, and more preferably 1.0 to 30% by mass, based on 100% by mass of all the monomers constituting the acrylic polyol (A1). Is more preferable. When the content is in the above range, crosslinking proceeds sufficiently, and good wet heat resistance is obtained.

<Polyether polyol (A2)>
Examples of the polyether polyol (A2) include, but are not limited to, oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, for example, water, ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol. , Dipropylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-butylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl-1, A reaction product obtained by polymerization using a low molecular weight polyhydric alcohol such as 5-pentanediol as an initiator is exemplified.

<Polyester polyol (A3)>
Examples of the polyester polyol (A3) are not limited to the following examples. For example, a polycondensate obtained by an esterification reaction between a dibasic acid and a low molecular weight polyhydric alcohol; And a valerolactone polymer, a methylvalerolactone polymer, a lactic acid polymer, a castor oil fatty acid polymer, and the like. Further, a reaction product of a hydroxyl group in the polycondensate with an acid anhydride may be used.

  Examples of the dibasic acid include, but are not limited to, adipic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, Examples include suberic acid, glutaric acid, 1,4-cyclohexyldicarboxylic acid, dimer acid, and hydrogenated dimer acid.

  As the low molecular weight polyhydric alcohol, those similar to the low molecular weight polyhydric alcohol described in the polyether polyol (A2) can be used.

Examples of the acid anhydride include, but are not limited to, phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride, and Ricacid TMEG-X (where X is 100, 200, 500, 600, and S), and trimellitic anhydride anhydrides such as RIKACID TMA-X (where X is C, 10, and 15).

<Polyurethane polyol (A4)>
The polyurethane polyol (A4) is not limited to the following examples. For example, an acrylic polyol (A1), a polyether polyol (A2), a polyester polyol (A3) and, for example, 2,4-tolylene diisocyanate, Reaction products with polyisocyanates such as 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

In addition to the above (A1) to (A4), polycarbonate polyols, polybutadiene polyols and the like can be used as long as the adhesive properties are not impaired.

The polycarbonate polyol is not limited to the following examples. For example, the polycarbonate polyol is obtained by a reaction between the low-molecular-weight polyhydric alcohol described in the polyether polyol (A2) and dimethyl carbonate, diphenyl carbonate, diethylene carbonate, phosgene, or the like. Reactants and the like.

The polybutadiene polyol is not limited to the following examples. For example, it is based on a butadiene skeleton having a 1,2-vinyl structure, a 1,2-vinyl structure, a 1,4-trans structure, and a 1,4-trans structure. Examples of the unit include polyols and hydrogenated products thereof.

The number average molecular weight of the polyol component (A) is preferably from 300 to 100,000, and more preferably from 450 to 30,000. When the number average molecular weight of the polyol component (A) is 300 or more, a sufficient cohesive force can be obtained, thereby improving the adhesive force and preventing delamination after a wet heat test. When the number average molecular weight is 100,000 or less, an increase in viscosity can be suppressed, good coatability can be obtained, and further, compatibility with the compound (C) having a hydroxyl group and a steroid skeleton is improved, A good coating appearance can be obtained.

Among them, when the adhesive composition of the present invention is used as a solvent-free adhesive, it is more preferably from 300 to 5,000 in terms of viscosity, and when used as a solvent-based adhesive composition, It is more preferably from 10,000 to 50,000 in terms of viscosity and adhesive strength.

The hydroxyl value of the polyol component (A) is preferably from 5 to 200 mgKOH / g, more preferably from 6 to 150 mgKOH / g. When the hydroxyl value of the polyol component (A) is 5 mgKOH / g or more, crosslinking proceeds sufficiently, and good wet heat resistance is obtained. When the hydroxyl value is 200 mgKOH / g or less, an increase in crosslink density can be suppressed, and good adhesive strength can be obtained.

Above all, when the adhesive composition of the present invention is used as a solventless adhesive, it is more preferably 70 to 150 mgKOH / g, and when it is used as a solvent adhesive composition, it is 5 to 30 mgKOH / g. g is more preferable.

The acid value of the polyol component (A) is preferably 100 mgKOH / g or less, more preferably 30 mgKOH / g or less. When the acid value of the polyol component (A) is 100 mgKOH / g or less, a good pot life can be obtained.

<< polyisocyanate component (B) >>
Although the action of the polyisocyanate component (B) is not limited to the above, mainly, the polyisocyanate component undergoes a crosslinking reaction with a hydroxyl group in the polyol component (A) and a hydroxyl group in the compound (C) having a hydroxyl group and a steroid skeleton. It is used for the purpose of forming a network-like crosslinked structure and imparting high elasticity to be used as an adhesive and adhesion to a substrate. The polyisocyanate component (B) is not particularly limited as long as it can form a crosslinked structure with the hydroxyl group in the polyol component (A) and the hydroxyl group in the compound (C) having a hydroxyl group and a steroid skeleton. Aromatic isocyanates, aromatic isocyanates, araliphatic isocyanates, alicyclic isocyanates, and di- or more-functional isocyanate compounds such as burettes, nullates, adducts, and allophanates thereof.

Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also called HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like can be mentioned.

Examples of the aromatic isocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-tolidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate.

The araliphatic isocyanate means an aliphatic isocyanate having one or more aromatic rings in a molecule, for example, m- or p-xylylene diisocyanate (also called XDI), α, α, α ', α' -Tetramethylxylylene diisocyanate (alias: TMXDI) and the like.

Examples of the alicyclic isocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also called IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4. -Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

These polyisocyanate components can be used alone or in combination of two or more.

As the polyisocyanate component (B), it is preferable to use a burette form, a nullate form, an adduct form, or an allophanate form of an aliphatic isocyanate and / or an alicyclic isocyanate from the viewpoints of viscosity, pot life, and adhesive strength. From the viewpoint of heat resistance and heat resistance, it is more preferable that the polyisocyanate component (B) contains 15% by mass or more of the IPDI nurate in 100% by mass.

<<< Compound (C) having a hydroxyl group and a steroid skeleton >>>
The compound (C) having a hydroxyl group and a steroid skeleton is a compound having a hydroxyl group and having a cyclopentano-perhydrophenanthrene nucleus (synonymous with a steroid nucleus) as a basic skeleton. Can have a variety of structures, and many exist in plants.

Examples of the compound (C) having a hydroxyl group and a steroid skeleton include a compound having a cyclopentano-perhydrophenanthrene nucleus having a hydroxyl group, a compound having a double bond in an alicyclic ring of the nucleus, and a compound having a substituent thereon. Examples of the compound (C) include compounds represented by the following formulas [1] to [9]. (In the following formula, a broken line indicates that a C = C double bond may be used.)

Equation [1]

Equation [2]

Equation [3]

Equation [4]

Equation [5]

Equation [6]

Equation [7]

Equation [8]

Equation [9]

(In the formula, n represents 1 to 50.)

In the above formulas [1] to [9], R _{a to} R _i are each independently:
Hydrogen atom, oxygen atom, alkyl group, alkenyl group, alkynyl group, hydroxyl group, formyl group,
Alkylcarbonyl group, hydroxyalkylcarbonyl group, carboxyalkylcarbonyl group, formate alkylcarbonyl group, acetoxyalkylcarbonyl group,
Alkylcarboxy group, hydroxyalkylcarboxy group, carboxyalkylcarboxy group, formate alkylcarboxy group, acetoxyalkylcarboxy group,
Alkoxy group, hydroxyalkoxy group, carboxyalkoxy group, formate alkoxy group, acetoxyalkoxy group,
It is a benzoyloxy group or a group represented by any of the following formulas [10].
Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkenyl group include a vinyl group and an allyl group. Examples of the alkynyl group include an ethynyl group and a prop-2-yn-1-yl group.
("Formate" means "-O-CH = O". In the following formula, | * | indicates a bond.)

Formula [10]

Among them, the compound (C) having a hydroxyl group and a steroid skeleton preferably has one hydroxyl group in one molecule. By having one hydroxyl group in one molecule, a crosslinking reaction between the polyol component (A) and the polyisocyanate component (B) can be controlled, and high adhesive strength can be obtained.

The hydroxyl group of the compound (C) having a hydroxyl group and a steroid skeleton is preferably a primary hydroxyl group and / or a secondary hydroxyl group. By being a primary hydroxyl group and / or a secondary hydroxyl group, reactivity with the polyisocyanate component (B) is improved, and high wet heat resistance can be obtained.

The molecular weight of the compound (C) having a hydroxyl group and a steroid skeleton is preferably from 250 to 800, and more preferably from 300 to 500. When the molecular weight is 250 or more, a sufficient cohesive force can be obtained, and the adhesive force and the resistance to a high temperature and high humidity environment can be improved. When the molecular weight is 800 or less, excessive cohesion can be suppressed, and a decrease in adhesive strength can be suppressed.

In another preferred embodiment, the substituents R _{a to} R _{i in the} formulas [1] to [9] are each an alkyl group, an alkenyl group, or an alkynyl group having 5 or more carbon atoms. Is preferred. When the compound has an alkyl group, an alkenyl group, or an alkynyl group having 5 or more carbon atoms as a substituent, the adhesive strength and the moist heat resistance can be improved, and the compatibility with the polyol component (A) is further improved. .

Specific examples of the compound (C) having a hydroxyl group and a steroid skeleton described above include:
Desoxycorticosterone, 11-dehydrocorticosterone, NIKKOL BPS-X (X is 5, 10, 20, 30), NIKKOL BPSH-25, NIKKOL DHC-30, etc. available from Nikko Chemicals Co., Ltd. A compound having a steroid skeleton having a primary hydroxyl group;
Cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, testosterone, estrone, dehydroepiandrosterone, coprostanol, pregnenolone, epicholestanol, 7-dehydrocholesterol, tigogenin , A compound having a steroid skeleton having a secondary hydroxyl group such as hecogenin;
Compounds having a steroid skeleton having a tertiary hydroxyl group, such as methanedienone, cortisone acetate, and stenolone;
Steroids having a polyfunctional hydroxyl group such as β-estradiol, α-estradiol, boranediol, cortisone, prednisolone, corticosterone, aldosterone, 18-hydroxycorticosterone, 4-androstene-11α, 17β-diol-3-one, etc. Examples include compounds having a skeleton.
Among them, cholesterol, β-sitosterol, campesterol, stigmasterol, brassicasterol, lanosterol, ergosterol, β-cholestanol, coprostanol, epicholestanol, 7-dehydrocholesterol have one hydroxyl group in one molecule. Is more preferable because it has a molecular weight of 300 to 500 and the substituent has 5 or more carbon atoms.

These compounds (C) having a hydroxyl group and a steroid skeleton may be used alone or in a combination of two or more. Examples of the mixture of two or more types include phytosterol, which is a mixture of β-sitosterol, campesterol, stigmasterol, brassicasterol, and the like.

The content of the compound (C) having a hydroxyl group and a steroid skeleton is 0.1 to 20 parts by mass, preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the polyol component (A). More preferably, it is 2.0 to 13 parts by mass. When the content of the compound (C) having a hydroxyl group and a steroid skeleton is in the above range, high adhesive strength and high resistance to high-temperature and high-humidity environments can be obtained.

The adhesive composition of the present invention comprises an isocyanate group in the polyisocyanate component (B), a hydroxyl group in the polyol component (A), and an equivalent ratio of the hydroxyl group in the compound (C) having a hydroxyl group and a steroid skeleton (isocyanate group). / Hydroxy group) is preferably 0.6 to 5.0, more preferably 0.8 to 2.5. When the ratio of isocyanate group / hydroxyl group is 0.6 or more, crosslinking proceeds sufficiently and good adhesive strength is obtained, and when the ratio of isocyanate group / hydroxyl group is 5.0 or less, adhesive strength due to excessive cohesive force is obtained. And a decrease in acid resistance can be suppressed.

<< other components >>
The adhesive composition of the present invention may further contain an epoxy resin, a silane coupling agent, an oxygen acid of phosphorus or a derivative thereof, a catalyst, and the like for the purpose of further improving adhesive strength, heat resistance, and acid resistance.

The epoxy resin is not limited to the following examples, and includes, for example, a bisphenol A type epoxy resin. The bisphenol A type epoxy resin preferably has a number average molecular weight of 400 to 5,000. When the number average molecular weight is 400 or more, the water resistance and wet heat resistance of the adhesive composition can be sufficiently improved. When the number average molecular weight is 5,000 or less, it is possible to suppress a decrease in adhesive force due to a decrease in flexibility when forming an adhesive composition, and further reduce the viscosity of the adhesive composition, Workability can be improved.

The content of the epoxy resin is preferably 150 parts by mass or less, more preferably 10 to 60 parts by mass, based on 100 parts by mass of the polyol component (A). By adjusting the blending amount of the epoxy resin to 150 parts by mass or less, the flexibility of the adhesive composition can be more suitably adjusted, and by being 10 to 60 parts by mass, the adhesive force of the adhesive composition can be improved. Can be higher.

The silane coupling agent is not limited to the following examples, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, Aminosilanes such as N-β (aminoethyl) -γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,
epoxy silanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane;
Hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane and the like can be mentioned. One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

The content of the silane coupling agent is preferably 0.2 to 5 parts by mass based on 100 parts by mass of the polyol component (A). By using the silane coupling agent in the above range, for example, the adhesive strength when using a base material made of a metal material such as a metal foil can be further increased.

The oxyacid of phosphorus is not particularly limited as long as it has at least one free oxyacid, and examples thereof include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypophosphoric acid, and metaphosphoric acid. , Pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and condensed phosphoric acid such as ultraphosphoric acid.
Examples of the oxyacid derivative of phosphorus include those obtained by partially esterifying the above oxyacid of phosphorus with alcohols while leaving at least one free oxyacid, and the like. And aliphatic alcohols such as methanol, ethanol, ethylene glycol and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol and phloroglicinol.

The catalyst is used for the purpose of adjusting the curing time of the adhesive composition, but is not particularly limited, and examples thereof include known tertiary amines and organometallic compounds.
As the tertiary amine, for example, triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylbutanediamine or N, N, N ′, N′-tetramethylhexanediamine, pentamethyldiethylenetriamine, bis (dimethylaminopropyl) urea, 1,4, -dimethylpiperazine, 1,2-dimethylimidazole, 1-azobicyclo [3.3.0] octane, 1,4-diazobicyclo [2.2.2] octane, alkanolamine compound, triethanolamine, triisopropanolamine, N-methyldiethanolamine , N-ethyldiethanolamido , Dimethylethanolamine and the like.
As the organometallic compound, for example, tin (II) salts of organic carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexanoate, tin (II) laurate, dibutyltin diacetate, dibutyltin Dialkyltin (IV) salts of organic carboxylic acids such as dilaurate, dibutyltin maleate, dioctyltin diacetate, dioctyltin laurate, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxy Alkoxide organic titanium compounds such as titanium, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisoprot Poki Solvent-based chelated organic titanium compounds such as bis (ethyl acetoacetate), titanium diisopropoxy bis (triethanolaminate), titanium lactate ammonium salt, titanium lactate, an aqueous chelated organotitanium compounds such as titanium lactate and the like.

Also, for the purpose of suppressing the yellowing of the adhesive over time due to ultraviolet rays of the sun and the like, and the yellowing of the adhesive over time due to heat such as solar heat, known phosphorus-based or phenol-based antioxidants and ultraviolet stabilizers. , A metal deactivator.

Among these, in particular, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxymethyl-2,6-diphenol -T-butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4′-bis (2,6-di- t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), 4,4'-methylene -Bis (6-t-butyl-o-cresol), 4,4'-methylene-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-cyclohexyl) Phenol), 4,4'-bu Tylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-t-butylbenzyl) ) Sulfide, 4,4′-thiobis (6-t-butyl-o-cresol), 2,2′-thiobis (4-methyl-6-t-butylphenol), 2,6-bis (2′-hydroxy- 3'-t-butyl-5'-methylbenzyl) -4-methylphenol, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzenesulfonic acid, 2,2'-dihydroxy-3,3 ' -Di (α-methylcyclohexyl) -5,5′-dimethyl-diphenylmethane, α-octadecyl-3 (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 6- (hydroxy -3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol-bis [β- (3,5-di-t-butyl-4) -Hydroxyphenol) propionate], N, N'-hexamethylene-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio [diethyl-bis-3 (3 5-di-t-butyl-4-hydroxyphenyl) propionate], dioctadecyl ester of 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid, tetrakis [methylene-3 (3,5-di-t -Butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 1,1,3-tris (2-methyl-4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [ Hindered phenolic antioxidants such as β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanurate are preferred,
A hindered phenol-based antioxidant having a molecular weight of 500 or more, such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, is more preferable.

The adhesive composition of the present invention, in addition to the above components, if necessary, a filler, a softener, an antioxidant, a stabilizer, an adhesion promoter, a leveling agent, an antifoaming agent, a plasticizer, an inorganic filler, and an adhesive Additives such as imparting resins, fibers, usable time extenders, hydrolysis inhibitors, fungicides, thickeners, plasticizers, and coloring agents such as pigments can be contained.

Examples of the tackifying resin include, but are not limited to, terpene resins, aliphatic petroleum resins, aromatic petroleum resins, cumarone-indene resins, phenol resins, terpene-phenol resins, and rosin derivatives (rosin). Rosin, polymerized rosin, hydrogenated rosin, and their esterified products with polyhydric alcohols such as glycerin and pentaerythritol, resin acid dimer, etc.).

  The use form of the adhesive composition of the present invention may be a solventless adhesive or a solvent adhesive, but when used as a solvent adhesive, it contains the following organic solvent. Can be.

Examples of the organic solvent include, but are not limited to, acetone, methyl acetate, ethyl acetate, propyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, isopropanol, and the like. One of these organic solvents may be used alone, or two or more thereof may be used in combination.

<Laminate>
As a method for producing a laminate using the adhesive composition of the present invention, a known method can be used. For example, first, an adhesive composition is applied to one surface of one base material (first base material) using a comma coater or a dry laminator, and if necessary, the solvent is volatilized. (The second substrate), and aged and cured at room temperature or under heating.
The application temperature is usually 20 to 100 ° C., preferably 50 to 80 ° C. in consideration of workability at the time of application and viscosity of the adhesive composition under heating, and aging is performed at 20 to 60 ° C. It is preferable to leave still for 3 to 7 days. The coating amount is appropriately selected depending on the type of the base material, the coating conditions, and the like. For food packaging, 1 to 5 g / m ² , and for the solar cell back surface protection sheet, 1 to 5 g / m ² . It is preferably 50 g / m ² .

As the base material, any base material can be used in any number depending on the application, and is not limited to the following examples.For example, a plastic film, a metal foil, a metal oxide or An example is a vapor-deposited film on which a nonmetal oxide is vapor-deposited. The first substrate and the second substrate may be the same or different.

Examples of the plastic film include polyester resin films such as polyethylene terephthalate (hereinafter abbreviated as PET) and polynaphthalene terephthalate, high-density polyethylene (hereinafter abbreviated as HDPE), low-density polyethylene (hereinafter abbreviated as LDPE), Polyethylene resin film such as high density polyethylene (hereinafter abbreviated as LLDPE), polypropylene resin film such as unstretched polypropylene (hereinafter abbreviated as CPP), biaxially oriented polypropylene (hereinafter abbreviated as OPP), nylon resin film, polyamide system Resin film, polyvinyl chloride resin film, polycarbonate resin film, polysulfone resin film, poly (meth) acrylic resin film, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoro Ethylene, polyethylene tetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene - fluorocarbon resin film such as hexafluoropropylene copolymer.
Further, a film coated with an acrylic or fluorine-based paint using these plastic films as a support, or a multilayer film formed by laminating polyvinylidene fluoride, an acrylic resin, or the like by co-extrusion can be used. Further, a sheet-like member in which a plurality of the above-described plastic films are laminated via a urethane-based adhesive layer or the like may be used.

Examples of the metal foil include metal foils of aluminum, tin, iron, nickel, steel, lead, zinc, and the like, and metal foils of alloys of these metals. Examples of the metal oxide or nonmetallic inorganic oxide to be deposited include oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium.

  The application of the adhesive and the laminate of the present invention is not particularly limited. However, since the adhesive and the laminate have high adhesion and high temperature and high humidity resistance, they can be suitably used for packaging materials. The packaging material is not particularly limited as long as it is intended to wrap and protect a part or all of the article, and examples thereof include food packaging, medical product packaging, cosmetic packaging, and solar cell panel protective materials.

In the case of food packaging, for example, thermoplastic resin films such as OPP, PET, and stretched nylon, which have water resistance, heat resistance, and impact resistance, and are excellent in moisture resistance and gas barrier properties, and melted by heat, A thermoplastic resin film such as LDPE, LLDPE, CPP, etc., which can be fused to and has excellent cold resistance, impact resistance and low-temperature sealability, is suitably used.

In the case of a solar cell panel protective material represented by a back protective sheet for a solar cell, for example, in order to satisfy performances such as weather resistance, water vapor permeability, electrical insulation, mechanical properties, workability, etc., the resistance to temperature is required. Excellent, polyester-based resin film such as PET, polynaphthalene terephthalate, polycarbonate-based resin film, and metal foil, metal oxide, or non-metal that excels in water vapor barrier properties to prevent output reduction due to water in solar cells A plastic film on which an inorganic oxide is vapor-deposited, a fluorine-based resin film having excellent weather resistance for preventing appearance failure due to light deterioration, and the like are preferably used.

Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

<Measurement of nonvolatile content>
About 1 g of the sample solution was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the residual ratio was calculated to determine the nonvolatile content (nonvolatile content).

<Measurement of number average molecular weight (Mn)>
The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC). GPC "GPC-104" manufactured by Shodex was used as a measuring instrument. The column used was one in which two Shodex GPC LF-604 manufactured by Shodex were connected in series. The measurement was performed at 40 ° C. using tetrahydrofuran (THF) as a solvent (eluent). In addition, the number average molecular weight (Mn) was a converted value using polystyrene as a standard.

<Measurement of hydroxyl value (OHV)>
1 g of a sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and 100 ml of pyridine was added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make the volume 100 ml) was added, stirred for 1 hour, and titrated with a 0.5N-alcoholic potassium hydroxide solution. The hydroxyl value (unit: mgKOH / g) was determined by the following equation. The hydroxyl value was the value of the dried sample.
Hydroxyl value = [{(ba) × F × 28.05} / S] / (non-volatile concentration / 100) + D
S: Sample collection amount (g)
a: consumption of 0.5N-alcoholic potassium hydroxide solution (ml)
b: consumption of 0.5N-alcoholic potassium hydroxide solution in blank experiment (ml)
F: Factor of 0.5N-alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Measurement of acid value (AV)>
1 g of a sample is precisely weighed and placed in a stoppered Erlenmeyer flask, dissolved in 100 ml of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1), and then added to a 0.1N-alcoholic potassium hydroxide solution. And titrated. The acid value (unit: mgKOH / g) was determined by the following equation. The acid value was the value of the dried sample.
Acid value = {(5.61 × a × F) / S} / (non-volatile concentration / 100)
S: Sample collection amount (g)
a: consumption of 0.1N-alcoholic potassium hydroxide solution (ml)
F: Factor of 0.1N-alcoholic potassium hydroxide solution

<Measurement of isocyanate value (NCO value)>
A 10 g sample is precisely weighed and placed in a stoppered Erlenmeyer flask, and 25 ml of orthodichlorobenzene, di-n-butylamine / o-dichlorobenzene (mass ratio: di-n-butylamine / o-dichlorobenzene = 1 / 24.8). 10 ml of the mixture was added and dissolved. To this solution, 80 g of methanol and bromophenol blue reagent were added as indicators and titrated with a 0.1N alcoholic hydrochloric acid solution. The point at which the solution turned yellow-green and was held for 30 seconds or longer was regarded as the end point. The NCO value (unit:%) was determined by the following equation.
NCO value = {0.42 × (B−C) × F} / W
W: sampled amount (g)
B: consumption of 0.1N alcoholic hydrochloric acid solution required for sample titration (ml)
C: consumption of 0.1N alcoholic hydrochloric acid solution required for titration in blank test (ml)
F: Factor of 0.1N alcoholic hydrochloric acid solution

<Synthesis of polyol>
(Synthesis example 1)
A polymerization reactor equipped with a reaction tank, a stirrer, a thermometer, and a nitrogen inlet tube was prepared. 17.5 parts of isophthalic acid, 32.0 parts of adipic acid, 4.9 parts of benzoic acid, 7.6 parts of ethylene glycol, and 38.0 parts of neopentyl glycol are charged into a reaction vessel, and stirred under a nitrogen gas stream for 150 minutes. C. to 240.degree. C. to carry out an esterification reaction. When the acid value reached 2.1, the reaction temperature was raised to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes, and then cooled to 110 ° C. Thereafter, 0.5 part of trimellitic anhydride was added and the mixture was acid-modified at 110 ° C. to obtain a polyester polyol. The number average molecular weight of the obtained polyester polyol was 750, the hydroxyl value was 104, the acid value was 3.6, and the nonvolatile content was 100%.

(Synthesis example 2)
A polymerization reactor equipped with a reaction tank, a stirrer, a thermometer, and a nitrogen inlet tube was prepared. A reaction vessel was charged with 58.9 parts of isophthalic acid, 14.3 parts of ethylene glycol, and 26.9 parts of neopentyl glycol, and heated to 150 ° C. to 240 ° C. while stirring under a nitrogen gas stream to perform an esterification reaction. . When the acid value reached 1.5, the reaction temperature was raised to 200 ° C., the pressure inside the reaction vessel was gradually reduced, the reaction was carried out at 1.3 kPa or less for 30 minutes, and then cooled to 110 ° C. Thereafter, 0.7 part of trimellitic anhydride was added and the mixture was acid-modified at 110 ° C. to obtain a polyester polyol. The number average molecular weight of the obtained polyester polyol was 850, the hydroxyl value was 92.5, the acid value was 5.1, and the nonvolatile content was 100%.

(Synthesis example 3)
A polymerization reactor equipped with a reaction tank, a stirrer, a thermometer, and a nitrogen inlet tube was prepared. 74.5 parts of polytetramethylene glycol having a number average molecular weight of 2.000 (product name “PTG2000SN”, manufactured by Hodogaya Chemical Co., Ltd.), 6.6 parts of 3-methyl-1,5-pentanediol, isophorone diisocyanate Nine parts were charged into a reaction vessel and heated at 170 ° C. for 2 hours while stirring under a nitrogen gas stream to carry out a urethanization reaction. Thereafter, a solution containing a polyurethane polyol was obtained by adding 100 parts of ethyl acetate. The obtained polyurethane polyol had a number average molecular weight of 17,000, a hydroxyl value of 9.4, and a nonvolatile content of 50%.

(Synthesis example 4)
A polymerization reactor equipped with a reaction tank, stirrer, thermometer, reflux condenser, dropping tank, and nitrogen inlet tube was prepared. 100 parts of ethyl acetate was charged into a reaction vessel and heated to 80 ° C. while stirring under a nitrogen gas stream. Then, 39.9 parts of n-butyl acrylate, 58.2 parts of ethyl methacrylate, 1.9 parts of 2-hydroxyethyl acrylate, and azobisisobutyronitrile (product name "V-60", manufactured by Wako Pure Chemical Industries, Ltd.) ) A monomer mixture previously mixed with 0.6 part was dropped from the dropping tank over 2 hours. After the completion of the dropwise addition, the mixture was reacted for 1 hour while stirring, and 0.2 parts of azobisisobutyronitrile was further added thereto and reacted for 5 hours. After the reaction, the solution was cooled to room temperature to obtain a solution containing an acrylic polyol. The obtained acrylic polyol had a number average molecular weight of 35,000, a hydroxyl value of 8.7 and a nonvolatile content of 50%.

<Synthesis of resin other than (A)>
(Synthesis example 5)
A polymerization reactor equipped with a reaction tank, stirrer, thermometer, reflux condenser, dropping tank, and nitrogen inlet tube was prepared. 100 parts of ethyl acetate was charged into a reaction vessel and heated to 80 ° C. while stirring under a nitrogen gas stream. Then, 39.9 parts of n-butyl acrylate, 58.2 parts of ethyl methacrylate, 1.9 parts of acrylic acid, and azobisisobutyronitrile (product name “V-60”, manufactured by Wako Pure Chemical Industries, Ltd.) were added. A monomer mixture prepared by previously mixing 6 parts was dropped from the dropping tank over 2 hours. After the completion of the dropwise addition, the mixture was reacted for 1 hour while stirring, and 0.2 parts of azobisisobutyronitrile was further added thereto and reacted for 5 hours. After the reaction, the solution was cooled to room temperature to obtain a solution containing an acrylic resin. The resulting acrylic resin had a number average molecular weight of 35,000, an acid value of 13.8, and a nonvolatile content of 50%.

<< Embodiment 1 (adhesive for food packaging) >>

(Examples 1-1 to 1-12, Comparative Examples 1-1 to 1-5)
<Production of adhesive composition>
The polyol component (A), the polyisocyanate component (B), the compound (C) having a hydroxyl group and a steroid skeleton obtained in Synthesis Examples 1 and 2, the compounds other than (C), and the additives are shown in terms of nonvolatile components. The mixture was heated and mixed at the compounding ratio shown in Example 1 to prepare the solvent-free adhesive compositions of Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-5.

The compounds described in Table 1 are shown below.
<Polyisocyanate component (B)>
HDI burette: (Product name "Banasort HB-100", manufactured by BASF)
IPDI Nurate (1): (Product name "VESTANT T1890 / 100", manufactured by Evonik)

<Compound (C) having a hydroxyl group and a steroid skeleton>
Phytosterol: (Product name "Phytosterol CO", manufactured by Tama Seikagaku Co., Ltd.), number of hydroxyl groups: 1
Cholesterol: molecular weight 386.7, hydroxyl group 1
Desoxycorticosterone: molecular weight 330.5, hydroxyl group number 1
Dehydroepiandrosterone: molecular weight 288.4, hydroxyl group 1
Boranediol: molecular weight 276.4, number of hydroxyl groups 2

<Compounds other than (C)>
Cholesterol acetate: molecular weight 428.7

<Additives>
KBM-403: silane coupling agent (product name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.)
phosphoric acid

<Creation of laminate>
(Preparation of Laminate 1)
A dry laminating adhesive for high retort (product name “TM-250HV / CAT-RT86L-60”, manufactured by Toyo Morton Co., Ltd.) is applied to polyethylene terephthalate (thickness: 12 μm, hereinafter referred to as PET) using a dry laminator at 3.5 g / m 2. ² and a laminated aluminum foil (thickness: 9 μm), and the resulting laminate was aged in a 40 ° C. environment for 3 days to obtain a PET / aluminum foil laminate. Was.
Next, the solvent-free adhesive composition of Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-5 was applied to the aluminum foil surface of the PET / aluminum foil laminate by using a solvent-free test coater. At 70 ° C. so as to give a coating amount of 3 g / m ^2, and after bonding the coated surface to unstretched polypropylene (thickness: 70 μm, hereinafter referred to as CPP), the obtained laminate is placed in an environment of 40 ° C. For 3 days to obtain a laminate of PET / adhesive layer / aluminum foil / adhesive layer / CPP.

<Evaluation>

<Pot life>
For Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-5, the viscosities after 40 minutes of uniform mixing at 70 ° C. were measured, and judged according to the following criteria. Table 1 shows the results.
：: The viscosity is less than 8,000 mPa · s.
Δ: Viscosity is 8,000 mPa · s or more and less than 12,000 mPa · s.
X: The viscosity is 12,000 mPa · s or more.

About the laminated body 1 obtained in Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-5, each physical property of adhesive strength and retort resistance was evaluated by the following methods. Table 1 shows the results.

<Adhesive strength>
The laminate 1 prepared by the above method is cut into a width of 15 mm, and is pulled at a peeling rate of 300 mm / min using a tensile tester in an environment of 25 ° C. and 50% relative humidity, and the TPP between the CPP and the aluminum foil is reduced. The mold peel strength (N / 15 mm) was measured, and the adhesive strength was determined according to the following criteria.
◎ Excellent in practical use: 8 N / 15 mm or more ○ Practical range: 6 N / 15 mm or more, less than 8 N / 15 mm 下限 Lower practical limit: 4 N / 15 mm or more, less than 6 N / 15 mm × Unpracticable: less than 4 N / 15 mm

<Retort resistance (adhesive strength after heat sterilization)>
For the laminate 1 prepared by the above method, a bag having a size of 14 cm × 18 cm was prepared under the heat sealing condition of 190 ° C. for 1 second so that the CPP was on the inside. The contents were filled with a mixture of 3% acetic acid aqueous solution / ketchup / salad oil in a weight ratio of 1/1/1. The bag was subjected to hot water sterilization under a pressurized condition of 30 rpm, 135 ° C., and 30 minutes using a rotary retort tester, and then the T-type between the CPP / aluminum foil was measured in the same manner as the above-mentioned adhesive force measurement. The peel strength (N / 15 mm) was measured, and the adhesive strength was determined according to the following criteria.
◎ Excellent in practical use: 8 N / 15 mm or more ○ Practical range: 6 N / 15 mm or more, less than 8 N / 15 mm 下限 Lower practical limit: 4 N / 15 mm or more, less than 6 N / 15 mm × Unpracticable: less than 4 N / 15 mm

<< Embodiment 2 (adhesive for back protective sheet for solar cell) >>

(Examples 2-1 to 2-13, Comparative Examples 2-1 to 2-7)
<Production of adhesive composition>
Polyol component (A) obtained in Synthesis Examples 3 and 4, resins other than (A) obtained in Synthesis Example 5, polyisocyanate component (B), compounds having hydroxyl group and steroid skeleton (C), (C) Compounds other than the above and additives were heated and mixed at the compounding ratios shown in Tables 2 and 3 in terms of non-volatile components, respectively, and solvent-type adhesives of Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-7 were obtained. The composition was adjusted.

The compounds described in Tables 2 and 3 are shown below.
<Polyisocyanate component (B)>
IPDI Nurate (2): (Product name "DESMODUR Z 4470 BA", manufactured by Sumika Bayer Urethane Co.)
HDI-TMP: (Product name "Takenate D160N", manufactured by Mitsui Chemicals, Inc.)

<Compound (C) having a hydroxyl group and a steroid skeleton>
Phytosterol: (Product name "Phytosterol CO", manufactured by Tama Seikagaku)
Cholesterol: molecular weight 386.7
Desoxycorticosterone: molecular weight 330.5
Dehydroepiandrosterone: molecular weight 288.4
Boranediol: molecular weight 276.4

<Compounds other than (C)>
Cholesterol acetate: molecular weight 428.7

<Additives>
YD-012: bisphenol A type epoxy resin (product name "YD-012", manufactured by Toto Kasei Co., Ltd.)
KE-359: hydrogenated rosin ester (product name "Pine Crystal KE-359", manufactured by Arakawa Chemical Industries, hydroxyl value 43.9)
KBE-403: silane coupling agent (product name "KBE-403", manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-403: silane coupling agent (product name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.)
Phosphoric acid IRGANOX: antioxidant (product name "IRGANOX 1010", manufactured by BASF)
U-810: dioctyltin dilaurate (product name "Neostan U-810", manufactured by Nitto Kasei Corporation)

<Creation of laminate>
(Preparation of Laminate 2)
Adhesives of Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-6 on a corona-treated surface of a polyester film (thickness: 50 μm, product name “E5100”, manufactured by Toyobo Co., Ltd .; hereinafter, referred to as E5100) The composition was applied using a dry laminator such that the dry application amount was 4 to 5 g / m ² . After the solvent is volatilized, the polyester film (thickness: 50 μm, product name “Lumirror X-10S”, manufactured by Toray Industries, hereinafter referred to as X-10S) is adhered to the corona-treated surface under laminating conditions of 60 ° C. and 0.5 MPa. I combined. Thereafter, the laminate was aged in an environment of 40 ° C. for 5 days to obtain a laminate of X-10S / adhesive layer / E5100.

(Preparation of laminated body 3)
Using the adhesive compositions of Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-7, ETFE (50 μm thick, product name “Fluon”, Asahi Glass (Made by the company) / adhesive layer / E5100.

<Evaluation>
For the laminates 2 to 3 obtained in Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-7, the physical properties of the adhesive force and the adhesive force after the wet heat resistance test were evaluated by the following methods. Was done. The results are shown in Tables 2 and 3.

<Adhesive strength>
The formed laminates 2 to 3 were cut to a width of 15 mm, allowed to stand for 6 hours in an environment of 25 ° C. and a relative humidity of 65%, and then pulled under the same environment using a tensile tester at a peeling rate of 300 mm / min. The T-peel strength (N / 15 mm) between X-10S / adhesive layer / E5100 and between ETFE / adhesive layer / E5100 was measured, and the adhesive strength was determined according to the following criteria.
◎ Excellent in practical use: 5 N / 15 mm or more ○ Practical range: 4 N / 15 mm or more and less than 5 N / 15 mm 下限 Lower practical limit: 2 N / 15 mm or more, less than 4 N / 15 mm × Unpractical: less than 2 N / 15 mm

<Adhesive strength after wet heat resistance test>
The formed laminates 2 and 3 were cut to a width of 15 mm, and left for 1,000 hours and 2,000 hours in an environment of 85 ° C. and a relative humidity of 85%. Then, after leaving still in an environment of 25 ° C. and a relative humidity of 65% for 6 hours, under the same environment, the film was pulled at a peeling rate of 300 mm / min using a tensile tester, and between X-10S / adhesive layer / E5100 and The T-peel strength (N / 15 mm) between ETFE / adhesive layer / E5100 was measured, and the adhesive strength was determined according to the following criteria.

◎ Excellent in practical use: 5 N / 15 mm or more ○ Practical range: 4 N / 15 mm or more and less than 5 N / 15 mm 下限 Lower practical limit: 2 N / 15 mm or more, less than 4 N / 15 mm × Unpractical: less than 2 N / 15 mm

<Adhesive strength under heating conditions>
The prepared laminate 2 was cut to a width of 15 mm, and was pulled at a peeling rate of 300 mm / min using a tensile tester at 85 ° C. in an environment of 85 ° C. to obtain a T-shaped peel strength between X-10S / adhesive layer / E5100 (N / 15 mm), and the adhesive strength was determined based on the following criteria.
◎ Excellent in practical use: 2 N / 15 mm or more ○ Practical range: 1 N / 15 mm or more and less than 2 N / 15 mm 下限 Practical lower limit: 0.5 N / 15 mm or more, less than 1 N / 15 mm × Unpractical: less than 0.5 N / 15 mm

Claims (4)

An adhesive composition comprising a polyol component (A), a polyisocyanate component (B), a compound (C) having a hydroxyl group and a steroid skeleton,
The polyol component (A) contains at least one selected from the group consisting of an acrylic polyol (A1), a polyether polyol (A2), a polyester polyol (A3), and a polyurethane polyol (A4);
An adhesive composition comprising 0.1 to 20 parts by mass of the compound (C) based on 100 parts by mass of the polyol component (A). 2. The adhesive composition according to claim 1, wherein the compound (C) has one hydroxyl group in one molecule. The equivalent ratio of the isocyanato group in the polyisocyanate component (B), the hydroxyl group in the polyol component (A), and the hydroxyl group in the compound (C) (isocyanato group / hydroxyl group) is 0.6 to 5.0. The adhesive composition according to claim 1, wherein: A laminate in which at least two sheet-like substrates are laminated with the adhesive composition according to claim 1.