JP5634944B2 - Polyurethane adhesive and laminate film - Google Patents

Description

  The present invention relates to a polyurethane adhesive and a laminate film, and more particularly, to a polyurethane adhesive and a laminate film obtained using the polyurethane adhesive.

  As a packaging material used in various industrial fields, a laminate film, specifically, a laminate obtained by laminating a plastic film, a metal foil such as aluminum, a metal vapor-deposited film, a silica vapor-deposited film, etc. with an adhesive. Films are known.

  Examples of the adhesive used in the production of such a laminate film include organic polyisocyanate, polyol, and phosphorus oxygen acid or derivatives thereof (for example, mono-2-ethylhexyl orthophosphate, di-2-orthophosphate). A composition for polyurethane adhesives containing ethyl hexyl and the like has been proposed (see, for example, Patent Document 1).

  According to the composition for polyurethane adhesives shown in Patent Document 1, a coating film having excellent adhesive strength, heat resistance and chemical resistance can be obtained.

JP 58-122977 A

  On the other hand, in the packaging material field, depending on the application, there is a case where it is desired to peel the laminated film once produced. In such a case, it can be easily peeled, that is, it has excellent easy peelability. An adhesive capable of obtaining a coating film excellent in mechanical strength is required.

  An object of the present invention is to provide a polyurethane adhesive excellent in easy peelability and excellent in mechanical strength of a coating film, and a laminate film obtained using such a polyurethane adhesive.

  In order to achieve the above object, the polyurethane adhesive of the present invention comprises a polyisocyanate component, a polyol component, and an internal mold release agent containing an orthophosphoric acid derivative represented by the following general formula (1). Yes.

(In the formula, R1 and R2 are the same or different from each other and each represent a hydrocarbon group having 9 to 24 carbon atoms, or one of them represents a hydrocarbon group having 9 to 24 carbon atoms, and the other represents Indicates a hydrogen atom.)
Moreover, in the polyurethane adhesive of this invention, it is preferable that the content rate of the said internal mold release agent is 0.01-3 mass parts with respect to 100 mass parts of solid content of the said polyisocyanate component and the said polyol component. Is preferred.

  Moreover, in the polyurethane adhesive of this invention, it is suitable that the elongation at break at 23 degreeC measured based on JISK7312 (1996) of the coating film obtained by hardening is 100 to 900%. is there.

  In addition, the polyurethane adhesive of the present invention is preferably a film laminating adhesive that bonds a plurality of substrates made of a resin film and / or a metal foil.

  In addition, the laminate film of the present invention is characterized in that it is obtained by bonding a plurality of substrates with the above polyurethane adhesive.

  In the laminate film of the present invention, the base material is at least one selected from the group consisting of a polyethylene terephthalate film, an aluminum foil, a copper foil, a corona-treated polyethylene film, and a corona-treated polypropylene film. Preferably it is a seed.

  In the laminate film of the present invention, it is preferable that the peel strength between the substrates bonded by the polyurethane adhesive is 1.5 N / 15 mm width or less.

  The polyurethane adhesive of the present invention is excellent in easy peelability and excellent in the mechanical strength of a coating film obtained by curing.

  Moreover, the laminate film of the present invention obtained using the polyurethane adhesive of the present invention has excellent mechanical strength and can be easily peeled off.

  The polyurethane adhesive of the present invention contains a polyisocyanate component, a polyol component, and an internal release agent.

  Examples of the polyisocyanate component include a polyisocyanate monomer, a polyisocyanate derivative, and an isocyanate group-terminated prepolymer.

  Examples of the polyisocyanate monomer include polyisocyanates such as aromatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), Examples include aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Methyl xylylene diisocyanate or a mixture thereof (TMXDI), aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexylisocyanate, these Trans, Trans - body, Trans, Cis body, Cis, Cis body, or mixtures _thereof)) (H 12 _MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane Isocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane Or a mixture thereof) (H ₆ XDI) and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate and other aliphatic diisocyanates Can be mentioned.

  Examples of the polyisocyanate derivative include a multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazinedione-modified product), pentamer, 7) of the polyisocyanate monomer described above. , Etc.), allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-mentioned polyisocyanate monomers and alcohols), polyol-modified products (for example, polyisocyanate monomers and alcohols) Polyol-modified products (alcohol adducts, etc.) produced from the reaction, biuret-modified products (for example, biuret-modified products produced by the reaction of the polyisocyanate monomer described above with water or amines), urea-modified products ( For example, the urea modification produced by the reaction of the above-mentioned polyisocyanate monomer and diamine. Etc.), oxadiazine trione-modified products (for example, oxadiazine trione produced by reaction of the above-mentioned polyisocyanate monomer and carbon dioxide gas), carbodiimide-modified products (decarboxylation of the above-mentioned polyisocyanate monomer) Carbodiimide modified products produced by condensation reaction), uretdione modified products, uretonimine modified products, and the like.

  The isocyanate group-terminated prepolymer is a urethane prepolymer having at least two isocyanate groups at the molecular ends, and is a polyisocyanate (polyisocyanate selected from polyisocyanate monomers, polyisocyanate derivatives and isocyanate group-terminated prepolymers, preferably Is a polyisocyanate selected from a polyisocyanate monomer and a polyisocyanate derivative) and a polyol component (described later), and the equivalent ratio (NCO / OH) of the polyisocyanate to the hydroxyl group of the polyol component (described later) is from 1 It can be obtained by a urethanization reaction at a rate of increasing, preferably at a rate of 1.5 to 50.

  The urethanization reaction can be based on a known method. The reaction temperature in the urethanization reaction is, for example, 50 to 120 ° C., preferably 50 to 100 ° C., and the reaction time is, for example, 0.5 to 15 hours, preferably 1 to 10 hours.

  In the urethanization reaction, if necessary, an organic solvent is blended, and in the presence thereof, an isocyanate group-terminated prepolymer can be prepared (solution polymerization).

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; nitriles such as acetonitrile; alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; Aliphatic hydrocarbons such as hexane, n-heptane, and octane, for example, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, such as methyl cellosolve acetate , Ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxy Glycol ether esters such as butyl acetate and ethyl-3-ethoxypropionate, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, iodine Halogenated aliphatic hydrocarbons such as methylene chloride and dichloroethane, for example, polar aprotics such as N-methylpyrrolidone, dimethylformamide, N, N′-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc. .

  These organic solvents can be used alone or in combination of two or more.

  The mixing ratio of the organic solvent is appropriately set depending on the purpose and application.

  In the urethanization reaction, for example, a known urethanization catalyst such as an organic acid, tin, lead, or amine may be added as necessary. The free (unreacted) polyisocyanate from the polymer may be removed by a known removal means such as distillation or extraction.

  The isocyanate group equivalent of the isocyanate group-terminated prepolymer is, for example, 200 to 2000, preferably 300 to 1000. Moreover, content of unreacted polyisocyanate is 15 mass% or less, for example, Preferably, it is 5 mass% or less, More preferably, it is 1 mass% or less.

  In addition, an isocyanate group equivalent is synonymous with an amine equivalent, and can be calculated | required by A method or B method of JISK1603-1. The content of unreacted polyisocyanate can be determined, for example, by HPLC measurement.

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

  The polyisocyanate component is preferably a single use of a polyisocyanate derivative or a combined use of a polyisocyanate derivative and an isocyanate group-terminated prepolymer.

  When the polyisocyanate derivative and the isocyanate group-terminated prepolymer are used in combination, their blending ratio (solid content) is, for example, 100 parts by mass of the solid content of the polyisocyanate component. 1-99 mass parts, Preferably, it is 10-90 mass parts, and an isocyanate group terminal prepolymer is 1-99 mass parts, for example, Preferably, it is 10-90 mass parts.

  Moreover, a polyisocyanate component can also be prepared as a solution of an above-described solvent, In that case, the solid content concentration is 10-90 mass%, for example, Preferably, it is 20-80 mass%.

  Moreover, the isocyanate group content rate (based on JISK1556 (2006)) of a polyisocyanate component is 0.8-8.5 mass%, for example, Preferably, it is 1.4-6.0 mass%. Moreover, the amine equivalent (based on JISK1556 (2006)) of this urethane prepolymer is 500-5000, for example, Preferably, it is 700-3000.

  Examples of the polyol component include a low molecular weight polyol and a high molecular weight polyol.

  The low molecular weight polyol is an organic compound having two or more hydroxyl groups and a number average molecular weight of less than 400, and examples thereof include a low molecular weight diol, a low molecular weight triol, and a low molecular weight polyol having four or more hydroxyl groups.

  Examples of the low molecular weight diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 3,3-dimethylol C2-22 alkanediols such as heptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, such as 2-butene-1,4-diol, Alkene diols such as 2,6-dimethyl-1-octene-3,8-diol What aliphatic diol. Further, examples of the low molecular weight diol include alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, or a C2-4 alkylene oxide adduct thereof. Examples of the low molecular weight diol include aromatics such as resorcin, xylylene glycol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, bisphenol A, bisphenol S, bisphenol F, and C2-4 alkylene oxide adducts of the above bisphenols. Diols are mentioned. Examples of the low molecular weight diol include ether diols such as diethylene glycol, triethylene glycol, and dipropylene glycol.

  Examples of the low molecular weight triol include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, and trimethylolethane. , Trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol and others And aliphatic triols (8 to 24 carbon atoms).

  Examples of the low molecular weight polyol having 4 or more hydroxyl groups include tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, D-mannitol and the like.

  These low molecular weight polyols can be used alone or in combination of two or more.

  The high molecular weight polyol is an organic compound having two or more hydroxyl groups and a number average molecular weight of 400 or more. For example, polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol , Polyolefin polyol, urethane polyol and the like.

  The polyether polyol is a polyalkylene oxide, for example, polyethylene glycol, polypropylene glycol obtained by addition reaction of an alkylene oxide such as ethylene oxide and / or propylene oxide using the above low molecular weight polyol as an initiator. Polyethylene polypropylene glycol (random or block copolymer). Examples thereof include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

  As the polyester polyol, for example, a condensation reaction between a polyhydric alcohol selected from one or more of the above-described low molecular weight polyols, a polybasic acid, an alkyl ester thereof, an acid anhydride thereof, and an acid halide thereof. Or the polyester polyol obtained by transesterification is mentioned.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (11 to 13 carbon atoms), hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid And het acid.

  Examples of the alkyl ester of polybasic acid include methyl ester and ethyl ester of polybasic acid described above.

  Examples of the acid anhydride include acid anhydrides derived from the above-mentioned polybasic acids. For example, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (carbon number 12-18) ) Succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride and the like.

  Examples of the acid halide include acid halides derived from the polybasic acids described above, and examples include oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.

  Further, as the polyester polyol, for example, a hydroxyl group-containing vegetable oil fatty acid (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, lactic acid, etc.) using the above-described low molecular weight polyol as an initiator. And vegetable oil-based polyester polyols obtained by condensation reaction of hydroxycarboxylic acids such as those under known conditions.

  Furthermore, the polyester polyol includes, for example, the above-described low molecular weight polyol as an initiator, for example, lactones such as ε-caprolactone and γ-valerolactone, and lactides such as L-lactide and D-lactide. Examples thereof include polyester polyols such as polycaprolactone polyol and polyvalerolactone polyol obtained by ring-opening polymerization.

  Examples of the polycarbonate polyol include polycarbonate polyols obtained by using the above-described low molecular weight polyol as an initiator and carbonates such as ethylene carbonate and dimethyl carbonate. The polycarbonate polyol includes an amorphous polycarbonate diol composed of a copolymer of 1,5-pentanediol and 1,6-hexanediol, and a copolymer of 1,4-butanediol and 1,6-hexanediol. An amorphous polycarbonate diol composed of amorphous polycarbonate diol and 3-methyl-1,5-pentanediol.

  Examples of the acrylic polyol include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups and another monomer copolymerizable therewith.

  Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, and polyhydroxy. Examples thereof include alkyl maleates and polyhydroxyalkyl fumarate.

  Moreover, as another monomer copolymerizable therewith, for example, (meth) acrylic acid, alkyl (meth) acrylate (C1-12), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanato-2-propyl) -α-methylstyrene, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate.

  The acrylic polyol can be obtained by copolymerizing these monomers in the presence of an appropriate solvent and a polymerization initiator.

  Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

  Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and coconut oil.

  As the silicone polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as γ-methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.

  As the fluorine polyol, for example, in the copolymerization of the above-mentioned acrylic polyol, a copolymer containing a vinyl group-containing fluorine compound, for example, tetrafluoroethylene, chlorotrifluoroethylene, etc., as another copolymerizable monomer Etc.

  Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

  The urethane polyol has the above-described low molecular weight polyol and / or high molecular weight polyol and the above polyisocyanate component, and the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the low molecular weight polyol is less than 1. It can obtain by making urethanation reaction in the ratio which becomes.

  Moreover, as low molecular weight polyol and / or high molecular weight polyol, Preferably, low molecular weight diol, low molecular weight triol, and polyether polyol are used together.

  The hydroxyl equivalent of the urethane polyol is, for example, 150 to 10000, preferably 200 to 80000, and the number average molecular weight is, for example, 300 to 30000, preferably 400 to 25000.

  These high molecular weight polyols can be used alone or in combination of two or more.

  As the high molecular weight polyol, polyester polyol and urethane polyol are preferable.

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

  The polyol component can also be prepared as a solution of the above-described solvent. In that case, the solid content concentration is, for example, 10 to 90% by mass, preferably 20 to 80% by mass.

  Moreover, the hydroxyl group equivalent of a polyol component is 150-10000, for example, Preferably, it is 200-8000, and a number average molecular weight is 300-30000, for example, Preferably, it is 400-24000.

  The internal mold release agent contains an orthophosphoric acid derivative represented by the following general formula (1) (hereinafter referred to as a high carbon number orthophosphoric acid derivative).

(In the formula, R1 and R2 are the same or different from each other and each represent a hydrocarbon group having 9 to 24 carbon atoms, or one of them represents a hydrocarbon group having 9 to 24 carbon atoms, and the other represents Indicates a hydrogen atom.)
In said formula (1), R1 shows a C9-C24 hydrocarbon group or a hydrogen atom (only when R2 shows a C9-C24 hydrocarbon group).

  Examples of the hydrocarbon group having 9 to 24 carbon atoms include an alkyl group having 9 to 24 carbon atoms, an alkenyl group having 9 to 24 carbon atoms, an alkynyl group having 9 to 24 carbon atoms, and an aryl group having 9 to 24 carbon atoms. Is mentioned.

  Examples of the alkyl group having 9 to 24 carbon atoms include 1-nonyl, isononyl, 1-decyl, isodecyl, 1-undecyl, isoundecyl, 1-dodecyl, isododecyl, 1-tridecyl, isotridecyl, 1-tetradecyl, isotetradecyl. 1-pentadecyl, isopentadecyl, 1-hexadecyl, isohexadecyl, 1-heptadecyl, isoheptadecyl, 1-octadecyl, isooctadecyl, 1-nonadecyl, isononadecyl, 1-icosyl, isoicosyl, 1-eicosyl, isoeicosyl, 1- Examples include hencicosyl, isochenicosyl, 1-heneicosyl, isohenecosyl, 1-docosyl, isodocosyl, 1-tricosyl, isotricosyl, 1-tetracosyl, isotetracosyl and the like.

  Examples of the alkenyl group having 9 to 24 carbon atoms include nonenyl, isononenyl, decenyl, isodecenyl, undecenyl, isoundecenyl, dodecenyl, isododecenyl, tridecenyl, isotridecenyl, tetradecenyl, isotetradecenyl, pentadecenyl, isopentadecenyl, hexadecenyl , Isohexadecenyl, heptadecenyl, isoheptadecenyl, octadecenyl (lauryl), isooctadecenyl, nonadecenyl, isononadecenyl, icocenyl, isoicocenyl, eicosenyl, isoeicosenyl, henococenyl, isohenicocenyl, dococenyl, isdocosenyl, Tricocenyl, isotricosenyl, tetracocenyl, isotetracocenyl and the like can be mentioned.

  Examples of the alkynyl group having 9 to 24 carbon atoms include noninyl, isononinyl, decynyl, isodecinyl, undecynyl, isoundecinyl, dodecinyl, isododecyl, tridecynyl, isotridecynyl, tetradecynyl, isotetradecynyl, pentadecynyl, isopentadecynyl, isodecadecyl, isodecynyl, Hexadecynyl, heptadecynyl, isoheptadecynyl, octadecynyl, isooctadecynyl, nonadecynyl, isononadecinyl, icosinyl, isoicosinyl, eicosinyl, isoeicosinyl, heicosinyl, isohenicosinyl, docosinyl, isodocosinyl, tricosinyl, isotricosynyl, Nil and the like.

  Examples of the aryl group having 9 to 24 carbon atoms include biphenyl, trimethylphenyl, naphthyl, anthracyl, phenanthryl and the like.

  Preferred examples of the hydrocarbon group having 9 to 24 carbon atoms include an alkyl group having 9 to 24 carbon atoms and an alkenyl group having 9 to 24 carbon atoms.

  In said formula (1), R2 shows a C9-C24 hydrocarbon group or a hydrogen atom (only when R1 shows a C9-C24 hydrocarbon group).

  Examples of the hydrocarbon group having 9 to 24 carbon atoms include the above alkyl group having 9 to 24 carbon atoms, the above alkenyl group having 9 to 24 carbon atoms, the above alkynyl group having 9 to 24 carbon atoms, and the above 9 carbon number. -24 aryl groups and the like.

  In the above formula (1), when both R1 and R2 represent a hydrocarbon group having 9 to 24 carbon atoms, these hydrocarbon groups are the same or different from each other in R1 and R2. Preferably, they are identical to each other.

  That is, the orthophosphoric acid derivative having a high carbon number is preferably an orthophosphoric acid derivative in which R1 and R2 in the above formula (1) represent the same hydrocarbon group having 9 to 24 carbon atoms.

  Further, as the high carbon number orthophosphoric acid derivative, preferably, in the above formula (1), either R1 or R2 represents a hydrocarbon group having 9 to 24 carbon atoms, and the other represents a hydrogen atom. Also included are acid derivatives.

  Specific examples of such a high carbon number orthophosphoric acid derivative include, for example, mono-1-nonyl phosphate, di-1-nonyl phosphate, monoisononyl phosphate, diisononyl phosphate, mono-1-decyl phosphate, Di-1-decyl phosphate, monoisodecyl phosphate, diisodecyl phosphate, mono-1-undecyl phosphate, di-1-undecyl phosphate, monoisoundecyl phosphate, diisoundecyl phosphate, mono-1-dodecyl phosphate , Di-1-dodecyl phosphate, monoisododecyl phosphate, diisododecyl phosphate, mono-1-tridecyl phosphate, di-1-tridecyl phosphate, monoisotridecyl phosphate, diisotridecyl phosphate, mono-phosphate 1-tetradecyl, di-1-tetradecyl phosphate, monoisotetradecyl phosphate, diisotetradecyl phosphate, monophosphate 1-pentadecyl, di-1-pentadecyl phosphate, monoisopentadecyl phosphate, diisopentadecyl phosphate, mono-1-hexadecyl phosphate, di-1-hexadecyl phosphate, monoisohexadecyl phosphate, phosphorus Diisohexadecyl phosphate, mono-1-heptadecyl phosphate, di-1-heptadecyl phosphate, monoisoheptadecyl phosphate, diisoheptadecyl phosphate, mono-1-octadecyl phosphate, di-1-phosphate Octadecyl, monoisooctadecyl phosphate, diisoctadecyl phosphate, mono-1-nonadecyl phosphate, di-1-nonadecyl phosphate, monoisononadecyl phosphate, diisononadecyl phosphate, mono-1-icosyl phosphate, di-phosphate -1-icosyl, monoisoicosyl phosphate, diisoicosyl phosphate, mono-1-eicosyl phosphate, Di-1-eicosyl phosphate, monoisoeicosyl phosphate, diisoeicosyl phosphate, mono-1-henicosyl phosphate, di-1-henicosyl phosphate, monoisohenicosyl phosphate, diisohenicosyl phosphate, Mono-1-henecosyl phosphate, di-1-henecosyl phosphate, monoisoheneicosyl phosphate, diisoheneicosyl phosphate, mono-1-docosyl phosphate, di-1-docosyl phosphate, phosphoric acid Monoisodocosyl, diisodocosyl phosphate, mono-1-tricosyl phosphate, di-1-tricosyl phosphate, monoisotricosyl phosphate, diisotricosyl phosphate, mono-1-tetracosyl phosphate, di-1-tetracosyl phosphate, phosphorus Monoisotetracosyl acid, diisotetracosyl phosphate, monooleyl phosphate, dioleyl phosphate, etc. The

  These high carbon number orthophosphoric acid derivatives can be used alone or in combination of two or more.

  If such a high carbon number orthophosphoric acid derivative is contained in the internal mold release agent, excellent easy peelability of the polyurethane adhesive can be secured.

  The internal mold release agent can contain, for example, an orthophosphoric acid derivative represented by the following general formula (2) (hereinafter referred to as a low carbon number orthophosphoric acid derivative).

(In the formula, R3 and R4 are the same as or different from each other, and each represents a hydrocarbon group having 1 to 8 carbon atoms, or one of them represents a hydrocarbon group having 1 to 8 carbon atoms, and the other represents Indicates a hydrogen atom.)
In said formula (2), R3 shows a C1-C8 hydrocarbon group or a hydrogen atom (only when R4 shows a C1-C8 hydrocarbon group).

  Examples of the hydrocarbon group having 1 to 8 carbon atoms include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 8 carbon atoms. Is mentioned.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl. , Isooctyl, 2-ethylhexyl and the like.

  Examples of the alkenyl group having 2 to 8 carbon atoms include ethenyl, propenyl, isopropenyl, butynyl, isobutynyl, sec-butynyl, tert-butynyl, pentenyl, isopentenyl, sec-pentenyl, hexenyl, isohexenyl, heptenyl, isoheptenyl, octenyl, Examples include isooctenyl and 2-ethylhexenyl.

  Examples of the alkynyl group having 2 to 8 carbon atoms include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, sec-butynyl, tert-butynyl, pentynyl, isopentynyl, sec-pentynyl, hexynyl, isohexynyl, heptynyl, isoheptynyl, octynyl, isooctynyl, 2-ethylhexynyl etc. are mentioned.

  Examples of the aryl group having 6 to 8 carbon atoms include phenyl, tolyl, xylyl and the like.

  As a C1-C8 hydrocarbon group, Preferably, a C1-C8 alkyl group is mentioned.

  Moreover, in said formula (2), R4 shows a C1-C8 hydrocarbon group or a hydrogen atom (only when R3 shows a C1-C8 hydrocarbon group).

  Examples of the hydrocarbon group having 1 to 8 carbon atoms include the above-described alkyl group having 1 to 8 carbon atoms, the above-described alkenyl group having 1 to 8 carbon atoms, the above-described alkynyl group having 1 to 8 carbon atoms, and the above-described 1 carbon atom. -8 aryl groups and the like.

  In the above formula (2), when R3 and R4 each represent a hydrocarbon group having 1 to 8 carbon atoms, these hydrocarbon groups are the same or different from each other in R1 and R2, preferably Are identical to each other.

  That is, the low carbon number orthophosphoric acid derivative is preferably a low carbon number orthophosphoric acid derivative in which R3 and R4 in the above formula (2) represent the same hydrocarbon group having 1 to 8 carbon atoms.

  Further, as the low carbon number orthophosphoric acid derivative, preferably, in the above formula (2), either R3 or R4 represents a hydrocarbon group having 1 to 8 carbon atoms, and the other represents a hydrogen atom. Also included are acid derivatives.

  As such a low carbon number orthophosphoric acid derivative, specifically, for example, monomethyl phosphate, dimethyl phosphate, diethyl phosphate, monoethyl phosphate, monopropyl phosphate, dipropyl phosphate, monoisopropyl phosphate, phosphoric acid Diisopropyl, monobutyl phosphate, dibutyl phosphate, monoisobutyl phosphate, diisobutyl phosphate, mono-sec-butyl phosphate, di-sec-butyl phosphate, mono-tert-butyl phosphate, di-tert-butyl phosphate, mono-phosphate Pentyl, dipentyl phosphate, monoisopentyl phosphate, diisopentyl phosphate, monosec-pentyl phosphate, disec-pentyl phosphate, monohexyl phosphate, dihexyl phosphate, monoisohexyl phosphate, diisohexyl phosphate, phosphoric acid Monoheptyl, diheptyl phosphate, monophosphate Sohepuchiru, Jiisohepuchiru phosphoric acid, phosphoric acid mono octyl, dioctyl phosphate, mono isooctyl, diisooctyl phosphate, mono-2-ethylhexyl, and the like phosphoric acid di 2-ethylhexyl.

  These low carbon number orthophosphoric acid derivatives can be used alone or in combination of two or more.

  The internal mold release agent can further contain, for example, a modified silicone oil.

  The modified silicone oil is a silicone oil having a structure in which a part of methyl group of dimethyl silicone is substituted with a functional group. Specifically, for example, polyether modified silicone, epoxy modified silicone, amino modified silicone, carboxyl modified Examples include silicone, mercapto-modified silicone, carbinol-modified silicone, methacryl-modified silicone, and long-chain alkyl-modified silicone.

  These modified silicone oils can be used alone or in combination of two or more.

  When the internal mold release agent contains a high carbon number orthophosphoric acid derivative and a low carbon number orthophosphoric acid derivative and / or a modified silicone oil, their content is based on 100 parts by mass of the internal mold release agent. The high carbon number orthophosphoric acid derivative is, for example, 10 to 95 parts by mass, preferably 20 to 90 parts by mass, and the low carbon number orthophosphoric acid derivative and / or modified silicone oil (the total amount when used together) Is, for example, 5 to 90 parts by mass, preferably 10 to 80 parts by mass.

  The content of such an internal release agent (the total amount of the high carbon number orthophosphoric acid derivative as an essential component and the low carbon number orthophosphoric acid derivative and / or modified silicone oil as an optional component) is the polyisocyanate component. And it is 0.005-5 mass parts with respect to 100 mass parts of solid content total amount of a polyol component, Preferably, it is 0.01-3 mass parts, More preferably, it is 0.05-2 mass parts.

  If the content rate of such an internal mold release agent is the said range, the outstanding releasability of a polyurethane adhesive can be ensured.

  The polyurethane adhesive of the present invention is prepared, for example, as a two-component curable adhesive or a one-component curable adhesive.

  In the two-component curable adhesive, the above-described polyol component (main agent) and the above-described polyisocyanate component (curing agent) are respectively prepared and blended at the time of use.

  In the two-component curable adhesive, the internal mold release agent is prepared separately from, for example, a polyol component and a polyisocyanate component, and is blended in the above-described ratio together with the polyol component and the polyisocyanate component at the time of use. Moreover, an internal mold release agent can also be previously mix | blended in the above-mentioned ratio, for example in any one or both of a polyol component and a polyisocyanate component.

  In addition, the two-component curable adhesive can be prepared without a solvent, but if necessary, a solvent can be blended with either or both of the polyisocyanate component and the polyol component.

  The solvent is not particularly limited, and examples thereof include the organic solvents described above.

  The mixing ratio of the solvent is appropriately set depending on the purpose and application.

  Furthermore, in the two-component curable adhesive, at least one selected from the group consisting of a polyisocyanate component, a polyol component, and an internal release agent may be used, for example, an antioxidant, an ultraviolet absorber, a light stabilizer. Agent, filler, silane coupling agent, epoxy resin, catalyst, coatability improver, leveling agent, nucleating agent, lubricant, mold release agent, antifoaming agent, plasticizer, surfactant, pigment, dye, organic or Known additives such as inorganic fine particles, antifungal agents, flame retardants and the like can be blended.

  In addition, the mixture ratio of an additive is suitably set according to the purpose and application.

  In such a two-part curable adhesive, when diluted with a solvent to form a solution, the viscosity (25 ° C.) of the polyol component is, for example, 100 to 20000 mPa · s, preferably 200 to 10000 mPa · s. The viscosity (25 ° C.) of the polyisocyanate component is, for example, 5 to 10000 mPa · s, preferably 10 to 8000 mPa · s.

  In such a two-component curable adhesive, when there is no solvent, the viscosity (25 ° C.) of the polyol component is, for example, 100 to 2,000,000 mPa · s, preferably 1,000 to 100,000 mPa · s. The viscosity (25 ° C.) of, for example, is, for example, 100 to 2,000,000 mPa · s, or preferably 1,000 to 100,000 mPa · s.

  The viscosity can be measured by using a rotary viscometer or the like.

  In the two-component curable adhesive, the blending ratio of the polyol component and the polyisocyanate component at the time of use is, for example, the equivalent ratio R (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component is, for example, , 0.5 to 5, preferably 0.6 to 3.

  Examples of the one-component curable adhesive include a moisture curable adhesive that is cured by moisture or steam (such as amine steam).

  Such a one-component curable adhesive comprises a urethane prepolymer having an isocyanate group at the molecular end obtained by reacting the above-described polyisocyanate component and the above-described polyol component, and the above-described internal release agent. It is contained in one liquid.

  In order to prepare the urethane prepolymer, the polyisocyanate component and the polyol component are mixed and reacted so that the isocyanate group of the polyisocyanate component is excessive with respect to the hydroxyl group of the polyol component.

  More specifically, for example, the equivalent ratio R (NCO / OH) of the isocyanate group of the polyisocyanate component to the hydroxyl group of the polyol component exceeds, for example, 1 and preferably 1 The reaction is carried out at a reaction temperature of 50 to 140 ° C., for example, for 1 to 5 hours, for example, in a ratio of 1.2 to 5.0, more preferably 1.2 to 5.0.

  In addition, when the equivalent ratio R (NCO / OH) of the polyisocyanate group to the hydroxyl group is less than 1.1, the viscosity of the polyurethane adhesive becomes very high and it is difficult to apply to the base material (described later). Or it may gel.

  In this reaction, for example, known urethanization catalysts such as organic acid, tin, lead, and amine can be used as necessary.

  And the isocyanate group content rate (based on JISK1556 (2006)) of the urethane prepolymer obtained in this way is 0.8-8.5 mass%, for example, Preferably, it is 1.4-6. 0% by mass. Moreover, the amine equivalent (based on JISK1556 (2006)) of this urethane prepolymer is 500-5000, for example, Preferably, it is 700-3000.

  In the one-component curable adhesive, the internal mold release agent is blended, for example, in one or both of the polyisocyanate component and the polyol component before preparation of the urethane prepolymer at the above-described ratio. Moreover, it can also mix | blend with the urethane prepolymer after preparation, for example.

  Furthermore, in the one-component curable adhesive, the above-described additives can be blended with at least one selected from the group consisting of a polyisocyanate component, a polyol component, and an internal release agent, if necessary.

  In addition, the mixture ratio of an additive is suitably set according to the purpose and application.

  The one-component curable adhesive can be prepared without a solvent, but can also be prepared in the presence of a solvent if necessary.

  The solvent is not particularly limited, and examples thereof include the organic solvents described above.

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

  The mixing ratio of the solvent is appropriately set depending on the purpose and application.

  Such a polyurethane adhesive (including a two-component curable adhesive and a one-component curable adhesive) is excellent in easy peelability as described later, and further includes, for example, a polyisocyanate component, a polyol component and an internal component. The peel strength (described later) between substrates bonded by the adhesive can be easily controlled by adjusting the blending ratio of the release agent.

  Furthermore, such a polyurethane adhesive is excellent in the mechanical strength and heat resistance of the coating film obtained by curing.

  The elongation at break at 23 ° C. measured according to JIS K 7312 (1996) of the cured coating film of the polyurethane adhesive is, for example, 50 to 1000%, preferably 100 to 900%, more preferably, 300-700%.

  When the elongation at break of the coating film is within the above range, a laminate film (described later) having excellent mechanical strength can be obtained.

  Therefore, such a polyurethane adhesive is suitably used as a film laminating adhesive for producing a laminated film by adhering a plurality of substrates made of a resin film and / or a metal foil. .

  Examples of the resin film include olefin polymers (for example, polyethylene and polypropylene), polyester polymers (for example, polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalates, and their polyalkylene arylates. Copolyester having a main component), polyamide polymer (eg nylon 6, nylon 66 etc.), vinyl polymer (eg polyvinyl chloride, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer) And a plastic film made of a polymer.

  The thickness of the resin film is, for example, 5 to 250 μm.

  As such a resin film, any of an unstretched film (unstretched polyethylene, polypropylene, etc.) or a uniaxial or biaxially stretched film (biaxially stretched polypropylene, polyalkylene terephthalate, nylon, etc.) can be used. .

  Moreover, a resin film can also be prepared as various co-extrusion films or the composite film which stuck resin films beforehand.

  Furthermore, the surface of the resin film may be subjected to a surface treatment such as a corona treatment (corona discharge treatment) or a primer treatment with an anchor coating agent or the like.

  Examples of the metal foil include aluminum foil, stainless steel foil, iron foil, copper foil, and lead foil.

  The thickness of the metal foil is, for example, 5 to 100 μm, preferably 5 to 30 μm, and more preferably 5 to 20 μm.

  These base materials can be used alone or in combination of two or more.

  From the viewpoint of adhering well with a polyurethane adhesive and ensuring easy peelability as a substrate, preferably a polyethylene terephthalate film, a polyethylene film subjected to corona treatment, a polypropylene film subjected to corona treatment, an aluminum foil, a copper foil Is mentioned.

  In the production of a laminate film, a polyurethane adhesive containing a polyisocyanate component, a polyol component and an internal release agent is applied to a substrate.

  Specifically, when the polyurethane adhesive is a one-component curable adhesive, the one-component curable adhesive is applied to, for example, one surface of the base material, and then the other base material is coated. Affix to the surface. Thereafter, the one-component curable adhesive is moisture-cured, for example.

  Further, when the polyurethane adhesive is a two-component curable adhesive, the polyisocyanate component, the polyol component, and the internal release agent are blended in the above-described proportions, and the resulting mixture is, for example, 10 to 100 ° C. In (1), it is applied to one of the surfaces of the substrate. Thereafter, the coated surface is adhered to the surface of the other substrate, and then cured and cured at room temperature or under heating.

  As a laminate film, a plurality of substrates may be attached (primary laminate) to produce a primary laminate film, and another substrate is attached to at least one surface of the primary laminate film. It is possible to produce a secondary laminate film by sticking (secondary laminate).

  Specifically, the primary laminate film is a two-layer laminate film in which a resin film and a metal foil are bonded, a two-layer laminate film in which resin films are bonded, a two-layer laminate film in which metal foils are bonded, and the like. Is mentioned.

  The secondary laminate film is formed by adhering the above-mentioned primary laminate film and a resin film, a metal foil or a separately prepared primary laminate film.

  In the production of the secondary laminate film, the urethane adhesive of the present invention may be used in both the primary laminate and the secondary laminate, or in any one of the primary laminate and the secondary laminate, the present invention. On the other hand, other adhesives can also be used.

  In the production of such a laminate film, the application method is not particularly limited, and for example, a known laminating apparatus can be used.

The coating amount of the polyurethane adhesive, in each laminating step, for example, 0.5 to 10 g / ^{m 2,} preferably, 1 to 5 g / ^{m 2,} more preferably, is 1.5~4.5g / ^{m 2} . If the coating amount is less than 0.5 g / m ² , the adhesiveness may not be sufficiently developed and the appearance may be poor. On the other hand, if the coating amount exceeds 10 g / m ² , the end of the laminate film In some cases, the adhesive leaks out of the film, resulting in poor quality of the laminated film.

  And the above-mentioned polyurethane adhesive is excellent in easy peelability, and, for example, by adjusting the blending ratio of the polyisocyanate component, the polyol component and the internal mold release agent, between the substrates bonded by the adhesive The peel strength (described later) can be easily controlled.

  Specifically, the peel strength between the substrates bonded by the polyurethane adhesive is, for example, 2.0 N / 15 mm width or less, preferably 1.5 N / 15 mm width or less, more preferably 1.0 N. / 15 mm width or less, usually 0.01 N / 15 mm width or more.

  When the peel strength between the substrates is not more than the above upper limit, the laminate films can be easily separated from each other.

  Further, the peel strength between the substrates at 23 ° C. (T peel test measurement value) is, for example, 2.0 N / 15 mm width or less, preferably 1.5 N / 15 mm width or less, more preferably 1.0 N / 15 mm. Less than width, usually more than 0.01N / 15mm width.

  The peel strength between the substrates at 5 ° C. (free peel test measurement value) is, for example, 2.0 N / 15 mm width or less, preferably 1.5 N / 15 mm width or less, more preferably 1.0 N / 15 mm. Less than width, usually more than 0.01N / 15mm width.

  And the ratio of the peeling strength in 23 degreeC with respect to the peeling strength in 5 degreeC is 0.1-20, for example, Preferably, it is 0.1-10.

  If the ratio of the peel strength is within the above range, the base material of the laminate film can be peeled stably and easily without being greatly influenced by the use environment temperature.

  Moreover, such a polyurethane adhesive is excellent in the mechanical strength of the coating film obtained by hardening as mentioned above, and also excellent in heat resistance.

  That is, the laminate film of the present invention obtained using the polyurethane adhesive of the present invention has excellent mechanical strength and heat resistance and can be easily peeled off.

  Therefore, the polyurethane adhesive of the present invention and the laminate film of the present invention are laminated films in various industrial fields that require easy peelability, specifically, protective sheets and packaging materials that can be peeled and reattached. And is preferably used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Production Example 1 (Production of polyisocyanate component A)
A 4-liter flask having a capacity of 1 liter equipped with a stirrer, a thermometer, a cooler and a nitrogen gas inlet tube was charged with 150 g of 4,4′-diphenylmethane diisocyanate, 136 g of ethyl acetate, polyoxypropylene glycol (Mitsui Chemicals, D -1000, number average molecular weight 1000) 275 g and polyoxypropylene glycol (Mitsui Chemicals, D-2000, number average molecular weight 2000) 185 g are charged, and the reaction temperature is adjusted in the range of 70 to 80 ° C. under a nitrogen stream. Then, urethanization reaction was performed for 4 hours to obtain an isocyanate group-terminated prepolymer.

  Then, it cooled to 40 degreeC and 254g of Takenate A-3 (The Mitsui Chemicals make, solid content concentration 75 mass% ethyl acetate solution, tolylene diisocyanate derivative (trimethylol propane modified body)) was added.

  As a result, a polyisocyanate component A having a solid content concentration of 80% by mass, a viscosity (25 ° C.) of 3800 mPa · s measured by a rotational viscometer, and an isocyanate group content of 5.2% by mass was obtained.

Production Example 2 (Production of polyol component A)
In a 1-liter four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, 467 g of polyoxypropylene glycol (Mitsui Chemicals, D-1000, number average molecular weight 1000) and 70 g of dipropylene glycol And 5 g of trimethylolpropane, 158 g of tolylene diisocyanate (manufactured by Mitsui Chemicals, T-80), and 300 g of ethyl acetate, and while adjusting the reaction temperature in the range of 60 to 70 ° C. in a nitrogen stream, 2 The reaction was urethanated for a period of time.

  Next, 0.2 g of tin octylate was added to the reaction solution, and urethanization reaction was further performed for 4 hours while adjusting the reaction temperature in the range of 70 to 80 ° C. to obtain a urethane polyol. After confirming that the peak of the isocyanate group had completely disappeared by FT-IR, a polyol component A having a solid content concentration of 70% by mass and a viscosity (25 ° C.) of 7000 mPa · s measured by a rotational viscometer was obtained.

Production Example 3 (Production of polyol component B)
In a 1-liter four-necked flask equipped with a stirrer, thermometer, rectification column and nitrogen gas inlet tube, 185 g of terephthalic acid, 246 g of isophthalic acid, 164 g of adipic acid, 88 g of ethylene glycol, and 149 g of neopentyl glycol And 168 g of 1,6-hexanediol were charged and esterified at 200 to 230 ° C. for 8 hours. After distilling a predetermined amount of water, 0.1 g of tetrabutyl titanate was added, the pressure was gradually reduced, and the mixture was condensed at 1.3 to 2.7 hPa and 230 to 250 ° C. for 5 hours. As a result, a polyester polyol having an acid value of 1.0 mgKOH / g and a hydroxyl value of 12 mgKOH / g was obtained.

The obtained polyester polyol was adjusted to a solid content of 60% by mass with ethyl acetate to obtain a polyol component B having a viscosity (25 ° C.) of 1300 mPa · s measured by a rotational viscometer.
<Two-part curable adhesive>
Examples 1-16 and Comparative Examples 1-4
A polyisocyanate component, a polyol component, and an internal release agent were blended in the proportions shown in Table 1 to obtain a two-component curable polyurethane adhesive.

  As polyisocyanate component B, Takenate A-65 (manufactured by Mitsui Chemicals, solid content of 100% by mass, hexamethylene diisocyanate derivative (biuret modified)) was used.

Table 1 shows the content ratio of the internal release agent as a ratio relative to 100 parts by mass of the total solid content of the polyisocyanate component and the polyol component.
<One-part curable adhesive>
Production Example 4 (Production of polyisocyanate component C)
An apparatus similar to Production Example 3 was charged with 330 g of isophthalic acid, 290 g of adipic acid, 143 g of ethylene glycol, and 238 g of diethylene glycol, and subjected to an esterification reaction at 200 to 230 ° C. for 6 hours. 1 g was added and further esterified for 3 hours to obtain a polyester polyol having an acid value of 0.8 mgKOH / g and a hydroxyl value of 56.1 mgKOH / g.

  Subsequently, 533 g of the obtained polyester polyol, 107 g of 4,4′-diphenylmethane diisocyanate (Cosmonate PH, manufactured by Mitsui Chemicals), and 350 g of ethyl acetate were provided with a stirrer, a thermometer, a cooler, and a nitrogen gas introduction tube. The mixture was charged into a 2-liter four-necked flask and subjected to a urethanization reaction for 3 hours while adjusting the reaction temperature in the range of 65 to 75 ° C. in a nitrogen stream. Then, it cooled to 40 degreeC and Takenate A-3 (The Mitsui Chemicals make, solid content concentration 75 mass% ethyl acetate solution, tolylene diisocyanate derivative (trimethylol propane modified body)) 100g was added. As a result, a polyisocyanate component C having a solid content concentration of 65% by mass, a viscosity (25 ° C.) measured by a rotational viscometer of 1500 mPa · s, and an isocyanate group content of 2.2% by mass was obtained.

Examples 17-19 and Comparative Examples 5-6
Polyisocyanate component C and internal mold release agent were blended in the proportions shown in Table 1 to obtain a one-component curable polyurethane adhesive.

  Moreover, in Table 1, the content rate of an internal mold release agent is shown as a ratio with respect to 100 mass parts of solid content total amount of a polyisocyanate component.

Details of the abbreviations in Table 1 are shown below.
Internal release agent a: ZELEC UN (manufactured by Stepan Company, in the following formula (3), R5 represents a hydrocarbon group having 8 to 14 carbon atoms, and R6 represents a hydrogen atom or a hydrocarbon group having 8 to 14 carbon atoms) Compound mixture [high carbon number orthophosphoric acid derivative / low carbon number orthophosphoric acid derivative (mass ratio) = 68/32 (measurement method: HPLC / evaporative light scattering detector and LC / MS)])

Internal mold release agent b: AP-10 (Daihachi Chemical, mixture of monoisodecyl orthophosphate and diisodecyl orthophosphate)
Internal mold release agent c: Dihexadecyl orthophosphate Internal mold release agent d: JP-518-O (Johoku Chemical Co., Ltd., mixture of monooleyl orthophosphate and dioleyl orthophosphate)
Internal mold release agent e: JP-524 (Johoku Chemical Co., Ltd., mixture of monotetracosyl orthophosphate and ditetracosyl orthophosphate)
Internal mold release agent f: JP-508 (a mixture of mono-2-ethylhexyl orthophosphate and di-2-ethylhexyl orthophosphate manufactured by Johoku Chemical)
Evaluation Mechanical strength (Elongation at break of coating film)
The polyurethane acetate ethyl acetate solution shown in Table 1 was poured into a mold and the solvent was diffused under a nitrogen stream, followed by curing by heating in an oven at 60 ° C. for 5 days, and a thickness of about 1 mm. An adhesive coating (cured film) was prepared.

  Next, according to JIS K 7312 “Physical Test Method for Thermosetting Polyurethane Elastomer Moldings”, the No. 4 dumbbell was punched out, and using an Instron type tensile tester, a 23 ° C. atmosphere and a tensile speed of 300 mm / min. The elongation at break was measured. The results are shown in Table 2.

Adhesion test (peel strength of laminate film)
The polyurethane adhesive shown in Table 1 was diluted with ethyl acetate so that the coating amount was 2 g / m ² (after drying), and applied on a polyethylene terephthalate film (thickness: 38 μm) at room temperature using a bar coater. The solvent was volatilized with a dryer.

  Thereafter, the adhesive application surface and an aluminum foil (30 μm thick) were bonded together, and cured at 50 ° C. for 2 days to cure the adhesive, thereby producing a two-layer laminate film (AL / PET).

  In the same manner as above, a polyurethane adhesive is applied to an aluminum foil (30 μm thickness), dried, and then coated with an adhesive and a corona-treated polyethylene (linear low density polyethylene, LLDPE) film (60 μm thickness). The corona-treated surface was bonded and cured at 50 ° C. for 2 days to cure the adhesive, thereby producing a two-layer laminate film (AL / LLDPE).

  A test piece having a length of 150 mm and a width of 15 mm was cut out from each laminate film, and T-Peel (23 ° C.) and Free− were used at a peeling rate of 300 mm / min using an Instron tensile tester with a thermostatic bath. Peel strength was measured with Peel (5 ° C.). The results are shown in Table 2.

Heat resistance test The laminated sample of each AL / LLDPE laminate film subjected to the adhesion test was aligned so that the LLDPE surfaces were in contact with each other, and a heat sealer was used at 160 ° C. and 0.1 MPa for 0.6 seconds. Heat sealed.

  As a result, it was confirmed that there was no floating in the seal portion of the laminate film obtained using the polyurethane adhesive obtained in each Example.

Claims (6)

A polyisocyanate component, a polyol component, and an internal mold release agent containing an orthophosphoric acid derivative represented by the following general formula (1) ,
It is an adhesive for film lamination that adheres between a plurality of substrates made of a resin film and / or a metal foil,
Polyurethane adhesive.

(In the formula, R1 and R2 are the same or different from each other and each represent a hydrocarbon group having 9 to 24 carbon atoms, or one of them represents a hydrocarbon group having 9 to 24 carbon atoms, and the other represents Indicates a hydrogen atom.) The content ratio of the internal release agent is
2. The polyurethane adhesive according to claim 1, which is 0.01 to 3 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate component and the polyol component.   The coating film obtained by curing has an elongation at break at 23 ° C measured according to JIS K 7312 (1996) of 100 to 900%, according to claim 1 or 2. Polyurethane adhesive. A laminate film obtained by bonding a plurality of substrates with the polyurethane adhesive according to any one of claims 1 to 3 . The substrate is
Polyethylene terephthalate film, a polyethylene film subjected aluminum foil, copper foil, corona treatment, and, characterized in that at least one member selected from the group consisting of polypropylene film subjected to corona treatment, according to claim 4 Laminating film. The laminate film according to claim 4 or 5 , wherein a peel strength between the substrates bonded by the polyurethane adhesive is 1.5 N / 15 mm width or less.