JP2011116917A - Adhesive for dry laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a two-pack type adhesive for dry laminates that has a good adhesion to plastics having a low polarity and a good water resistance. <P>SOLUTION: The two-pack type adhesive for dry laminates includes (A) a urethane prepolymer, and (B) a hardener. At least either the (A) or the (B) is obtained by reacting a mixture of (a1) an alkylene oxide adduct of an aliphatic polyol and (a2) an alkylene oxide adduct of a bisphenol compound with (b) an isocyanate, or a mixture of the (a1) and the (a2). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to an adhesive for dry lamination. More specifically, the present invention relates to an adhesive for dry lamination used for bonding plastics and metals.

Conventionally, adhesives used for laminating low-polarity plastic films or sheets are generally adhesives designed with low-polar compositions such as polydiene polyols and polyether polyols (Patent Document 1), An adhesive using a diene polyol or a polyether polyol together with a highly polar polyol such as a polyester polyol is disclosed. (Patent Document 2)

JP-A-9-67556 JP 2000-198971

However, adhesives designed with low-polar compositions such as polydiene polyols and polyethers have low adhesion, and adhesives designed with high-polarity polyols such as polyester polyols to improve this are Although the adhesive strength is high, it contains an ester bond, and there is a concern that the adhesive strength may decrease due to hydrolysis during long-term use.
An object of the present invention is to obtain an adhesive for a two-pack type dry laminate that is excellent in adhesiveness with a low-polarity plastic and excellent in water resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have included an alkylene oxide adduct of a bisphenol-based compound in an alkylene oxide adduct of an aliphatic polyol as a polyol component. The present inventors have found that an adhesive for two-pack type dry laminate excellent in adhesiveness, transparency, and water resistance can be obtained, and reached the present invention.

That is, the present invention comprises two liquids of a urethane prepolymer (A) and a curing agent (B), and at least one of (A) and (B) is an alkylene oxide adduct (a1) of an aliphatic polyol and a bisphenol compound. A two-component adhesive composition for dry lamination, comprising a mixture of the alkylene oxide adduct (a2) and the isocyanate (b) or a mixture of (a1) and (a2) A laminated film bonded with the adhesive composition.

The adhesive comprising the adhesive composition for two-pack type dry laminate of the present invention is excellent in adhesiveness with a low polarity plastic and excellent in water resistance.

The adhesive in the present invention comprises two liquids, a urethane prepolymer (A) and a curing agent (B), and an alkylene oxide adduct (a1) of an aliphatic polyol and an alkylene oxide adduct (a2) of a bisphenol compound are bonded. It is contained in the agent. (A1) and (a2) themselves or those prepolymerized may be contained in (A) or (B) or in both (A) and (B).

As the alkylene oxide adduct (a1) of the aliphatic polyol constituting the urethane prepolymer (A) in the present invention, an alkylene oxide adduct (a11) and a polyalkylene oxide (a12) of an aliphatic polyol are included.
The aliphatic polyol of (a11) is preferably a bifunctional or trifunctional low molecular polyol having a molecular weight per hydroxyl group of 30 to 200, more preferably 30 to 100, such as ethylene glycol, propylene glycol, 1,4-butanediol. 1,6-hexanediol, glycerin, trimethylolpropane, and a mixture of two or more thereof.
Examples of the alkylene oxide include ethylene oxide (abbreviated as EO), propylene oxide (abbreviated as PO), tetrahydrofuran (abbreviated as THF), and a mixture of two or more thereof.
The added mole number of alkylene oxide is 10 to 70 mol, preferably 12 to 56 mol.
Specific examples of (a11) include, for example, THF, 13 mol adduct, 1,4-butanediol, PO15 mol adduct, and the like.

Examples of (a12) include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, and a mixture of two or more thereof.
Of these, polyoxytetramethylene glycol and tetrahydrofuran adduct are preferable from the viewpoint of polarity.

The number average molecular weight of the alkylene oxide adduct (a1) of the aliphatic polyol is preferably 800 to 3,000, more preferably 1,000 to 2,500. When the number average molecular weight is 800 or more, the flexibility of the obtained adhesive is sufficient, and when it is 3,000 or less, the adhesiveness to the substrate is sufficient.

Examples of the bisphenol compound of the alkylene oxide adduct (a2) of the bisphenol compound constituting the urethane prepolymer (A) in the present invention include bisphenol A, bisphenol B, bisphenol E, bisphenol F, and the like. And those described in 2008-126108.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, tetrahydrofuran, and a mixture of two or more thereof.

The added mole number of alkylene oxide is preferably 2 to 20 moles, and more preferably 2 to 10 moles from the viewpoint of adhesive strength.
Specific examples of (a2) include ethylene oxide, propylene oxide or tetrahydrofuran adduct of bisphenol A, ethylene oxide, propylene oxide or tetrahydrofuran adduct of bisphenol B, and the like.
Of these, preferred is an ethylene oxide adduct of bisphenol A because of the cohesive strength of the adhesive and the industrial availability.
The number average molecular weight of (a2) is preferably 200 to 2,000, and more preferably 200 to 1,000 from the viewpoint of adhesive strength.

The polyisocyanate (b) constituting the urethane prepolymer (A) in the present invention is the following polyisocyanate having 2 to 6 or more (preferably 2 to 3, more preferably 2) isocyanate groups. And mixtures of two or more of these.

  C (excluding carbon in the NCO group, the same shall apply hereinafter) 2-18 aliphatic polyisocyanates: diisocyanates (hereinafter abbreviated as DI) such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octa Methylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanate Natoethylcaproate, bis (2-isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) carbonate and trifunctional or higher polyisocyanates (such as triisocyanate) such as 1,6,1-undecane triisocyanate, 1, 8-diisocyanate-4-isocyanate Leoctane, 1,3,6-hexamethylene triisocyanate, and lysine ester triisocyanate (phosgenates of the reaction product of lysine and alkanolamine, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2 -And / or 3-isocyanatopropyl-2,6-diisocyanatohexanoate, etc.).

C4-15 alicyclic polyisocyanate: DI, for example isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanatoethyl) ) -4-cyclohexylene-1,2-dicarboxylate and / or 2,6-norbonane DI; and trifunctional or higher polyisocyanates (such as triisocyanates), such as bicycloheptane triisocyanate.

C8-15 araliphatic polyisocyanates: m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ′, α ′,-tetramethylxylylene DI (TMXDI);
C6-20 aromatic polyisocyanates: DI, such as 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4,4'- and / or Or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane and 1,5-naphthylene DI; and trifunctional or higher polyisocyanates (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate) .

And modified polyisocyanates: (for example, modified products having carbodiimide, urethane, urea, isocyanurate, uretoimine, allophanate, biuret, oxazolidone and / or uretdione groups), for example, urethane modified such as MDI, TDI, HDI, IPDI, etc. (NCO-terminated urethane prepolymer obtained by reacting polyol with excess polyisocyanate), biuret modified product, isocyanurate modified product, trihydrocarbyl phosphate modified product, and mixtures thereof.
The polyol used for urethane modification includes the above-mentioned polyether polyol and polyhydric alcohol. Preferred are polyols having an OH equivalent of 500 or less, particularly 30 to 200, such as glycol (ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), dipropylene glycol (DPG), etc.), triol (trimethylol). Propane (TMP), glycerol (GR), tetrafunctional or higher functional polyols (pentaerythritol (PE), sorbitol (SO), etc.) and their AO (ethylene oxide and / or propylene oxide) (1 to 40 mol) Adducts, especially glycols and triols.
The equivalent ratio (NCO / OH ratio) of polyisocyanate and polyol in urethane modification is usually 1.1 to 10, preferably 1.4 to 4, and more preferably 1.5 to 2.
The content of free isocyanate groups in the modified polyisocyanate is usually 8 to 33%, preferably 10 to 30%, more preferably 12 to 29%.

In the urethane prepolymer (A) in the present invention, the equivalent ratio of the total hydroxyl group of the alkylene oxide adduct (a1) of the aliphatic polyol and the alkylene oxide adduct (a2) of the bisphenol compound to the isocyanate group of the polyisocyanate (b) (NCO / OH ratio) is preferably 0.5 to 3.0, more preferably 0.75 to 1.5. When the equivalence ratio is 0.5 to 3.0, the initial adhesive strength of the adhesive is sufficient, and tunneling (floating) hardly occurs.

  Moreover, the preferable weight ratio of the alkylene oxide adduct (a1) of the aliphatic polyol and the alkylene oxide adduct (a2) of the bisphenol compound is 30:70 to 95: 5, more preferably 50:50 to 90:10. More preferably, it is 60: 40-80: 20. When the content of (a2) is 5% by weight or more, the initial adhesive strength of the adhesive is sufficient and tunneling (floating) is less likely to occur, and when it is 70% by weight or less, the adhesiveness to the film to be bonded is good.

The curing agent (B) in the present invention has a functional group capable of reacting with the urethane prepolymer (A), and has two or more active hydrogen groups or two or more NCO groups. When (A) has an NCO group, (B) has two or more active hydrogen groups and is not particularly limited. However, the polyether polyol, polyhydric alcohol, the following nitrogen-containing polyol, low Examples thereof include molecular OH-terminated polymers.

Nitrogen-containing polyols (tertiary amino group-containing polyols and quaternary ammonium group-containing polyols): nitrogen-containing polyols such as C1-12 aliphatic, alicyclic, and aromatic primary monoamines [methylamine, ethylamine, 1-and 2-propylamine, (iso) amylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 1-, 2- and 3-aminoheptane, nonylamine, decylamine, undecylamine, dodecylamine, cyclo Propylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, etc.] bishydroxyalkyl (C2-4) compounds [bis (2-hydroxyethyl) products, bis (hydroxypropyl) products, etc., for example, US Pat. No. 4,271 No.217 And a quaternized product thereof [quaternized product with a quaternizing agent or dialkyl carbonate described in the above-mentioned US Patent], for example, 4 described in the above-mentioned US Patent Specification. Secondary nitrogen atom-containing polyols; and trihydric to octahydric or higher nitrogen-containing polyols such as trialkanol (C2-4) amines (such as triethanolamine) and C2-12 aliphatic, alicyclic, aromatic and Heterocyclic polyamines [ethylenediamine, cyclohexanediamine, tolylenediamine, aminoethylpiperazine, etc.] polyhydroxyalkyl (C2-4) compounds [poly (2-hydroxyethyl) products, bis (hydroxypropyl) products, etc .: for example, tetrakis (2 -Hydroxypropyl) ethylenediamine and pentakis (2-hydro Xylpropyl) diethylenetriamine], and their quaternized compounds as described above.

Low molecular OH-terminated polymers include those having an OH equivalent weight of less than 250. For example, a low-polymerization alkylene oxide (hereinafter abbreviated as AO) ring-opening polymer and a low-mol AO adduct of an active hydrogen atom-containing polyfunctional compound [for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (hereinafter referred to as PEG, respectively) PPG and PTMG), etc., and bis (hydroxyethoxy) benzene and bisphenol A ethylene oxide (hereinafter abbreviated as EO) 2 to 4 mol adduct].
AO includes C2-12 or more (preferably C2-4) AO, such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran and 3 -Methyl-tetrahydrofuran (hereinafter abbreviated as EO, PO, BO, THF, and MTHF), 1,3-propylene oxide, isoBO, C5-12 α-olefin oxide, substituted AO such as styrene oxide and epihalohydrin (epichlorohydrin, etc.) ), And combinations of two or more of these (random addition and / or block addition).

As the curing agent (B) having two or more functions in the present invention, a prepolymer having an OH group at the terminal obtained by reacting the polyol and the polyisocyanate can also be used.

In addition, when (A) has an OH group, (B) has two or more NCO groups and is not particularly limited, but the polyisocyanate and / or the polyisocyanate and the polyol are reacted. And a prepolymer having an NCO group at the terminal obtained.

A preferred blending ratio of the prepolymer (A) and the curing agent (B) is isocyanate group / hydroxyl group = 0.8 to 3, more preferably 0.9 to 2, from the viewpoint of cohesive strength and the finished appearance of the film. When the isocyanate group / hydroxyl group is 0.8 or more, the cohesive strength of the adhesive is sufficient. When the isocyanate group / hydroxyl group is 3 or less, the appearance of the finished film is not caused by white turbidity or foaming due to the reaction between moisture and the isocyanate group. Is good.

If necessary, the adhesive of the present invention can contain a tackifier (C) as long as the effects of the present invention are not impaired. By including the tackifier (C), the adhesiveness of the adhesive to various films is further improved.

Examples of the tackifier (C) include terpene resins, terpene phenol resins, phenol resins, aromatic hydrocarbon modified terpene resins, rosin resins, modified rosin resins, synthetic petroleum resins (aliphatic, aromatic and alicyclic synthesis). Petroleum resins, etc.), coumarone-indene resins, xylene resins, styrene resins, dicyclopentadiene resins, and hydrogenated products of these having hydrogenated unsaturated double bonds. (C) may be used alone or in combination of two or more. The amount of (C) used is usually 100% or less based on the total weight of the adhesive compositions (A) and (B), and preferably 5 to 50% from the viewpoint of the adhesive strength of the adhesive.

In the adhesive of the present invention, an antioxidant (D1), an ultraviolet absorber (D2), a plasticizer (D3), a filler (D4), a pigment (D5), if necessary, as long as the effects of the present invention are not impaired. At least one additive (D) selected from the group consisting of the catalyst (D6) and the like can be contained.

Antioxidants (D1) include hindered phenol compounds [triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like Phosphite compound [Tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di -T-Butylphenyl) pentaerythritol di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-bif Ylene - di - phosphonite, etc.] and the like. These antioxidants may be used alone or in combination of two or more. The amount of (D1) used is usually 5% or less based on the total weight of the adhesive compositions (A) and (B), preferably from 0.05 to 1 from the viewpoint of the antioxidant effect and the adhesive strength of the adhesive. %.

Examples of the ultraviolet absorber (D2) include salicylic acid derivatives (phenyl salicylate, salicylic acid-P-octylphenyl, salicylic acid-P-tert-butylphenyl, etc.), benzophenone compounds [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy. Benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2- Hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2 2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, bis (2-methoxy-4-hydroxy-5) -Benzoylphenyl) methane etc.], benzotriazole compounds {2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl- Phenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methyl-phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5 ′) -Di-t-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-n-octoxy) Benzyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, -[2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,1 3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like}, cyanoacrylate compounds (2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2- Cyano-3,3′-diphenyl acrylate) and the like. The ultraviolet absorbers may be used alone or in combination of two or more. The amount of (D2) used is usually 5% or less based on the total weight of the adhesive compositions (A) and (B), preferably 0.1 to 1 from the viewpoint of the ultraviolet absorption effect and the adhesive strength of the adhesive. %.

As the plasticizer (D3), hydrocarbon [process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, chlorinated paraffin, paraffin wax, copolymer of ethylene and α-olefin (C3-20) (weight) Ratio 99.9 / 0.1-0.1 / 99.9) oligomer (Mw 5,000-100,000), copolymer oligomer of α-olefin (C4-20) excluding propylene and ethylene (weight ratio 99.99). 9 / 0.1 to 0.1 / 99.9) oligomer (Mw 5,000 to 100,000)]; chlorinated paraffin; ester [phthalic acid ester [diethyl phthalate (DEP), dibutyl phthalate (DBP), di- 2-ethylhexyl phthalate (DOP), didecyl phthalate, dilauryl phthalate, distearies Ruphthalate, diisononyl phthalate, etc.], adipic acid ester [di (2-ethylhexyl) adipate (DOA), dioctyl adipate, etc.] and sebacic acid ester (dioctyl sebacate, etc.)]; And hydrogenated products of those having an unsaturated double bond capable of being hydrogenated. You may use a plasticizer 1 type or in combination of 2 or more types. The amount of the plasticizer used is usually 100% or less based on the total weight of the adhesive compositions (A) and (B), preferably 0.5 to 30% from the viewpoint of adhesive strength and cohesive strength of the adhesive. is there.

As filler (D4), carbonate (magnesium carbonate, calcium carbonate, etc.), sulfate (aluminum sulfate, calcium sulfate, barium sulfate, etc.), sulfite (calcium sulfite, etc.), molybdenum disulfide, silicate (silicate) Aluminum silicate, calcium silicate, etc.), diatomaceous earth, quartzite powder, talc, silica, zeolite and the like. The filler is a fine particle having a volume average particle diameter of preferably about 0.01 to 5 μm, and may be used alone or in combination of two or more. The amount of the filler used is usually 250% or less based on the total weight of the adhesive compositions (A) and (B), and preferably 0.5 to 100% from the viewpoint of the cohesive strength of the adhesive.

As the pigment (D5), inorganic pigments (alumina white, graphite, titanium oxide, ultrafine titanium oxide, zinc white, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, resurge, lithopone , Barite, cadmium red, cadmium mercury red, bengara, molybdenum red, red lead, yellow lead, cadmium yellow, barium yellow, strontium yellow, titanium yellow, titanium black, chromium oxide green, cobalt oxide, cobalt green, cobalt chrome green , Ultramarine blue, bituminous blue, cobalt blue, cerulean blue, manganese violet, cobalt violet, etc.) and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dyed lakes, etc.). The pigment is a fine particle having a volume average particle diameter of preferably about 0.01 to 5 μm, and may be used alone or in combination of two or more. The amount of the pigment used is usually 250% or less based on the total weight of the adhesive compositions (A) and (B), and preferably 0.1 to 50% from the viewpoint of the cohesive strength of the adhesive.

The adhesive of the present invention may contain an effect promoting catalyst (D6) as necessary for the purpose of accelerating the curing reaction between the prepolymer (A) and the curing agent (B).
Examples of (D6) include alkyl (C2-20) phosphonic acid metal (potassium, sodium, etc.) salts; C8-20 fatty acid metal (sodium, potassium, nickel, cobalt, cadmium, barium, calcium, zinc, etc.) Salts; organic tin compounds [dibutyltin dilaurate, dioctyltin maleate, dibutyldibutoxytin, bis (2-ethylhexyl) tin oxide, 1,1,3,3-tetrabutyl-1,3-diacetoxydistanoxane, etc.]; Amines (triethylamine, triethylenediamine, N-pentamethyldiethylenetriamine, etc.); organic titanium compounds (tetrabutoxytitanium, tetrapropoxytitanium, isopropoxy-trisdioctylphosphonyl titanium, isopropoxy-trisisostearate titanium, etc.); and these Mixtures of two or more thereof.
Of these, organic tin compounds, amines and organic titanium compounds are preferable from the viewpoint of reactivity, and dibutyltin dilaurate, dioctyltin maleate and isopropoxy triisostearate titanium are more preferable.

The adhesive for dry laminate of the present invention is useful for dry laminate adhesion between various plastic films; dry laminate adhesion between the plastic film and an inorganic plate, a plastic molded plate or a metal plate. Among these, it is particularly preferably used for dry laminate bonding with a plastic molded plate.

Examples of the plastic film include a polypropylene film, a polyethylene film, a polyester film, a polyacrylic film, a polyvinyl chloride film, a polystyrene film, a nylon film, an ethylene vinyl alcohol copolymer film, and a polyvinyl alcohol film. Examples thereof include a plastic film subjected to vapor deposition treatment with silica or coating treatment with polyvinylidene chloride.

Examples of the inorganic board include a slate board, a calcium silicate board, a gypsum board, a wood cement board, and a foamed concrete board.
Examples of the plastic molded plate include an ABS resin molded plate, a polystyrene resin molded plate, a polyester resin molded plate, an acrylic resin molded plate, a polycarbonate resin molded plate, a polyvinyl chloride resin molded plate, and a melamine resin molded plate.
Examples of the metal plate include a stainless plate, a galvanized steel plate, a chemical conversion treated steel plate, and an aluminum plate.

A gravure coater, a reverse roll coater, a comma coater, or the like is used for coating the adhesive in bonding the plastic films. The coating amount (solid content) of the adhesive at the time of coating is usually 1 to 50 g / m ² , preferably ² to 40 g / m ² .
In addition, a comma coater, a die coater, a knife coater, or the like is used for coating an adhesive in bonding a plastic film to an inorganic plate, a plastic molded plate, or a metal plate. The coating amount (solid content) of the adhesive at the time of coating is usually ^{2 to} 500 g / cm ² , preferably 3 to 450 g / m ^{2 for} an inorganic plate, and usually 1 to ^{3 for} a plastic molded plate and a metal plate. 300 g / cm ² , preferably ² to 250 g / m ² .
A normal dry laminator extrusion laminator is used for laminating (laminating films). Laminate films (those bonded to each other) are usually cured at 20 to 50 ° C. for 20 to 150 hours, whereby the adhesive is completely cured.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not a thing limited to this. In the examples, “parts” and “%” respectively represent “parts by weight” and “% by weight” unless otherwise specified.

[Production Method of Urethane Prepolymer (A)]
Production Example 1
113.1 parts of bisphenol A PPG [trade name “Sanix PP-1000”, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight (Mn, hereinafter the same): about 1,000, the same hereinafter]] Of ethylene oxide [trade name “BPE-20T”, manufactured by Sanyo Chemical Industries, Ltd., the same shall apply hereinafter] 263.8 parts, uniformly stirred at 105 ° C., cooled to 60 ° C., and hydrogenated MDI [trade name “Death Module W”, manufactured by Sumika Bayer Urethane Co., Ltd., and so on. ] 123.2 parts were charged, stirred and mixed in a nitrogen stream, reacted at 90 to 110 ° C. for 8 hours, 500 parts of ethyl acetate was added and stirred uniformly, and the number average molecular weight was about 1,100 (hereinafter abbreviated as Mn). A solution of OH-terminated urethane prepolymer (A1) having a solid content concentration of 50% was obtained.

Production Example 2
In Production Example 1, in place of 113.1 parts of PPG (PP-1000), PTMG [trade name “PTMG1000”, manufactured by Mitsubishi Chemical Corporation, Mn: about 1,000] 233.5 parts, BPE-20T 263. Use 58.4 parts instead of 8 parts, and cool to 60 ° C after uniform stirring at 105 ° C. Replace with 123.2 parts of hydrogenated MDI, MDI [trade name “MILLIONATE MT”, Nippon Polyurethane Industry Co., Ltd. ), The same below] 208.1 parts were charged, stirred and mixed in a nitrogen stream, reacted at 80-100 ° C. for 5 hours, 500 parts of ethyl acetate was added and stirred uniformly, Mn about 1,900, solid content A solution of NCO-terminated urethane prepolymer (A2) having a concentration of 50% was obtained.

Production Example 3
In Production Example 1, instead of 113.1 parts of PPG (PP-1000), 264.6 parts of PTMG (PTMG1000), 113.4 parts of BPE-20T instead of 263.8 parts, and 123.2 parts of hydrogenated MDI Instead, a solution of OH-terminated urethane prepolymer (A3) having a Mn of about 7,800 and a solid content concentration of 50% was obtained in the same manner as in Production Example 1 except that 122.0 parts were used.

Production Example 4
In Production Example 2, in place of 233.5 parts of PTMG (PTMG1000) 231.5 parts of PPG (PP-1000), in place of 58.4 parts of BPE-20T, in place of 99.2 parts, MDI 208.1 parts A solution of an NCO-terminated urethane prepolymer (A4) having a Mn of about 9,100 and a solid content concentration of 50% was obtained in the same manner as in Production Example 2, except that 169.3 parts of the same were used.

Comparative Production Example 5
In Production Example 1, instead of 113.1 parts of PPG (PP-1000), 417.8 parts of PTMG (PTMG1000), 0 parts instead of 263.8 parts of BPE-20T, and 123.2 parts of hydrogenated MDI A solution of OH-terminated urethane prepolymer (A5) having a Mn of about 9,800 and a solid content concentration of 50% was obtained in the same manner as in Production Example 1 except that 82.2 parts of the same were used.

Production Example 6
In Production Example 2, PTMG (PTMG1000) replaced with 233.5 parts 0 parts, BPE-20T 58.4 parts replaced with 189.2 parts, MDI 208.1 parts replaced with hydrogenated MDI 310.8 parts A solution of a comparative NCO-terminated urethane prepolymer (A6) having a Mn of about 1,100 and a solid content concentration of 50% was obtained in the same manner as in Production Example 2 except that was used.

Comparative Production Example 7
In a reaction vessel equipped with a condenser, 48.8 parts of MDI, 226.0 parts of PPG (PP-1000) and 237.5 parts of ethyl acetate were charged and stirred and mixed in a nitrogen atmosphere at 70 to 80 ° C. The reaction was performed for 5 hours to obtain an OH-terminated prepolymer. The contents in the reaction vessel were cooled to 60 ° C., 150 parts of PPG (PP-1000) and 88.7 parts of MDI were added, and reacted at 70 to 80 ° C. for 5 hours. Next, 0.04 part of dibutyltin dilaurate was added and reacted for another 3 hours to obtain a solution of comparative NCO-terminated urethane prepolymer (A7) having Mn 4,600 and a solid content concentration of 68%.

Comparative Production Example 8
In a reaction vessel similar to Comparative Production Example 7, polyethylene adipate diol [trade name “San Ester 2620”, manufactured by Sanyo Chemical Industries, Ltd., the same shall apply hereinafter] 188 parts, PPG (PP-1000) 46 parts, polybutadiene polyol [commodity Name “NISSO-PB G-1000”, manufactured by Nippon Soda Co., Ltd., hereinafter the same] 32 parts, polycaprolactone triol [trade name “Placcel PCL-303”, manufactured by Daicel Chemical Industries, Ltd., the same hereinafter] 7 parts, ethyl acetate 280 parts and cyclohexane 70 parts were charged and uniformly mixed at a liquid temperature of 50 ° C. Subsequently, 77 parts of isophorone diisocyanate and 0.06 part of dibutyltin dilaurate were charged under stirring and reacted at 70 ° C. for 5 hours under a nitrogen stream to make a comparative NCO-terminated urethane prepolymer having a viscosity of 150 mPa · s (25 ° C.) and a solid content of 50%. A solution of polymer (A-8) was obtained.

Production Example 9
As a curing agent (B) having two or more NCO groups, a 75% ethyl acetate solution of a reaction product (B1) of TDI (3 mol) and TMP (1 mol) [trade name “Coronate L”, Nippon Polyurethane ( The same shall apply hereinafter. ]It was used.

Production Example 10
266.7 parts of PTMG (PTMG1000) and 311.1 parts of Coronate L were reacted in a reaction vessel at 80 to 100 ° C. for 5 hours under a nitrogen atmosphere to obtain an NCO terminal curing agent (B2), and 422 parts of ethyl acetate was added. Used with uniform stirring.

Production Example 11
As a curing agent (B3) having two or more OH groups, a product obtained by uniformly mixing 100 parts of glycerin PO adduct [trade name “SANNICS GP-3000”, manufactured by Sanyo Chemical Industries, Ltd.] with 100 parts of ethyl acetate It was used.

Production Example 12
In a reaction vessel, under a nitrogen atmosphere, 333.3 parts of PTMG (PTMG1000) and 166.7 parts of MDI were reacted at 80 to 100 ° C. for 4 hours, and then 10.2 parts of glycerin was further added and reacted at 80 to 100 ° C. for 5 hours. What was obtained by adding 510.2 parts of ethyl acetate to the OH-terminal curing agent (B4) and stirring uniformly was used.

Comparative Production Example 13
N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 100 parts of OH terminal curing agent (B5), uniformly mixed with 100 parts of ethyl acetate was used.

Example 1
A urethane prepolymer (A1) solution, a curing agent (B1) solution, and ethyl acetate were mixed at a blending ratio shown in Table 1 to obtain an adhesive (X1).
(X1) was applied to the first base nylon shown in Table 2 with a solvent-type dry laminator so that the coating amount was 2.5 to 3.5 g / m ² (solid content), and dried with hot air at 70 to 90 ° C. After drying with a machine for about 1 minute and volatilizing the solvent, the coated surface was bonded to the second substrate linear low density polyethylene shown in Table 2 to obtain Sample Q1.
In addition, sample Q2 was obtained in the same manner as described above using aluminum-deposited polyester as the first substrate and linear low-density polyethylene as the second substrate. Using these samples, the finished appearance of the film, the initial adhesive strength, the adhesive strength with time, the adhesion to the metal surface, and the water resistance were evaluated.

Examples 2 to 5 (adhesive for two-component dry laminate), Comparative Examples 1 to 2, 4 (adhesive for two-component dry laminate), 3 (adhesive for one-component dry laminate)
In the same manner as in Example 1, adhesives and films were prepared and evaluated according to Tables 1 and 2. The results are shown in Table 3.

The evaluation method is as follows, and the average value of 5 samples is shown unless otherwise specified.
(1) Finished appearance of film Samples Q1, Q3, Q5, Q7, Q9, Q11, Q13, Q15, Q17 Immediately after the creation and after 48 hours of winding curing (40 ° C.), the finished appearance is visually as follows. Evaluated by criteria.
Excellent transparency of the film, no coating unevenness, cracks, floating (tunneling, the same applies hereinafter) etc.
○ Transparency is slightly good and coating unevenness, cracks, floats, etc. are not recognized at all.
Δ: Transparency is slightly good, but some coating unevenness, cracks, floats, etc. are observed.
X: Scratches are clearly observed, coating unevenness, cracks, floating, etc. are observed.

(2) Initial adhesive strength Samples Q1, Q3, Q5, Q7, Q9, Q11, Q13, Q15, Q17 were cut into a size of 200 mm × 15 mm within 1 hour after preparation, and T-type peel strength (g / 15 mm). The larger the value, the better the initial adhesive strength.
<T-type peel test conditions> [The same applies to (4) and (5) described later. ]
T-type peel strength was measured at 23 ° C. using an Instron type tensile tester. Pulling speed 300mm / min, unit is g / 15mm.

(3) Adhesive strength over time Samples Q1, Q3, Q5, Q7, Q9, Q11, Q13, Q15, Q17 were prepared, then placed in a constant temperature bath at 40 ° C., and T-type peel strength (g / 15 mm) after 48 hours was obtained. It was measured.

(4) Adhesion with metal surface After preparing samples Q2, Q4, Q6, Q8, Q10, Q12, Q14, Q16, Q18, and curing at 40 ° C. for 24 hours, T-type peel strength (g / 15 mm) It was measured. The larger the value, the better the adhesion to the metal surface.

(5) Evaluation of water resistance After preparing samples Q1, Q3, Q5, Q7, Q9, Q11, Q13, Q15, Q17, and curing them at 40 ° C for 48 hours, immersing them in warm water at 60 ° C for 1 week The T-type peel strength (g / 15 mm) was measured for 24 hours at 23 ° C. and 50% Rh.

The evaluation results show the following.
<Finished appearance of film, initial adhesive strength, adhesive strength with time, adhesion to metal surface and water resistance>
The adhesive of the present invention is excellent in finished appearance, has a large initial adhesive force, and reaches the final strength at 40 ° C. for 48 hours. Furthermore, the adhesiveness to a metal surface is excellent, and the adhesive force does not decrease after immersion in warm water at 60 ° C. for 1 week.

Since the adhesive of the present invention has the above effects, film materials [resin film (polyethylene, polypropylene, polyethylene terephthalate, nylon, cellophane, polystyrene, polyvinyl chloride, polyvinylidene chloride, etc.), metal (aluminum, copper, etc.) deposition Film and metal (aluminum, copper, etc.) foil, etc.] are used as adhesives by dry laminating method, and plastic building materials such as polyvinyl chloride, ABS resin, melamine resin, iron, aluminum, etc. It is also useful as an adhesive for laminating a metal building material and the resin film.

Claims (9)

It consists of two liquids, a urethane prepolymer (A) and a curing agent (B), and at least one of (A) and (B) is an alkylene oxide adduct (a1) of an aliphatic polyol and an alkylene oxide adduct of a bisphenol compound. An adhesive composition for two-pack type dry laminate, comprising a mixture of (a2) and isocyanate (b) or containing a mixture of (a1) and (a2). The equivalent ratio of the hydroxyl group of the alkylene oxide adduct (a1) of the aliphatic polyol and the hydroxyl group of the alkylene oxide adduct (a2) of the bisphenol compound and the isocyanate group of the isocyanate (b) is isocyanate group / hydroxyl group = 0.5- The adhesive composition according to claim 1, which is 3. The adhesive composition according to claim 1 or 2, wherein a weight ratio of the alkylene oxide adduct (a1) of the aliphatic polyol and the alkylene oxide adduct (a2) of the bisphenol compound is 30:70 to 95: 5. The adhesive composition according to any one of claims 1 to 3, wherein the alkylene oxide addition product (a2) of the bisphenol compound has 2 to 20 moles of alkylene oxide addition. The adhesive composition according to any one of claims 1 to 4, wherein the curing agent (B) is a compound having two or more active hydrogen groups or two or more NCO groups. The adhesive composition according to any one of claims 1 to 5, wherein a blending ratio of the urethane prepolymer (A) and the curing agent (B) is isocyanate group / hydroxyl group = 0.8 to 3. The adhesive composition according to any one of claims 1 to 6, further comprising a tackifier (C). The adhesive composition according to any one of claims 1 to 7, which is used for bonding between plastics or between a plastic and a metal. A laminate film bonded with the adhesive composition according to claim 1.