JP5394450B2 - Adhesive for dry lamination - Google Patents

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.

  As an adhesive for dry laminate used for laminating a plastic film or a sheet, a two-component solventless adhesive composed of a polyurethane or a polyisocyanate using a polyurethane polyol and an aromatic polyisocyanate is known. (For example, refer to Patent Document 1).

Japanese Patent Laid-Open No. 03-182584

However, the adhesive has a problem that the cohesive force of the adhesive decreases with time and the adhesiveness is deteriorated under heating conditions and wet heat conditions.
An object of the present invention is to provide an adhesive for dry laminating with little deterioration of the adhesive even under heating conditions and wet heat conditions, and with little performance deterioration during long-term use.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the deterioration of the resin can be suppressed by containing an ethylenically unsaturated bond in the adhesive and have reached the present invention. That is, the present invention provides a two-component curable adhesive comprising a main agent containing an active hydrogen component (A) and a curing agent containing an isocyanate component (B), or a urethane prepolymer (C) having an isocyanate group at the terminal. a one-pack curing type adhesive comprising, as the active hydrogen component (a) and / or the isocyanate component (B) and the urethane prepolymer (C) is an ethylenically unsaturated bond-containing group (x) A (meth) acryloyl group introduced by at least one selected from the group consisting of glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate and pentaerythritol di (meth) acrylate ; An adhesive for dry laminating, characterized by comprising: It is a laminate film formed by.

  The adhesive for dry laminate of the present invention captures and crosslinks an ethylenically unsaturated bond containing a radical that is a cause of resin deterioration in the adhesive, thereby improving the strength of the resin. Even under conditions in which molecular cleavage occurs due to humidity or the like, the strength of the resin is hardly lowered and a certain adhesive force can be maintained.

  The adhesive for dry laminate of the present invention has an ethylenically unsaturated bond-containing group (x), and is composed of a main agent containing an active hydrogen component (A) and a curing agent containing an isocyanate component (B). It can be used as a two-component curable adhesive or a one-component curable adhesive containing a urethane prepolymer (C) having an isocyanate group at the terminal.

  Examples of the ethylenically unsaturated bond-containing group (x) in the present invention include a (meth) acryloyl group and a (meth) allyl group, and a (meth) acryloyl group is preferred from the viewpoint of reactivity.

  Examples of the method for introducing the ethylenically unsaturated bond-containing group (x) into the adhesive of the present invention include a method using a compound (X1) having a reactive group and an ethylenically unsaturated bond-containing group (x). It is done.

  Examples of the compound (X1) having a reactive group and an ethylenically unsaturated bond-containing group (x) include a compound (X11) having a hydroxyl group and an ethylenically unsaturated bond-containing group (x), an amino group, and an ethylenically unsaturated group. Examples thereof include compound (X12) having a bond-containing group (x) and compound (X13) having an isocyanate group and an ethylenically unsaturated bond-containing group (x).

  Examples of the compound (X11) having a hydroxyl group and an ethylenically unsaturated bond-containing group (x) include dihydric alcohols such as ethylene glycol, propylene glycol, bisphenol A or a hydride thereof, or alkylene oxides having 2 to 4 carbon atoms thereof. (Hereinafter abbreviated as AO) 1-30 mol adduct (meth) acrylate; trivalent alcohol such as trimethylolpropane and glycerin or mono- or di (meth) acrylate of 1-30 mol adduct of these AO; pentaerythritol or Mono-, di- or tri (meth) acrylate of 1 to 30 mol adduct of AO; mono- or dihydroxyalkyl (meth) allyl ether having 2 to 6 carbon atoms of alkyl [2-hydroxyethyl (meth) allyl ether, 2-hydroxy Propyl (meth) allyl ether and 2 3- dihydroxypropyl (meth) allyl ether, etc.] and the like.

  Examples of the AO include ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), and 1,2-, 1,3-, 1,4- or 2 , 3-butylene oxide (hereinafter abbreviated as BO: 1,4-butylene oxide may be abbreviated as THF in some cases).

  Examples of the compound (X12) having an amino group and an ethylenically unsaturated bond-containing group (x) include (meth) allylamine.

  Examples of the compound (X13) having an isocyanate group and an ethylenically unsaturated bond-containing group (x) include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate. It is done.

  Of these, those having a (meth) acryloyl group are preferable from the viewpoint of reactivity, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerin (meth) acrylate, They are methylolpropane (meth) acrylate and pentaerythritol (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate.

  The adhesive of the present invention is a one-component curable or two-component curable urethane adhesive, and has one reactive group such as a hydroxyl group in the compound (X1) having an ethylenically unsaturated bond-containing group (x). When it is, since high molecular weight inhibition is inhibited at the time of hardening, what contains 2 or more reactive groups, such as a hydroxyl group, is preferable. Moreover, what has two or more reactive groups, such as a hydroxyl group, from a viewpoint which can introduce | transduce many ethylenically unsaturated bond containing groups (x) in a molecule | numerator is preferable. From these viewpoints, (X1) is particularly preferably glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate and pentaerythritol di (meth) acrylate.

  As the compound (X1) having a reactive group and an ethylenically unsaturated bond-containing group (x), one type may be used alone, or two or more types may be used in combination.

  The two-component curable adhesive of the present invention comprises a main agent containing an active hydrogen component (A) and a curing agent containing an isocyanate component (B).

  Examples of the active hydrogen component (A) include a low molecular polyol (a1) having a number average molecular weight (hereinafter abbreviated as Mn) of less than 300, a polymer polyol (a2) having a Mn of 300 or more, a hydroxyl group and ethylenic unsaturated. Compound (X11) having a bond-containing group (x), compound (X12) having an amino group and an ethylenically unsaturated bond-containing group (x), and these and isocyanates (b1), (b2) and (b3) described later , (B4) and / or an isocyanate-modified product (b5), and a prepolymer (a3) having a hydroxyl group at the terminal. The active hydrogen component (A) may be used alone or in combination of two or more.

  Mn in the present invention is measured by gel permeation chromatography using THF as a solvent and polyethylene glycol as a standard substance.

  The low molecular weight polyol (a1) having an Mn of less than 300 includes a polyol having a chemical formula weight of less than 300, specifically, a dihydric alcohol having 2 to 20 carbon atoms, and a trivalent to octavalent carbon having 3 to 20 carbon atoms. Or the polyol of C5-C20 which has functional groups other than the polyhydric alcohol and hydroxyl group more than that, etc. are mentioned.

  Examples of the dihydric alcohol having 2 to 20 carbon atoms include aliphatic dihydric alcohols having 2 to 12 carbon atoms (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3- , 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol 3-methylpentanediol, mono- or polyalkylene glycol such as dodecanediol); alicyclic ring having 6 to 10 carbon atoms Examples thereof include monohydric alcohols (1,4-cyclohexanediol, cyclohexanedimethanol and the like); araliphatic dihydric alcohols having 8 to 20 carbon atoms [xylylene glycol, bis (hydroxyethyl) benzene and the like] and the like.

  Examples of the polyhydric alcohol having 3 to 20 carbon atoms and having 3 to 8 or more carbon atoms include (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol, dithiols. Pentaerythritol, 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerols, etc., sugars and their derivatives [sucrose, glucose, fructose, mannose, lactose and glycosides (methyl) Glucoside, etc.)], and AO adducts of alkylenediamines such as N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine.

As a C5-C20 polyol which has functional groups other than a hydroxyl group, the polyol which has a carboxyl group, a sulfo group, or these salts etc. is mentioned, for example.
Examples of those having a carboxyl group include hydroxycarboxylic acids having 5 to 20 carbon atoms [for example, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butane. Acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2- Bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine and N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide] Is mentioned.

  As what has a sulfo group, the polyester polyol etc. which are obtained by making the dicarboxylic acid containing a C3-C20 sulfo group and one or more types of a polyol react, for example are mentioned. Examples of the dicarboxylic acid containing a sulfo group include 5-sulfoisophthalic acid and 2-sulfoterephthalic acid, and 5-sulfoisophthalic acid is preferable. Examples of the polyol include alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1, 6-hexanediol, etc.). The equivalent ratio (OH / COOH) of the hydroxyl group of the polyol and the carboxyl group of the dicarboxylic acid containing a sulfo group in the esterification is usually 1.1 / 1 to 5/1, preferably 1.5 / 1 to 3 /. 1.

  The counter ion when the carboxyl group or the sulfo group forms a salt is not particularly limited. Examples of the salt include alkali metal (sodium and potassium) salts, ammonium salts, primary amines (alkylamines such as methylamine, ethylamine, and butylamine). Amine and monoalkanolamines such as monoethanolamine), secondary amines (dialkylamines such as dimethylamine, diethylamine and dibutylamine and dialkanolamines such as diethanolamine) salts, tertiary amines (trimethylamine, triethylamine and tributylamine) Trialkylamines such as triethanolamine and the like, and alkyl dialkanolamines such as N-methyldiethanolamine) and quaternary ammonium salts (tetraalkylammonium) Beam, etc.) is a salt.

Among these, from the viewpoint of reactivity, a trihydric to octahydric or higher polyhydric alcohol having 3 to 20 carbon atoms is preferred, and glycerin, trimethylolpropane and pentaerythritol are more preferred.
Further, from the viewpoint of adhesiveness, a C5-C20 polyol having a functional group other than a hydroxyl group is preferable, and 2,2-bis (hydroxymethyl) propionic acid containing a carboxyl group and 2 are more preferable. , 2-bis (hydroxymethyl) butanoic acid.

  Examples of the polymer polyol (a2) having a Mn of 300 or more include polyether polyol (a21), polyester polyol (a22), and other polyol (a23).

  Examples of the polyether polyol (a21) include polyalkylene glycol [polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, poly-3-methyltetramethylene ether glycol, etc.], copolymer polyoxyalkylene diol [EO / PO copolymerization]. Diol, THF / EO copolymerized diol, THF / 3-methyltetrahydrofuran copolymer diol and the like (weight ratio is, for example, 1/9 to 9/1)] and an AO adduct of a bisphenol-based compound; For example, AO adducts of trihydric or higher polyhydric alcohols [AO adduct of glycerin and AO adduct of trimethylolpropane, etc.]; and those obtained by coupling one or more of these with methylene dichloride.

Examples of the bisphenol compound in the above include bisphenol A, bisphenol B, bisphenol E, bisphenol F, and the like, specifically those described in JP-A-2008-126108.
The number of moles of AO added in the above is preferably 2 to 100 moles, more preferably 2 to 50 moles, and particularly preferably 2 to 30 moles from the viewpoint of adhesive strength.
In the case of an AO adduct of a bisphenol compound, the number of moles of AO addition is preferably 2 to 10 moles, more preferably 2 to 6 moles, and particularly preferably 2 to 4 moles from the viewpoint of cohesive strength.

  Of these, polytetramethylene ether glycol is preferable from the viewpoint of durability, and an AO adduct of bisphenol compounds, particularly an EO adduct of bisphenol A, is preferable from the viewpoint of cohesion. From both viewpoints, the combined use of polytetramethylene ether glycol and an bisphenol-based AO adduct is preferred. When polytetramethylene ether glycol and an AO adduct of a bisphenol compound are used in combination, the weight ratio of the polytetramethylene ether glycol and the AO adduct of the bisphenol compound is preferably 30:70 to 95: 5, more preferably Is 40:60 to 90:10, particularly preferably 50:50 to 85:15.

  Examples of the polyester polyol (a22) include condensed polyester polyols, polylactone polyols, castor oil-based polyols, and polycarbonate polyols.

  As the condensed polyester polyol, a low molecular polyol (a1) or polyether polyol (a21) having an Mn of less than 300, a polycarboxylic acid or an ester-forming derivative thereof (an acid anhydride and an alkyl ester having 1 to 4 carbon atoms, etc.) And polycondensates thereof.

  Examples of the polycarboxylic acid include dicarboxylic acids and trivalent to tetravalent or higher polycarboxylic acids, and specifically, saturated or saturated with 2 to 30 or more carbon atoms (preferably 2 to 12 carbon atoms). Unsaturated aliphatic polycarboxylic acids [C2-C15 dicarboxylic acids (shu, succinate, malon, adipine, suberin, azelain, sebatin, dodecanedicarboxylic acid, malee, fumar, itaconic acid, etc.) and C6-C20 tricarboxylic acids (Tricarbaryl and hexanetricarboxylic acid)]; aromatic polycarboxylic acid having 8 to 15 carbon atoms [dicarboxylic acid such as terephthal, isophthal and phthalic acid, and tri or tetracarboxylic acid such as trimellit and pyromellitic acid]; carbon A alicyclic polycarboxylic acid of 6 to 40 (eg, dimer acid); and a sulfo group-containing polycarboxylic acid Those obtained by introducing a sulfo group into the polycarboxylic acid, such as sulfosuccinic acid, sulfomalon, sulfoglutar, sulfoadipine and sulfoisophthalic acid and their salts (for example, metal salts, ammonium salts, amine salts and quaternary ammonium salts); and Examples thereof include a polymer having a carboxyl group at the terminal.

  Examples of the polymer having a carboxyl group at the terminal include polyether polycarboxylic acid [for example, carboxymethyl ether of polyol such as low molecular polyol (a1) or polyether polyol (a21) having Mn of less than 300 (monochloroacetic acid in the presence of alkali). Obtained by reacting, etc.]]; polyamide and / or polyester polycarboxylic acid [for example, lactam having 4 to 15 carbon atoms using the above polycarboxylic acid as an initiator (caprolactam, enantolactam, laurolactam, undecanolactam, etc.) Or polylactam polycarboxylic acid and polylactone polycarboxylic acid obtained by ring-opening polymerization of lactones having 4 to 15 carbon atoms (γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc.).

  As the polylactone polyol, ring-opening addition of lactones having 4 to 15 carbon atoms (such as γ-butyrolactone, γ-valerolactone, and ε-caprolactone) using water or a low molecular polyol (a1) having an Mn of less than 300 as an initiator. Thing etc. are mentioned.

  Castor oil-based polyols include castor oil (ricinoleic acid triglyceride), partially dehydrated castor oil, partially acylated castor oil, hydrogenated castor oil, and modified products thereof (polyether polyol (a21) or low molecular weight Mn of less than 300). Ester polyol obtained by transesterification reaction between polyol (a1) and castor oil, partially dehydrated castor oil or hydrogenated castor oil, and polyether polyol (a21) or low molecular polyol (a1) having a Mn of less than 300 and castor oil Ester obtained by esterification reaction with fatty acid or hydrogenated castor oil fatty acid] and the like.

  Examples of the polycarbonate polyol include a ring-opening addition / polycondensation product of an alkylene carbonate having a low molecular weight polyol (a1) having an Mn of less than 300 as an initiator, and a polycondensation (transesterification) product of (a1) and a diphenyl or dialkyl carbonate. Can be mentioned.

  Examples of the other polyol (a23) include polymer polyol, polyolefin polyol, polyalkadiene polyol, acrylic polyol, and amino group-containing polyol.

The polymer polyol is obtained by dispersing and stabilizing polymer particles obtained by polymerizing a vinyl monomer having 3 to 24 carbon atoms (for example, styrene or acrylonitrile) in the presence of a radical polymerization initiator in one or more kinds of polyols. Examples include polyol (polymer content is, for example, 5 to 30% by weight).
Examples of the polyolefin polyol include polyisobutene polyol.
Examples of the polyalkadiene polyol include polyisoprene polyol, polybutadiene polyol, hydrogenated polyisoprene polyol, and hydrogenated polybutadiene polyol.

Examples of the acrylic polyol include a copolymer of an alkyl (meth) acrylate (alkyl 1 to 30 carbon atoms) ester [butyl (meth) acrylate and the like] and a hydroxyl group-containing acrylic monomer [hydroxyethyl (meth) acrylate and the like]. Can be mentioned.
As the amino group-containing polyol, for example, poly (n = 2-6) alkylene (2-6 carbon atoms) poly (n = 3-7) amine AO adduct [N, N, N ′, N ′, N ″ -Pentakis (2-hydroxypropyl) -diethylenetriamine etc.].

  Isocyanate (b1), (b2), (b3), (b4) and / or isocyanate-modified product (b5) in producing the prepolymer (a3) having a hydroxyl group at the terminal, (a1), (a2), The equivalent ratio (NCO / active hydrogen ratio) with (X11) and / or (X12) is usually 0.25 / 1 to 0.99 / 1, preferably 0.5 / 1 to 0.95 / 1, The ratio is preferably 0.6 / 1 to 0.9 / 1, particularly preferably 0.7 / 1 to 0.85 / 1.

  From the viewpoint of adhesiveness, as the active hydrogen component (A), polyether polyol (a21), polyester polyol (a22) and (a21) and / or (a22) and the later-described isocyanates (b1), (b2), ( It is preferable to contain at least one polyol selected from the group consisting of a prepolymer (a3) having a hydroxyl group at the terminal obtained by reacting b3), (b4) and / or an isocyanate-modified product (b5).

From the viewpoint of hydrolysis resistance, the polyether polyols (a21) and (a21) and the isocyanates (b1), (b2), (b3), (b4) and / or the isocyanate-modified product (b5) described later, It is preferable to contain at least one polyol selected from the group consisting of a prepolymer (a3) having a hydroxyl group at the terminal obtained by reacting.
Further, from the viewpoint of curability, the average number of functional groups of the active hydrogen component (A) is preferably 2 to 6 or more, more preferably 2 to 5, particularly preferably 2 to 4, and most preferably 2 to 3. is there.

As the isocyanate component (B) in the present invention, an aliphatic isocyanate (b1) having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), an alicyclic isocyanate having 4 to 15 carbon atoms (b2), C8-15 aromatic aliphatic isocyanate (b3), C6-20 aromatic isocyanate (b4), isocyanurate group, uretoimine group, allophanate group, biuret group, uretoimine group, carbodiimide group and / or Isocyanate-modified (b5) having a uretdione group, compound (X13) having an isocyanate group and an ethylenically unsaturated bond-containing group (x), and these and a low-molecular polyol (a1), a polymer polyol (a2), a compound ( Having an isocyanate group at the terminal obtained from X11) and / or compound (X12) Prepolymer (b6), and the like that.
An isocyanate component (B) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the aliphatic isocyanate (b1) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4 -Or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate and bis ( 2-isocyanatoethyl) carbonate and the like.

  Examples of the alicyclic isocyanate (b2) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2- And isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic isocyanate (b3) having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). Is mentioned.

  Examples of the aromatic isocyanate having 6 to 20 carbon atoms (b4) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'- or 2 , 4′-diphenylmethane diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3, Examples include 3′-dimethyl-4,4′-diisocyanatodiphenylmethane and 1,5-naphthylene diisocyanate.

  Isocyanate-modified product (b5) having an isocyanurate group, uretoimine group, allophanate group, biuret group, uretoimine group, carbodiimide group and / or uretdione group, a modified product having a uretoimine group of MDI, a modified product having a biuret group of HDI And modified products having an isocyanurate group of HDI.

  The prepolymer (b6) having an isocyanate group at the end is composed of a high-molecular polyol (a2), a low-molecular polyol (a1), a compound (X11) and / or a compound (X12), and excess isocyanate (b1) and (b2). , (B3), (b4) and / or an isocyanate-modified product (b5). In this case, it is preferable to use a polyol having a hydroxyl equivalent of 1,000 or less, particularly 30 to 500 (molecular weight per hydroxyl functional group, hereinafter the same) from the viewpoint of adhesive cohesive force and the like.

  Specific examples of the prepolymer (b6) having an isocyanate group at the terminal include, for example, a hydrogenated MDI (2 mol) adduct of glycerol mono (meth) acrylate (1 mol) and a TDI (4 mol) of pentaerythritol (1 mol). ) Adduct, HDI (3 mol) adduct of trimethylolpropane (1 mol), AO2 mol adduct of bisphenol A (1 mol), hydrogenated MDI (2 mol) adduct, and MDI of polypropylene glycol (1 mol) (2 mol) adducts and the like.

  The isocyanate component (B) is preferably a reaction product of a tri- to octavalent polyhydric alcohol and an isocyanate (b1), (b2), (b3) and / or (b4) from the viewpoints of cohesive strength and durability. And a modified product having an isocyanurate group of an aliphatic isocyanate (especially HDI) or an alicyclic isocyanate (especially IPDI and hydrogenated MDI), more preferably an HDI (3 mol) of trimethylolpropane (1 mol). An adduct and a modified product having an isocyanurate group of HDI (such as an HDI trimer).

  From the viewpoint of curability, the average number of functional groups of the isocyanate component (B) is preferably 2 to 6 or more, more preferably 2 to 5, and particularly preferably 3 to 4.

The NCO equivalent of the isocyanate component (B) (molecular weight per NCO functional group, the same shall apply hereinafter) is preferably 1000 or less, more preferably 500 or less, and particularly preferably 300 or less.
The isocyanate group content of the isocyanate component (B) is usually 0.5 to 50% by weight, preferably 1 to 35% by weight, more preferably 3 to 30% by weight, particularly preferably 4 to 25, most preferably 12 to 24% by weight.

  When used as a two-component curable adhesive, the equivalent ratio (NCO / active hydrogen ratio) of the isocyanate component (B) and the active hydrogen component (A) is preferably 0.7 / 1 to 2/1, more preferably Is 0.8 / 1 to 1.5 / 1, particularly preferably 0.9 / 1 to 1.3 / 1, most preferably 1/1 to 1.2 / 1.

When the adhesive of the present invention is used as a two-component curable adhesive, the ethylenically unsaturated bond-containing group (x) can be introduced into the adhesive by the following methods (1) to (6).
(1) The compound (X11) having a hydroxyl group and an ethylenically unsaturated bond-containing group (x) is used as at least a part of the active hydrogen component (A).
(2) The compound (X12) having an amino group and an ethylenically unsaturated bond-containing group (x) is used as at least a part of the active hydrogen component (A).
(3) Compound (X11) and / or compound (X12) and isocyanate (b1), (b2), (b3), (b4) and / or an isocyanate-modified product (at least part of the active hydrogen component (A)) A prepolymer having a hydroxyl group at the terminal obtained by reacting with b5) is used.
(4) The compound (X13) having an isocyanate group and an ethylenically unsaturated bond-containing group (x) is used as at least a part of the isocyanate component (B).
(5) The compound (X11) and / or the compound (X12) and the isocyanate (b1), (b2), (b3), (b4) and / or an isocyanate-modified product (b5) are included in at least a part of the isocyanate component (B). And a prepolymer having an isocyanate group at the terminal obtained from the above.
(6) The above (1) to (5) are arbitrarily combined.

The one-component curable adhesive of the present invention contains a urethane prepolymer (C) having an isocyanate group at the terminal.
The urethane prepolymer (C) having an isocyanate group at the terminal is an active hydrogen component (A) in the two-component curable adhesive (provided that the compound (X11) having a hydroxyl group and an ethylenically unsaturated bond-containing group (x)) The compound (X12) having an amino group and an ethylenically unsaturated bond-containing group (x) is an essential component. ] Is reacted with excess isocyanate (b1), (b2), (b3), (b4) and / or isocyanate-modified product (b5).
(X11), (X12), other active hydrogen components and (b1) to (b5) may be used alone or in combination of two or more.

From the viewpoint of adhesiveness, it is preferable to contain polyether polyol (a21) and / or polyester polyol (a22) in the active hydrogen component (A) in the production of the urethane prepolymer (C).
From the viewpoint of hydrolysis resistance, it is preferable that the polyether polyol (a21) is contained in the active hydrogen component (A) in the production of the urethane prepolymer (C).
Furthermore, from the viewpoint of curability, the average functional group number of (C) is preferably 2 to 6 or more, more preferably 2 to 5, and particularly preferably 2 to 4.

Active hydrogen containing isocyanate (b1), (b2), (b3), (b4) and / or isocyanate-modified product (b5) and compounds (X11) and (X12) in producing urethane prepolymer (C) The equivalent ratio (NCO / active hydrogen ratio) with the component (A) is preferably 1.1 / 1 to 5/1, more preferably 1.4 / 1 to 3/1, particularly preferably 1.5 / 1. ~ 2/1.
The isocyanate group content of the urethane prepolymer (C) is preferably 0.1 to 8% by weight, more preferably 0.5 to 6% by weight, and particularly preferably 1 to 4% by weight.

  The content of the ethylenically unsaturated bond-containing group (x) in the present invention is the active hydrogen component (A) in the case of the two-component curable type from the viewpoint of the deterioration resistance of the cured resin and the storage stability of the adhesive. In the case of the one-component curable type with respect to the total weight of the isocyanate component (B) and the urethane prepolymer (C), the number of moles of ethylenically unsaturated bonds is preferably 10 to 1,000 mmol / kg, more preferably Is 20 to 600 mmol / kg, particularly preferably 30 to 400 mmol / kg.

  The adhesive of the present invention is a solvent [for example, aromatic solvents (toluene, xylene, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), amide solvents (dimethylformamide, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.) And ether solvents (tetrahydrofuran, etc.)].

By containing the solvent, the handling property and leveling property at the time of application of the adhesive are improved.
The amount of solvent used is based on the total weight of the active hydrogen component (A) and the isocyanate component (B) in the case of the two-component curable type, and based on the weight of the urethane prepolymer (C) in the case of the one-component curable type. From the viewpoint of handling property and leveling property, it is preferably 80% by weight or less, more preferably 10 to 50% by weight.

  The adhesive of the present invention can further contain a tackifier (D) for improving the adhesive strength.

Examples of the tackifier (D) include terpene resins, terpene phenol resins, phenol resins, aromatic hydrocarbon modified terpene resins, rosin resins, modified rosin resins, synthetic petroleum resins (aliphatic, aromatic or alicyclic synthesis). Petroleum resins, etc.), coumarone-indene resins, xylene resins, styrene resins, dicyclopentadiene resins, and hydrogenated products of these having hydrogenated unsaturated double bonds. One tackifier may be used alone, or two or more tackifiers may be used in combination.
Among these, those having an acid value and / or a hydroxyl value are preferable from the viewpoint of adhesive strength, rosin resin, phenol resin, terpene phenol resin, xylene resin and hydrogenated products thereof are more preferable, terpene phenol resin and hydrogen thereof. Additives are particularly preferred.

  The acid value or hydroxyl value of the tackifier (D) (in the case of having both an acid group and a hydroxyl group in the molecule) is preferably from the viewpoint of compatibility between the adhesive force and the urethane resin. Is 10 to 400 mgKOH / g, more preferably 20 to 300 mgKOH / g, particularly preferably 50 to 250 mgKOH / g, and most preferably 100 to 220 mgKOH / g.

  The amount of tackifier (D) used is based on the total weight of the active hydrogen component (A) and the isocyanate component (B) in the case of the two-component curable type, and the urethane prepolymer (C in the case of the one-component curable type). ) From the viewpoint of adhesive strength and heat resistance of the adhesive, preferably 100% by weight or less, more preferably 1 to 50% by weight, particularly preferably 3 to 40% by weight, particularly preferably 5 to 35% by weight. %, Most preferably 10 to 30% by weight.

  The adhesive of the present invention can contain a catalyst usually used for polyurethane as necessary to accelerate the curing reaction. Specific examples of the catalyst include organic metal compounds [dibutyltin dilaurate, dioctyltin laurate, bismuth carboxylate, bismuth alkoxide, a chelate compound of bismuth with a compound having a dicarbonyl group, etc.], inorganic metal compounds [bismuth oxide, water, etc. Bismuth oxide, bismuth halide, etc.]; amines [triethylamine, triethylenediamine, diazabicycloundecene, etc.] and combinations of two or more of these. The amount of the catalyst used is not particularly limited, but in the case of the two-component curing type, based on the total weight of the active hydrogen component (A) and the isocyanate component (B), in the case of the one-component curing type, the urethane prepolymer (C) Is preferably 0.0001 to 0.3% by weight, more preferably 0.001 to 0.2% by weight, and particularly preferably 0.01 to 0.1% by weight.

The adhesive of the present invention can contain a polymerization inhibitor (hydroquinone, 4-methoxyphenol, p-benzoquinone, etc.) for improving storage stability.
The amount of the polymerization inhibitor used is based on the total weight of the active hydrogen component (A) and the isocyanate component (B) in the case of the two-component curable type, and the weight of the urethane prepolymer (C) in the case of the one-component curable type. Based on this, it is preferably 1,000 ppm or less, more preferably 1 to 500 ppm.

  The adhesive of the present invention can further contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a filler and a pigment as long as the effects of the present invention are not impaired.

  Antioxidants 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] and phosphorous acid Ester compounds [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'-biphenylene- - phosphonite, etc.] and the like. These antioxidants may be used alone or in combination of two or more. The amount of the antioxidant used is preferably based on the total weight of the active hydrogen component (A) and the isocyanate component (B) or the weight of the urethane prepolymer (C) from the viewpoint of the antioxidant effect and the adhesive strength of the adhesive. It is 5% by weight or less, more preferably 0.05 to 1% by weight.

  Examples of ultraviolet absorbers include salicylic acid derivatives (phenyl salicylate, salicylic acid-P-octylphenyl, salicylic acid-P-tert-butylphenyl, etc.), benzophenone compounds [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 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'-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-octoxyphenyl) Benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- [ 2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4- (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, etc.). An ultraviolet absorber may be used individually by 1 type, or may use 2 or more types together. The amount of the ultraviolet absorber used is preferably from the viewpoint of the ultraviolet absorption effect and the adhesive strength of the adhesive, based on the total weight of the active hydrogen component (A) and the isocyanate component (B) or the weight of the urethane prepolymer (C). 5 wt% or less, more preferably 0.1 to 1 wt%.

  Plasticizers include hydrocarbons [process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, chlorinated paraffin, paraffin wax, copolymerization of ethylene and α-olefin (carbon number 3 to 20) (weight ratio] 99.9 / 0.1 to 0.1 / 99.9) oligomer (Mw 5,000 to 100,000), copolymer oligomer of α-olefin (carbon number 4 to 20) excluding propylene and ethylene (weight ratio 99) .9 / 0.1-0.1 / 99.9) oligomer (Mw 5,000-100,000)]; chlorinated paraffin; ester [phthalate ester [diethyl phthalate (DEP), dibutyl phthalate (DBP), di -2-ethylhexyl phthalate (DOP), didecyl phthalate, dilauryl phthalate, disteary Ruphthalate, diisononyl phthalate, etc.], adipic acid ester [di (2-ethylhexyl) adipate (DOA), dioctyl adipate, etc.] and sebacic acid ester (dioctyl sebacate, etc.)]; And hydrogenated substances having unsaturated double bonds that can be hydrogenated, and the like. A plasticizer may be used individually by 1 type, or may use 2 or more types together. The amount of the plasticizer used is preferably 100% from the viewpoint of the adhesive strength and cohesive strength of the adhesive based on the total weight of the active hydrogen component (A) and the isocyanate component (B) or the weight of the urethane prepolymer (C). % Or less, more preferably 0.5 to 30% by weight.

  Fillers include carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, calcium sulfate, barium sulfate, etc.), sulfites (calcium sulfite, etc.), molybdenum disulfide, silicates (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 use amount of the filler is preferably 250% by weight or less from the viewpoint of the cohesive strength of the adhesive, based on the total weight of the active hydrogen component (A) and the isocyanate component (B) or the weight of the urethane prepolymer (C). More preferably, it is 0.5 to 100% by weight.

  Examples of pigments include 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, Bengala, Molybdenum red, Red lead, Yellow lead, Cadmium yellow, Barium yellow, Strontium yellow, Titanium yellow, Titanium black, Chrome oxide green, Cobalt oxide, Cobalt green, Cobalt chromium green, Ultramarine blue, Bitumen, cobalt blue, cerulean blue, manganese purple, cobalt purple, 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 preferably 250% by weight or less from the viewpoint of the cohesive strength of the adhesive, based on the total weight of the active hydrogen component (A) and the isocyanate component (B) or the weight of the urethane prepolymer (C). Preferably it is 0.1 to 50 weight%.

  As a production method of the prepolymer (a3) having a hydroxyl group at the terminal, the prepolymer (b6) having an isocyanate group at the terminal and the urethane prepolymer (C) having an isocyanate group at the terminal, a known urethane method can be used, Examples thereof include a method of reacting a necessary active hydrogen component and an isocyanate component in the presence or absence of a solvent (toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone, methyl ethyl ketone, tetrahydrofuran, etc.).

  For the reaction, a known reaction device (mixing tank equipped with a stirrer, static mixer, etc.) can be used, and the reaction temperature is preferably 10 to 160 ° C., more preferably 25 to 25 ° C. from the viewpoint of reactivity and suppression of thermal deterioration. It is preferably 120 ° C., and the gas phase is preferably substituted with nitrogen from the viewpoint of stability.

  Additives such as the above-mentioned solvent, tackifier (D), catalyst, polymerization inhibitor, antioxidant, ultraviolet absorber, plasticizer, filler and pigment are the main agent and curing agent in the case of a two-component curable adhesive. Although it may be added to any of the agents, it may be added at the time of blending the main agent and the curing agent, but it is preferably added to the main agent in advance. In the case of a one-component curable adhesive, it may be added to the adhesive in advance or may be added at the time of use.

  The adhesive for dry laminate of the present invention is particularly useful for dry laminate adhesion between various plastic films and for dry laminate adhesion between a plastic film and a metal vapor-deposited film, an inorganic plate, a plastic molded plate or a metal plate.

Examples of the plastic film include polypropylene film, polyethylene film, polyester film, polyacrylic film, polyvinyl chloride film, polystyrene film, nylon film, ethylene vinyl alcohol copolymer film, polyvinyl alcohol film, fluorine film, and ethylene vinyl acetate weight. Examples thereof include a combined film and a plastic film obtained by depositing the surface of these films with aluminum or silica or coating with polyvinylidene chloride.
The plastic film is preferably subjected to surface treatment such as corona treatment or plasma treatment from the viewpoint of adhesiveness.

Examples of the inorganic board include a slate board, a calcium silicate board, a gypsum board, a wood wool 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, a spin coater, a curtain coater, a slot coater, a bar coater, or the like can be used for coating an adhesive in the adhesion between plastic films. The coating amount (solid content) of the adhesive during coating is preferably 1 to 50 g / m ² , more 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 the adhesive in bonding the plastic film and the inorganic plate, the plastic molded plate, or the metal plate. The coating amount of the adhesive at the time of coating (solid content), preferably 2~500g / m ² in the case of inorganic board, and more preferably 3~450g / m ^2, when a plastic molded plate or a metal plate, preferably 1 to 300 g / m ² , more preferably ² to 250 g / m ² .

The coating temperature of the adhesive when applied to the support is preferably 10 to 160 ° C., more preferably 25 to 120 ° C. from the viewpoint of coating properties and thermal deterioration suppression, and the viscosity of the adhesive at the coating temperature. Is preferably from 0.01 to 100 Pa · s, more preferably from 0.02 to 50 Pa · s, from the viewpoint of moldability (can be thickly coated and free from appearance defects such as warping and sink marks after curing) and coating properties. Particularly preferred is 0.03 to 10 Pa · s.
A normal dry laminator or an extrusion laminator is used for laminating. After laminating, the adhesive is usually completely cured by curing at 10 to 50 ° C. for 20 to 150 hours.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the examples, unless otherwise specified, parts and% indicate parts by weight and% by weight, respectively. In addition, Example 6 below is a reference example.

[Production of active hydrogen component (A)]
Production Example 1
Polyester diol [trade name “San Ester 45625”, manufactured by Sanyo Chemical Industries, Ltd., Mn: 2,500] 353 parts, glycerin monomethacrylate [trade name “Blenmer GLM”, NOF (Made by Co., Ltd., molecular weight: 160) After 50 parts of ethyl acetate and 500 parts of ethyl acetate were charged and uniformly stirred, 97 parts of MDI [trade name “Millionate MT”, manufactured by Nippon Polyurethane Co., Ltd.] were charged and stirred and mixed in a nitrogen stream. And it was made to react at 70-80 degreeC for 6 hours, and the solution of the urethane prepolymer (A-1) which has a hydroxyl group at the terminal of solid content concentration 50% was obtained.

Production Example 2
In a reaction vessel equipped with a condenser, 209.6 parts of polytetramethylene ether glycol [trade name “PTMG1000”, manufactured by Mitsubishi Chemical Corporation, Mn: 1,000] and an EO adduct of bisphenol A [trade name “BPE -20T ", Sanyo Chemical Industries, Ltd., Mn: 310] 139.8 parts, uniformly stirred at 105 ° C, cooled to 60 ° C, and charged with 2.5 parts of glycerol monomethacrylate and 500 parts of ethyl acetate. After uniform stirring, 148.1 parts of hydrogenated MDI [trade name “Desmodur W”, manufactured by Sumika Bayer Urethane Co., Ltd.] were charged, stirred and mixed in a nitrogen stream, and reacted at 70 to 80 ° C. for 2 hours. Further, 0.2 part of a catalyst [trade name “Neostan U-600”, manufactured by Nitto Kasei Co., Ltd.] was charged and reacted for 8 hours to give a urea having a hydroxyl group at the terminal with a solid concentration of 50%. A solution of tan prepolymer (A-2) was obtained.

Production Example 3
Charge amount of polytetramethylene ether glycol to 236.8 parts, charge amount of EO adduct of bisphenol A to 101.5 parts, charge amount of glycerol monomethacrylate to 15.0 parts, charge amount of hydrogenated MDI A solution of a urethane prepolymer (A-3) having a hydroxyl group at the terminal with a solid content concentration of 50% was obtained in the same manner as in Production Example 2 except that 146.7 parts were changed.

Production Example 4
Polytetramethylene ether glycol charge to 286.7 parts, bisphenol A EO adduct charge to 50.6 parts, glycerol monomethacrylate charge to 25.0 parts, hydrogenated MDI charge A solution of a urethane prepolymer (A-4) having a hydroxyl group at the terminal with a solid content concentration of 50% was obtained in the same manner as in Production Example 2 except that 137.7 parts of was replaced.

Production Example 5
The amount of polytetramethylene ether glycol charged to 251.7 parts, the amount of bisphenol A EO adduct added to 107.9 parts, the amount of glycerol monomethacrylate charged to 3.6 parts, and the amount of hydrogenated MDI charged A solution of urethane prepolymer (A-5) having a hydroxyl group at the terminal having a solid content concentration of 50% was obtained in the same manner as in Production Example 2 except that 136.9 parts of the above components were replaced.

Production Example 6
In a reaction vessel equipped with a cooling tube, 247.0 parts of the polytetramethylene ether glycol and 105.8 parts of the bisphenol A EO adduct were charged, stirred uniformly at 105 ° C, cooled to 60 ° C, and glycerin monomethacrylate. 3.5 parts, 3.5 parts of 2,2-bis (hydroxymethyl) propionic acid and 500 parts of ethyl acetate were added and stirred uniformly, then 140.2 parts of the hydrogenated MDI was added and stirred and mixed under a nitrogen stream. And then reacting at 70 to 80 ° C. for 2 hours, further adding 0.2 part of the above catalyst (Neostan U-600) and reacting for 8 hours, a urethane prepolymer having a hydroxyl group at the terminal with a solid content concentration of 50% (A-6) ) Was obtained.

Production Example 7
Into a reaction vessel equipped with a cooling tube, 412.5 parts of polypropylene glycol [trade name “SANNICS PP-1000”, manufactured by Sanyo Chemical Industries, Ltd., Mn: 1,000] and 500 parts of ethyl acetate were charged and stirred uniformly. The temperature was adjusted to 60 ° C., 87.5 parts of MDI was added, stirred and mixed in a nitrogen stream, reacted at 70-80 ° C. for 6 hours, and a urethane prepolymer having a hydroxyl group at the terminal with a solid content concentration of 50%. A solution of (A-7) was obtained.

Production Example 8
Urethane prepolymer (A-8) having a hydroxyl group at the terminal with a solid content concentration of 50% in the same manner as in Production Example 7, except that the polypropylene glycol is replaced with polytetramethylene ether glycol ["PTMG1000" manufactured by Mitsubishi Chemical Corporation]. Solution was obtained.

Production Example 9
In a reaction vessel equipped with a cooling tube, 495 parts of the solution (A-8) obtained in Production Example 8, 2.5 parts of 2-hydroxyethyl acrylate and 2.5 parts of ethyl acetate were charged, stirred uniformly, and solid. A solution of urethane prepolymer (A-9) having a hydroxyl group at the terminal with a partial concentration of 50% was obtained.

[Production of urethane prepolymer (C) having an isocyanate group at the terminal]
Production Example 10
In a reaction vessel equipped with a cooling tube, polycarbonate diol [trade name “Kuraray polyol C-2090”, manufactured by Kuraray Co., Ltd., Mn: 2,000] 222.9 parts, polytetramethylene ether glycol [Mitsubishi Chemical Corporation] “PTMG1000”] 148.6 parts, 15.0 parts of glycerin monomethacrylate and 500 parts of ethyl acetate were added, and after stirring uniformly, the temperature was adjusted to 60 ° C. with water, and then 113.5 parts of MDI was added and stirred under a nitrogen stream. Then, the mixture was reacted at 70 to 80 ° C. for 6 hours to obtain a urethane prepolymer (C-1) solution having an isocyanate group at the terminal having a solid content concentration of 50%.

Comparative production example 1
Polycarbonate diol [“Kuraray polyol C-2090” manufactured by Kuraray Co., Ltd.] 246.2 parts, polytetramethylene ether glycol [“PTMG1000” manufactured by Mitsubishi Chemical Co., Ltd.] 164.2 parts in a reaction vessel equipped with a cooling pipe Then, 500 parts of ethyl acetate was added, and after uniform stirring, the temperature was adjusted to 60 ° C. after water, and 89.6 parts of MDI was added, stirred and mixed in a nitrogen stream, and reacted at 70-80 ° C. for 6 hours to obtain a solid concentration. A solution of urethane prepolymer (C′-1) having an isocyanate group at the end of 50% was obtained.

Examples 1-12 and Comparative Examples 1-2
The main component of the two-part curable adhesive is prepared by blending the active hydrogen component (A) in the number of parts shown in Table 1, ethyl acetate, and, if necessary, an adhesive resin (D), a catalyst and an antioxidant, and Table 1 The solution of (B-1) to (B-2) or (B-3) shown above in (B-3) (the numerical value is described) is used as the corresponding curing agent of the present invention comprising the main agent and the curing agent. Two-component curable adhesives (Y1) to (Y12) and comparative two-component curable adhesives (Z1) to (Z2) were obtained.

Example 13 and Comparative Example 3
The solution of urethane prepolymer (C) having an isocyanate group at the end of the number of parts shown in Table 1, ethyl acetate and, if necessary, an antioxidant are blended, and the one-part curable adhesive (Y13) of the present invention and 1 for comparison A liquid curable adhesive (Z3) was obtained.

The details of each component in Table 1 are as follows.
-Solutions of (A-1) to (A-9): a solution of a urethane prepolymer having a hydroxyl group at the terminal having a solid content concentration of 50% obtained in Production Examples 1 to 9;
-Tackifier (D-1): terpene phenol resin [trade name “Mighty Ace K-125”, hydroxyl value 200 mg KOH / g, manufactured by Yasuhara Chemical Co., Ltd.];
-Tackifier (D-2): Hydrogenated product of terpene phenol resin [trade name “YS Polystar TH-130”, hydroxyl value 60 mgKOH / g, manufactured by Yasuhara Chemical Co., Ltd.];
Catalyst: Bismuth catalyst [trade name “Neostan U-600”, manufactured by Nitto Kasei Co., Ltd.];
Antioxidant: Hindered phenol antioxidant [trade name “Irganox 1010”, manufactured by BASF Japan Ltd.];
-Solution of (B-1): 75% ethyl acetate solution of a reaction product (B-1) of TDI (3 mol) and TMP (1 mol) [trade name “Coronate L”, manufactured by Nippon Polyurethane Co., Ltd.] ;
-Solution of (B-2): 75% ethyl acetate solution of a reaction product (B-2) of HDI (3 mol) and TMP (1 mol) [trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.] ;
-(B-3): Isocyanurate modified product of HDI [trade name “Duranate TKA-100”, manufactured by Asahi Kasei Chemicals Corporation];
-(C-1) solution: a solution of a urethane prepolymer having an isocyanate group at the terminal having a solid content concentration of 50% obtained in Production Example 10;
-Solution of (C'-1): A solution of urethane prepolymer having an isocyanate group at the terminal having a solid content concentration of 50% obtained in Comparative Production Example 1.

In the case of a two-component curable adhesive, the obtained adhesive is blended with the main agent and the curing agent in the number of parts shown in Table 1 (the number of the main agent is that described in the total column), and then the first base material. A hot air dryer of 80 to 100 ° C. was applied to a corona-treated PET film (film thickness 100 μm) with a solvent-type dry laminator so that the solid content was 4.5 to 5.5 g / m ^2. After drying for about 1 minute to volatilize the solvent, the coated surface is bonded to a corona-treated PET film (film thickness 100 μm) as the second substrate, and cured at 40 ° C. for 3 days. Obtained. Table 2 shows the results of measuring the adhesive strength of the film by the following method using this laminate film.

  In addition, in the case of a two-component curable adhesive, the obtained adhesive was blended with the main agent and the curing agent in the number of parts shown in Table 1 (the number of parts of the main agent is described in the total column) and then dried. The film was cast to a thickness of 1 mm and dried and cured at room temperature for 2 days, at 40 ° C. for 3 days, and further under reduced pressure at 60 ° C. for 12 hours to obtain a 1 mm thick resin film. Table 2 shows the results of evaluating the durability (heat resistance and hot water resistance) of the adhesive by using the film by the following method together with the content of the ethylenically unsaturated bond-containing group (x) in each adhesive.

(1) Measuring method of adhesive force (1-1) Adhesive force before heating After curing the laminated film bonded with adhesives (Y1) to (Y13) or (Z1) to (Z3), the size becomes 200 mm × 25 mm. The T-type peel strength (unit: N / 25 mm) was measured using a tensile tester at 23 ° C. under a pulling speed of 300 mm / min. The measurement was performed on five samples, and the average values are shown in Table 2. The larger the value of T-type peel strength, the better the adhesion.
(1-2) Adhesive strength after heating After the laminate film was heated at 150 ° C. for 3 days and temperature-controlled at 23 ° C. for 1 day, the adhesive strength was measured by the above method. The measurement was performed on five samples, and the average values are shown in Table 2.

(2) Heat resistance evaluation method The resin film of the adhesive was heated at 180 ° C for 2 days. Before and after heating, the viscoelasticity of the film was measured by the following method, and the durability was evaluated according to the following criteria.
<Viscoelasticity measurement conditions>
Measuring apparatus: Rheogel-E4000 [manufactured by UBM Co., Ltd.]
Measurement jig: Solid shear measurement temperature: -20 to 200 ° C
Temperature increase rate: 5 ° C / min
Measurement frequency: 10Hz
Sample size: about 7mm (length) x about 6mm (width)
<Evaluation criteria>
The change in storage elastic modulus (G ′) at 150 ° C. was evaluated based on the following criteria.
A: Little change in viscoelasticity (storage modulus (G ′); the same applies hereinafter) before and after heating.
○: Viscoelasticity (G ′) after heating is increased by 30% or more.
Δ: Viscoelasticity (G ′) after heating decreases by 30% or more.
X: After heating, the resin flows and the viscoelasticity cannot be measured.

(3) Evaluation method of hot water resistance The laminate film was cut into a size of 100 mm × 100 mm and immersed in hot water at 100 ° C. for 4 hours, and then the presence or absence of floating peeling was visually evaluated based on the following criteria.
A: No lifting or peeling O: Slight lifting or peeling is observed at the end. (Area: Within 5%)
×: Floating off

  From Table 2, the adhesive of the present invention has excellent adhesive strength, little resin degradation, and the ethylenically unsaturated bond captures radicals generated by the influence of heat, oxidation, etc., so that degradation due to molecular cleavage or the like occurs. It can be seen that the viscoelasticity (G ′) of the adhesive due to the crosslinking effect can be improved by not only suppressing but also changing the content of the ethylenically unsaturated bond.

  Since the adhesive of the present invention has the above-mentioned effects, the film material [resin film (polyethylene, polypropylene, polyethylene terephthalate, nylon, cellophane, polystyrene, polyvinyl chloride and polyvinylidene chloride, fluorine resin, ethylene vinyl acetate copolymer resin) And polyester resin, etc.) and metal (aluminum and copper, etc.) vapor-deposited films and metal (aluminum and copper, etc.) foil, etc.], etc. Building materials, exterior materials, and sealing materials that are useful as adhesives for laminating plastic building materials such as resins and melamine resins, and metal building materials such as iron and aluminum, and the above resin films. It is particularly useful as an adhesive used in

Claims (9)

A two-component curable adhesive comprising a main agent containing an active hydrogen component (A) and a curing agent containing an isocyanate component (B), or a urethane prepolymer (C) having an isocyanate group at the terminal 1 A liquid curable adhesive, wherein the active hydrogen component (A) and / or the isocyanate component (B) and the urethane prepolymer (C) are glycerin mono (meth) as an ethylenically unsaturated bond-containing group (x ). It has a (meth) acryloyl group introduced by at least one selected from the group consisting of acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate and pentaerythritol di (meth) acrylate. Adhesive for dry lamination. The active hydrogen component (A) is a polyether polyol (a21), a polyester polyol (a22) and (a21) and / or (a22), an aliphatic isocyanate (b1) having 2 to 18 carbon atoms, or a carbon number 4 to 15 Are reacted with an alicyclic isocyanate (b2), an araliphatic isocyanate having 8 to 15 carbon atoms (b3), an aromatic isocyanate having 6 to 20 carbon atoms (b4) and / or a modified product thereof (b5). the adhesive according to claim 1, further comprising at least one polyol selected from the group consisting of prepolymer (a3) having a hydroxyl group becomes end. The prepolymer (C) is an active hydrogen component having a polyether polyol (a21) and / or a polyester polyol (a22) as essential components, an aliphatic isocyanate (b1) having 2 to 18 carbon atoms, and a 4 to 15 carbon atoms. An alicyclic isocyanate (b2), an araliphatic isocyanate having 8 to 15 carbon atoms (b3), an aromatic isocyanate having 6 to 20 carbon atoms (b4) and / or a modified product thereof (b5). the adhesive of claim 1, wherein a prepolymer having a terminal isocyanate group. The adhesive according to claim 2 or 3 , wherein the polyester polyol (a22) is a polycarbonate polyol. The adhesive according to any one of claims 2 to 4 , wherein the polyether polyol (a21) contains an alkylene oxide adduct of a bisphenol compound. Furthermore, the adhesive agent in any one of Claims 1-5 containing a tackifier (D). The adhesive according to claim 6, wherein the tackifier (D) is a terpene phenol resin and / or a hydrogenated product of a terpene phenol resin. The adhesive 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 according to any one of claims 1 to 8 .