TW202134383A - Two-part curable urethane adhesive, cured product of two-part curable urethane adhesive, and urethane adhesive sheet - Google Patents

Abstract

The purpose of the present invention is to provide a two-part curable urethane adhesive whereby it is possible to obtain an adhesive sheet that exhibits excellent cured film properties, can be peeled off with very little force, and exhibits little change in adhesive strength before and after a heat resistance test. The present invention is a two-part curable urethane adhesive including a main agent and a curing agent, wherein the main agent includes a urethane resin (P) that has a hydroxyl group and is obtained by reacting a polyol component (a) that has a polyfunctional polyoxyalkylene polyol (a1) having a hydroxyl value of 10-350 mgKOH/g as an essential component with a urethane prepolymer (b) having an isocyanate group. The polyfunctional polyoxyalkylene polyol (a1) is a polyoxyalkylene polyol (a11) having a hydroxypropyl group on the end of the molecule represented by general formula (1) and/or an ethylene oxide addition product (a12) thereof, and the curing agent includes a crosslinking agent (D) having an isocyanate group. In general formula (1), X is an m-valent residue obtained by removing all of the active hydrogen atoms from a compound having m of active hydrogen atoms, A is an alkylene group that has 2-12 carbons atoms and that may be substituted with a phenyl group, a halophenyl group, or a halogen atom, Z is a propylene group, m is an integer of 4-10, p is an integer of 0-199, q is an integer of 1-200, and the expression 1 ≤ p + q ≤ 200 is satisfied.

Description

2-component hardening urethane adhesive, hardened product of 2-component hardening urethane adhesive, and urethane adhesive sheet

The present invention relates to a two-component hardening type urethane adhesive, a hardened product of the two-component hardening type urethane adhesive, and a urethane adhesive sheet.

Regarding the optical member sheet, one with an adhesive layered on a base material (polyester, polyethylene, polypropylene, glass, etc.) can be used. The optical component sheet is used by manufacturers of optical components such as polarizing plates to protect the surface of optical components when they are shipped. In addition, in manufacturers of image display devices such as liquid crystal displays, it is used for the protection of optical members in the manufacturing process of display devices (liquid crystal modules) or the attachment of optical members to each other.

Although acrylic adhesives have been mainly used in such optical member sheets, urethane adhesives have been studied for reasons such as good followability to substrates and excellent adhesive properties (for example, Patent Document 1). However, in the urethane adhesive disclosed in Patent Document 1, in order to express the strength of the adhesive sheet, it is necessary to use a large amount of hardener, or increase the crosslinking point, or increase the urethane group concentration, and the resulting adhesive has poor flexibility. The hardened film becomes brittle, or the adhesive force changes before and after the heat resistance test. In addition, since the adhesive force of the adhesive sheet becomes insufficiently low, a large force is required to peel the sheet from the optical member, and there is a problem of poor workability. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2006-182795

[The problem to be solved by the invention]

The subject of the present invention is to provide a two-component hardening urethane adhesive, which exhibits excellent cured film properties, can be peeled off with a very small force, and changes in adhesion before and after the heat resistance test. Small adhesive piece. [Technical means to solve the problem]

The inventors of the present invention completed the present invention after intensive research in order to solve the above-mentioned problems. That is, the present invention is a two-component curing type urethane adhesive, a cured product of the above-mentioned two-component curing type urethane adhesive, and a urethane adhesive sheet formed by using the above-mentioned two-component curing type urethane adhesive. The curing type urethane adhesive contains a main agent and a hardening agent. The above main agent contains a urethane having a hydroxyl group formed by reacting a polyol component (a) with a urethane prepolymer having an isocyanate group (b) Resin (P), the above-mentioned polyol component (a) uses a multifunctional polyoxyalkylene polyol (a1) with a hydroxyl value of 10 to 350 mgKOH/g as an essential component, and the above-mentioned polyoxyalkylene polyol Alcohol (a1) is a polyoxyalkylene polyol (a11) and/or its ethylene oxide adduct (a12) having a hydroxypropyl group at the molecular end represented by the general formula (1). The curing agent contains Crosslinking agent with isocyanate group (D).

[In the general formula (1), X is an m-valent residue obtained by removing all active hydrogen atoms from a compound having m active hydrogen atoms; A is a carbon number of 2～ which can be substituted by phenyl, halophenyl or halogen atoms The alkylene of 12; Z is a propylene group; m is an integer from 4 to 10; p is an integer from 0 to 199, q is an integer from 1 to 200, and satisfies 1≦p+q≦200. ] [Compared with the effect of the previous technology]

The two-component hardening urethane adhesive of the present invention can obtain an adhesive sheet that exhibits excellent cured film properties, can be peeled off with a very small force, and has a small change in adhesive force before and after the heat resistance test. .

In the two-component curing type urethane adhesive of the present invention, the main agent contains a urethane resin (P) having a hydroxyl group formed by reacting a polyol component (a) with an isocyanate group-containing urethane prepolymer (b) .

The polyol component (a) in the present invention uses a multifunctional polyoxyalkylene polyol (a1) with a hydroxyl value of 10 to 350 mgKOH/g as an essential component. The polyfunctional polyoxyalkylene polyol (a1) is a polyoxyalkylene polyol (a11) having a hydroxypropyl group at the molecular end represented by the general formula (1) and/or its ethylene oxide addition The finished product (a12) is used as an essential ingredient.

[In the general formula (1), X is an m-valent residue obtained by removing all active hydrogen atoms from a compound having m active hydrogen atoms; A is a carbon number of 2～ which can be substituted by phenyl, halophenyl or halogen atoms Z is an alkylene group of 12; Z is a propylene group; m is an integer of 4-10; p is an integer of 0-199, q is an integer of 1-200, and satisfies 1≦p+q≦200. ]

X in the general formula (1) is an m-valent residue obtained by removing all active hydrogen atoms from a compound having m active hydrogen atoms, and m is an integer of 4-10. If m is less than 4, the peeling force of the obtained adhesive increases, the cured film becomes brittle, or the adhesive force is not low enough. If m exceeds 10, the viscosity of the polyfunctional polyoxyalkylene polyol (a1) will increase, the viscosity of the mixed solution of the main agent and the hardener will increase, and the cutting properties of the hardened product will also decrease. In addition, the cutting property of the above-mentioned hardened material refers to the property of suppressing the generation of swarf when the hardened material of the 2-component hardening urethane adhesive is cut with the blade of a cutter. More preferably, the cut surface is smooth. Generally speaking, the cutting property of the hardened material is the opposite property of the decrease of the peeling force. From the viewpoints of adhesion to the base material, reduction of the peeling force, and improvement of the cutability of the cured product, m is preferably 5-8, more preferably 6. Examples of compounds having m active hydrogen atoms that constitute residue X include: hydroxyl-containing compounds, amine-containing compounds, carboxyl-containing compounds, thiols, etc., having a hydroxyl group, a primary or secondary amine group, and a carboxyl group. And mercapto-based compounds, etc.

Examples of the above-mentioned hydroxyl-containing compounds include: 4- to 10-valent polyhydric alcohols (neopentitol, sorbitol, xylitol, mannitol, etc.); these intermolecular or intramolecular dehydrated products (such as di-neopentyl alcohol) Tetraol and sorbitol anhydride, etc.); polyglycerol (polymerization degree 2-8); sugars and their derivatives (such as glucose, sucrose, fructose, α-methyl glucoside and glycosides, etc.); with m hydroxyl groups Polymers or oligomers with a number average molecular weight of 2,000 or less {polydiene (carbon number 4-10) polyol (such as polybutadiene polyol and its hydride); hydroxyalkyl group (carbon number 2-4) ( (Co)polymer of meth)acrylate; polyvinyl alcohol (saponification degree above 60%), etc.}; and a mixture of two or more of these.

In addition, the number average molecular weight in the present invention can be measured by gel permeation chromatography, for example, under the following conditions. Installation: "Waters Alliance 2695" [manufactured by Waters Corporation] Column: "Guardcolumn Super H-L" (1 piece), "It is formed by connecting 1 piece each of TSKgel SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 (all manufactured by Tosoh Corporation)" Sample solution: 0.25% by weight tetrahydrofuran solution Solution injection volume: 10μl Flow rate: 0.6ml/min Measuring temperature: 40℃ Detection device: refractive index detector Reference material: standard polyethylene glycol

Examples of amine-containing compounds include: polyamines having 4 to 10 active hydrogen atoms [aliphatic diamines with 2 to 12 carbon atoms or more {alkylenes with 2 to 12 carbon atoms] Amines (such as ethylene diamine, propylene diamine, hexamethylene diamine, etc.), alicyclic diamines with 6 to 15 carbon atoms (1,4-diaminocyclohexane, isophorone diamine and 4, 4'-Diaminocyclohexylmethane, etc.)}, C6-15 aromatic diamine {m-phenylenediamine or p-phenylenediamine, toluenediamine, diethyltoluenediamine, 4,4'- Diaminophenylmethane and 2,2-bis(4,4'-diaminophenyl)propane, etc.}, C8-15 aromatic aliphatic diamine (m-xylylenediamine) Or p-xylylenediamine (p-xylylenediamine, etc.), heterocyclic polyamines with carbon number 4 to 10 {piper, amine alkyl (carbon number 2 to 4) piper (such as aminoethyl piper), Amino alkyl (carbon number 2 to 4) imidazole, etc.}, alkylene polyalkylene polyamine with carbon number of 2 to 4 {diethylenetriamine, dipropylenetriamine, triethylenetetramine, Polyethyleneimine and mono-, di-, or tri-alkyl (carbon number 1 to 4) polyalkylene polyamines with a number average molecular weight of 2,000 or less (such as dimethyl ethylenetetramine, etc.)} etc.]; hydroxyalkyl (C2～4) mono- or di-alkanol (C2～4) amine (N,N-bis(2-hydroxyethyl)ethylenediamine, etc.); with one or more amine groups A polymer or oligomer with a number average molecular weight of 2,000 or less [Amino alkyl (carbon number 2 to 4) (meth)acrylate (co)polymer, etc.]; and a mixture of two or more of these.

Examples of carboxyl group-containing compounds include aromatic polycarboxylic acids with 8 to 30 carbon atoms (for example, naphthalenetetracarboxylic acid and pyromellitic acid, etc.), unsaturated carboxylic acid polymers [with a number average molecular weight of 2,000 or less ( Meth)acrylic acid (co)polymer, etc.] and a mixture of two or more of these.

Examples of the mercaptans include 4- to 10-valent polythiols having 2 to 6 carbon atoms or more (for example, neopentyl erythritol (3-mercaptobutyrate), etc.).

Among these, from the viewpoint of hardening properties, preferred are hydroxyl-containing compounds and amine-containing compounds, and more preferred are 4-10 valent polyols {neopentitol, sorbitol, xylitol And mannitol, etc.}; these intermolecular or intramolecular dehydrates (such as dineopentaerythritol and sorbitol anhydride; polyglycerol (polymerization degree 2-8); sugars and their derivatives (such as glucose, fructose, Sucrose, α-methyl glucoside and glycoside, etc.).

In the general formula (1), A is an alkylene group having 2 to 12 carbon atoms which may be substituted by a phenyl group, a halophenyl group or a halogen atom, and examples include: straight chain or branched alkylene group having 2 to 12 carbon atoms, Cycloalkylenes having 6 to 10 carbon atoms and those in which at least a part of the hydrogen atoms are substituted with phenyl, halophenyl, or halogen atoms (Cl, Br, etc.), etc.

Specific examples of A include: ethylene, 1,2- or 1,3-butylene, 1,2-, 2,3-, 1,3- or 1,4-butylene, carbon Number 5-12, 1,2-alkylene (1,2-dodecylene group (1,2-dodecylene group), etc.), 1,2-cyclohexylene, chloropropylene, bromopropylidene , Phenyl ethylene and chlorophenyl ethylene and so on.

(A-O) in the general formula (1) is the AO-derived part obtained by adding alkylene oxide (hereinafter, abbreviated as AO) to a compound having m active hydrogen atoms constituting residue X . Examples of AO used include: ethylene oxide (hereinafter, abbreviated as EO), 1,2-propylene oxide (hereinafter, abbreviated as PO), 1,3-propylene oxide, 1,2-, 1 ,3-, 2,3- or 1,4-butylene oxide (hereinafter, butylene oxide is abbreviated as BO), α-olefin oxide (α-olefin oxide) with 5 to 12 carbon atoms, epihalogen Alcohol (epihalohydrin) (epihalohydrin, epibromohydrin, etc.), styrene oxide, styrene oxychloride, 1,2-epoxycyclohexane and a combination of two or more of these, p (A-O) consists of When two or more types of oxyalkylene are formed, the bonding style can be either block or random. Among these, from the viewpoint of the flexibility of the cured product, PO and 1,2-BO are preferable.

Z in the general formula (1) is propylene group, specifically, 1,2- or 1,3-propylene group. In the general formula (1), p is an integer from 0 to 199, and q is an integer from 1 to 200, and satisfies 1≦p+q≦200. From the viewpoint of adhesion to the substrate, the value of p+q is preferably 50 or less, and more preferably 30 or less.

In addition, the polyfunctional polyoxyalkylene polyol (a1) is preferably a polyol having a group represented by the general formula (2) and/or a group represented by the general formula (3) at the molecular terminal.

In general formula (2) and general formula (3), a is each independently an integer of 0 or more. When a is 0, the general formulas (2) and (3) represent the molecular end of the polyoxyalkylene polyol (a11), and when a is 1 or more, the general formulas (2) and (3) ) Represents the molecular end of the ethylene oxide adduct (a12) of the polyoxyalkylene polyol (a11). In addition, regarding the ratio of the total number of groups represented by the general formula (2) possessed by the polyfunctional polyoxyalkylene polyol (a1), from the viewpoint of the breaking strength and cutting properties of the cured product, the polyfunctional polyoxyalkylene The alkylene polyol (a1) has the number of groups represented by the general formula (2) and the number of the groups represented by the general formula (3) as a reference, preferably at least 40%, and more preferably Above 60%.

The confirmation that the polyoxyalkylene polyol (a11) has a hydroxypropyl group at the molecular end can be ^{performed, for example, by the 1} H-NMR method. The hydroxypropyl group includes a group containing a primary hydroxyl group (a hydroxyl group bonded to a primary carbon) represented by the following chemical formula (4) and a group containing a secondary hydroxyl group (bonded to a secondary carbon) represented by the following chemical formula (4') Hydroxy) base. The ratio of the number of primary hydroxyl-containing groups in the polyoxyalkylene polyol (a11) to the total number of primary hydroxyl-containing groups and secondary hydroxyl-containing groups, that is, the primary hydroxyl content (hereinafter, abbreviated as primary Rate), from the viewpoint of adhesion, it is preferably 40% or more, and more preferably 60% or more.

The first order rate can be obtained by measuring ^{the sample by the 1} H-NMR method after pretreatment (esterification) of the sample in advance.

The details of the ¹ H-NMR method are explained below. <Sample preparation method> Weigh approximately 30 mg of the measurement sample into a 5 mm diameter NMR sample tube, add approximately 0.5 ml of a deuterated solvent, and dissolve it. Then, about 0.1 ml of trifluoroacetic anhydride was added to prepare a sample for analysis. As the deuterated solvent, for example, a solvent capable of dissolving a sample can be appropriately selected from deuterated chloroform, deuterated toluene, deuterated dimethylsulfoxide, deuterated dimethylformamide, and the like. <NMR measurement> ¹ H-NMR measurement is performed under general conditions. <Calculation method of the first order rate> According to the aforementioned method of the previous treatment, the hydroxyl group at the end of the polyoxyalkylene polyol reacts with the added trifluoroacetic anhydride to form a trifluoroacetate. As a result, the signal from the methylene group bonded to the primary hydroxyl group is observed around 4.3 ppm, and the signal from the methine group bonded to the secondary hydroxyl group is observed around 5.2 ppm. The primary conversion rate is calculated by the following formula. Primary conversion rate (%)=[x/(x＋2×y)]×100 [where x is the integral value of the signal from the methylene group bonded to the primary hydroxyl group near 4.3ppm, and y is the integral value of the signal from the secondary hydroxyl group near 5.2ppm The integral value of the signal of the methine group to which the hydroxyl group is bonded. ]

Regarding the above-mentioned polyfunctional polyoxyalkylene polyol (a1), in other words, it is preferable that the following conditions are satisfied. When the polyfunctional polyoxyalkylene polyol (a1) is only the case of the polyoxyalkylene polyol (a11), it is preferable that the polyoxyalkylene polyol (a11) has a primary hydroxyl content of at least Is 40%. When there are two or more polyoxyalkylene polyols (a11), it is preferable that the primary hydroxyl content of the mixture is at least 40%. In addition, when the polyfunctional polyoxyalkylene polyol (a1) is only the case of the ethylene oxide adduct (a12), it is preferably the primary hydroxyl group of (a11) before the addition of ethylene oxide The content is at least 40%. When (a11) before the addition of ethylene oxide is two or more types, it is preferable that the primary hydroxyl content of the mixture is at least 40%. In addition, in the case where the polyfunctional polyoxyalkylene polyol (a1) is a mixture of the polyoxyalkylene polyol (a11) and the ethylene oxide adduct (a12), it is preferably assumed to exist (A12) In the case of a mixture of (a11) before the addition of ethylene oxide and (a11) contained in the polyfunctional polyoxyalkylene polyol (a1), the primary hydroxyl content of the mixture should be at least 40% . Furthermore, regarding the ratio of the total number of groups represented by the general formula (2) possessed by the polyfunctional polyoxyalkylene polyol (a1), from the viewpoint of the breaking strength of the cured product and the improvement of the cutting properties, the polyfunctional polyol (a1) The oxyalkylene polyol (a1) has the number of groups represented by the general formula (2) and the number of groups represented by the general formula (3) as a reference, and is more preferably 60% or more.

The polyoxyalkylene polyol (a11) can be produced, for example, by the method described in JP 2000-344881 A. As a preferable example of polyoxyalkylene polyol (a11), there can be mentioned: in the presence of ginseng (pentafluorophenyl) borane catalyst (hereinafter, abbreviated as TPB), the ring-opening addition polymerization of PO is The active hydrogen-containing compound (a0) represented by the following general formula (5), etc. When TPB is used as a catalyst to carry out PO ring-opening addition polymerization, there is a tendency for PO addition to proceed so that the hydroxyl group at the terminal selectively becomes the base of the chemical formula (4).

X, A, p, and m in the general formula (5) are the same as those in the above general formula (1).

As a specific example of the active hydrogen-containing compound (a0), when p is 0, the same as those exemplified for the compound having m active hydrogen atoms constituting the residue of the general formula (1) can be mentioned. In addition, in this specification, a compound obtained by adding PO to a compound in which p is 0 in the general formula (5) is a compound in which p is 0 and q is 1 or more in the general formula (1).

When p is 1 or more, the active hydrogen-containing compound (a0) is a polyol obtained by adding AO (co) to the compound constituting the residue X using a conventionally known catalyst (alkali metal hydroxide, etc.) . As a preferred example, there can be mentioned: the PO adduct of neopentylerythritol or the PO/1,2-BO co-adduct (block or random), the PO adduct of dineopentaerythritol or PO/1 ,2-BO co-adduct (block or random), PO adduct of polyglycerol or PO/1,2-BO co-adduct (block or random), PO adduct of sorbitol or PO /1,2-BO co-adducts (block or random), sucrose PO adducts or PO/1,2-BO co-adducts (block or random), etc.

The amount of TPB used in the production of polyfunctional polyoxyalkylene polyol (a1) by ring-opening addition polymerization of PO on the active hydrogen-containing compound (a0) is not particularly limited, based on the polyfunctional polyoxyalkylene polyol The weight of (a1) is preferably 0.00005 to 10% by weight, more preferably 0.0001 to 1% by weight.

The number of moles of PO added is 1 to 200 moles, preferably 2 to 100 moles, and more preferably 3 to 30 moles per active hydrogen atom of the active hydrogen-containing compound (a0) . The number of added moles of all AO per active hydrogen atom of the compound constituting residue X (the total of AO in the first stage and PO in the second stage) is 1 to 200 moles, preferably 3 to 100 Mol. If the number of these added moles exceeds 200 moles, the viscosity of the polyfunctional polyoxyalkylene polyol (a1) will increase, the viscosity of the mixture of the main agent and the hardening agent will increase, and the cutting properties of the hardened material will be increased. Also reduced.

Therefore, q in the general formula (1) is 1 to 200, preferably 2 to 100, and more preferably 3 to 30. In addition, p+q in the general formula (1) is 1 to 200, preferably 3 to 100.

The reaction temperature at the time of ring-opening addition polymerization of PO is preferably 0 to 250°C, and more preferably 20 to 180°C. From the viewpoint of controlling the reaction temperature, the following method is preferable: dropping PO to the mixture of the active hydrogen-containing compound (a0) and TPB, or dropping the mixture of PO and TPB to the active hydrogen-containing compound (a0).

Since the prepared addition polymer contains TPB, it is preferable to use synthetic silicate (magnesium silicate, aluminum silicate, etc.) and activated clay for adsorption removal treatment.

The EO adduct (a12) of polyoxyalkylene polyol (a11) can be obtained by adding EO to polyoxyalkylene polyol (a11) by a common method. Regarding the amount of the oxyethylene group added, based on the total weight of the oxyethylene group contained in the EO adduct (a12), it is 40% by weight or less, preferably 30% by weight or less, and particularly preferably 10% by weight the following.

Regarding the total content of the polyoxyalkylene polyol (a11) and/or EO adduct (a12) in the polyol component (a) of the present invention, based on the weight of the polyol component (a), it is preferably 50 % By weight or more, more preferably 70% by weight or more. If it is less than 50% by weight, it may be difficult to obtain the effects of the present invention.

The polyfunctional polyoxyalkylene polyol (a1) has a hydroxyl value of 10 to 350 mgKOH/g. When the hydroxyl value is less than 10mgKOH/g, the cutting property of the hardened material will become worse. When the hydroxyl value exceeds 350mgKOH/g, the peeling force will increase, and the bonding performance between the adhesive and the substrate will be poor (bubbles occur and the yield will be poor). From the viewpoint of improving the cutting properties of the cured product, the hydroxyl value of the polyfunctional polyoxyalkylene polyol (a1) is preferably 28 mgKOH/g or more, and more preferably 45 mgKOH/g or more. The hydroxyl value can be measured by the method described in JIS K 1557-1.

The polyoxyalkylene polyol (a11) and its EO adduct (a12) can also be used in combination of two or more types. As a combined use aspect, for example, there may be mentioned: bases [compounds with m active hydrogen atoms constituting residue X in the general formula (1)] of different types [for example, polyols (sorbitol, etc.) are used as Those with a matrix and those with polyamines (ethylenetetramine, etc.) as the matrix], the number of functional groups [m in the general formula (1)] [for example, 4 to 5 functional compounds (neopentyl erythritol, etc.) as the matrix Those with 5-10 functional compounds (dineopentylerythritol, sorbitol, sucrose, etc.) as the matrix], hydroxyl value or AO addition molar number [p＋q in general formula (1)] different [hydroxyl value Combination of 300mgKOH/g or more and less than 300mgKOH/g (preferably 30mgKOH/g or more but less than 300mgKOH/g)].

Preferable specific examples of the polyfunctional polyoxyalkylene polyol (a1) constituting the polyol component (a) in the present invention include: PO adducts of neopentylerythritol and PO/1,2- BO co-adduct (block), PO adduct of dineopentaerythritol and PO/1,2-BO co-adduct (block), PO adduct of polyglycerol and PO/1, 2 －BO co-adduct (block), sorbitol PO adduct and PO/1,2-BO co-adduct (block), sucrose PO adduct and PO/1,2-BO co-adduct Adducts (blocks) and so on. Among these, from the viewpoint of "the film strength of the adhesive" and "there is no floating, it can be easily peeled off when peeling off", and more preferably the PO adduct of sorbitol and PO/1,2- The BO co-adduct (block) is particularly preferably a PO50-200 mol adduct of sorbitol.

The polyol component (a) in the present invention may contain other polyols (a2) in addition to the above-mentioned polyfunctional polyoxyalkylene polyol (a1).

As other polyols (a2), those other than polyfunctional polyoxyalkylene polyols (a1) include: polyether alcohols, polyester polyols, polyolefin polyols, polydiene polyols Alcohol (polyalkadiene polyol) and acrylic polyol (acrylic polyol), etc.

Examples of polyether alcohols include polyethylene glycol, polytetramethylene ether glycol, poly-3-methyltetramethylene ether glycol, and copolymerized polyoxyalkylene glycol [without the terminal Hydroxypropyl EO/PO copolymer diol, THF/EO copolymer diol, THF/3-methyltetrahydrofuran copolymer diol, etc. (weight ratio, for example, 1/9-9/1)] and bisphenol It is the AO adduct of a compound that does not have a hydroxypropyl group at the end; it is a polyether alcohol with more than trifunctional and a hydroxyalkyl group other than the hydroxypropyl group at the end, for example, the AO addition of a polyol with more than trivalent [AO adducts of glycerol and AO adducts of trimethylolpropane, etc.]; and one or more of these that have been coupled with dichloromethane, etc.

Examples of polyester polyols include castor oil fatty acid ester polyols (such as castor oil, partially dehydrated castor oil, and castor oil fatty acid esters); From poly(n=2～3 or more) carboxylic acid [aliphatic saturated or unsaturated polycarboxylic acid (carbon number 2～40, such as oxalic acid, adipic acid, azelaic acid, dodecanoic acid, maleic acid) Acid, fumaric acid, itaconic acid and dimerized linoleic acid), polycarboxylic acids containing aromatic rings (carbon number 8-15, such as phthalic acid, isophthalic acid, terephthalic acid and 2,6- Naphthalene dicarboxylic acid) and alicyclic polycarboxylic acid (carbon number 7-15, such as 1,3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid), etc.] and polyol [such as the above Linear or branched polyester polyols formed by hydroxyl-containing compounds, polyfunctional polyoxyalkylene polyols (a1) and other polyols (a2), etc.]; Polylactone polyol [For example, one or a mixture of two or more of the above-mentioned hydroxyl-containing compounds (2-3 valence) is used as a base for catalysts (organometallic compounds, metal chelate compounds, and In the presence of fatty acid metal acyl compounds, etc.), the (substituted) caprolactone (carbon number 6-10, such as ε-caprolactone, α-methyl-ε-caprolactone and ε-methyl-ε- Caprolactone) polyols obtained by addition polymerization to the base (such as polycaprolactone polyols)]; for addition polymerization of AO (EO and PO, etc.) to polyesters with carboxyl and/or hydroxyl groups at the end The obtained polyether ester polyol is neither polyoxyalkylene polyol (a11) nor its EO adduct (a12); Polycarbonate polyol, etc.

Examples of polyolefin polyols include polyisobutylene polyols and the like. Examples of polydiene polyols include polyisoprene polyols, polybutadiene polyols, hydrogenated polyisoprene polyols, hydrogenated polybutadiene polyols, and the like.

Examples of acrylic polyols include: (meth)acrylic acid alkyl (the carbon number of the alkyl group is 1-30) ester [(meth)acrylate etc.] and a hydroxyl-containing acrylic monomer [(meth)acrylic hydroxy Ethyl ester etc.] copolymers and so on. When other polyol (a2) is used, its content is preferably 0.1 to 5% by weight based on the total weight of the polyol component (a).

The hydroxyl equivalent (number average molecular weight per hydroxyl group) of the polyol component (a) in the present invention is preferably 500 or more.

The urethane prepolymer (b) having isocyanate groups in the present invention is a urethane prepolymer having isocyanate groups composed of a polyol component (ap) and a polyisocyanate component (bp).

As said polyol component (ap), polyether alcohol, polyester polyol, polyolefin polyol, polydiene polyol, acrylic polyol, etc. can be used. Among them, from the viewpoint of the strength of the obtained urethane adhesive sheet and the reduction of the peeling force, polyether alcohol, polyester polyol and acrylic polyol are preferred, difunctional polyether alcohol is more preferred, and bifunctional polyol is particularly preferred. Polypropylene glycol and bifunctional polytetramethylene ether glycol or their derivatives (compounds in which the hydrogen atom of the methylene group is substituted with an alkyl group having 1 to 4 carbon atoms, etc.). Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, and the like. In addition, from the viewpoint of improving the cutting properties of the cured product and reducing the peeling force, bifunctional polytetramethylene ether glycol or its derivative is preferred.

The polyisocyanate component (bp) in the present invention includes those having 2 to 3 or more isocyanate groups, for example: chain aliphatic polyisocyanate (bp1) with 4 to 22 carbon atoms, 8 to carbon atoms Alicyclic polyisocyanate of 18 (bp2), aromatic polyisocyanate with carbon number of 8 to 26 (bp3), aromatic aliphatic polyisocyanate with carbon number of 10 to 18 (bp4) and modification products of these polyisocyanates (bp5) Wait. The polyisocyanate component (bp) may be used singly or in combination of two or more.

Examples of chain aliphatic polyisocyanates (bp1) having 4 to 22 carbon atoms include: ethylene diisocyanate, butyl diisocyanate, and hexamethylene diisocyanate (hereinafter, abbreviated as HDI), dodecamethylene diisocyanate (dodecamethylene), 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-Diisocyanatomethylhexanoate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl)carbonate and 2-iso Cyanatoethyl-2,6-diisocyanatohexanoate, etc.

烷二異氰酸酯等。Examples of alicyclic polyisocyanates (bp2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4'-dicyclohexylmethane diisocyanate (hereinafter, abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate and 2,5-or 2,6-down

Alkyl diisocyanate and so on.

Examples of the aromatic polyisocyanate (bp3) having 8 to 26 carbon atoms include: 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate ( Hereinafter, abbreviated as TDI), crude TDI, 4,4'- or 2,4'-diphenylmethane diisocyanate (hereinafter, abbreviated as MDI), crude MDI, polyaryl polyisocyanate, 4,4'-di Isocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl Methyl methane, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate and occasional p-isocyanatophenylsulfonyl isocyanate, etc.

As the araliphatic polyisocyanate (bp4) having 10 to 18 carbon atoms, for example, there may be exemplified: occasional para-diisocyanate and α,α,α',α'-tetramethyl sulfonyl diisocyanate, and the like.

Examples of (bp1) to (bp4) polyisocyanate modified materials (bp5) include: the above-mentioned polyisocyanate modified materials (containing urethane group, carbodiimide group, allophanate group, urea group) , Biuret group, uretdione (uretdione) group, uretonimine (uretonimine) group, isocyanurate (isocyanurate) group or azolidine ketone group modification, etc.; free isocyanate group content is 8 ~ 33 weight %, preferably 10-30% by weight, especially 12-29% by weight), such as modified MDI (amine ester modified MDI, carbodiimide modified MDI, and trihydrocarbylphosphate modified MDI Etc.), modified polyisocyanates such as TDI modified by urethane, HDI modified by biuret, HDI modified by isocyanate and IPDI modified by isocyanate.

Among these polyisocyanate components (bp), from the viewpoint of the strength and adhesion of the obtained urethane adhesive sheet, chain aliphatic polyisocyanate (bp1) with 4 to 22 carbon atoms and 8 to 18 carbon atoms are preferred. The alicyclic polyisocyanate (bp2) is more preferably HDI and IPDI.

The urethane prepolymer (b) is preferably a compound represented by the general formula (6).

In the general formula (6), L is a divalent group obtained by removing isocyanate groups from the polyisocyanate component (bp), U represents a urethane bond, R is each independently a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, b It is an integer of 20 to 70, and the average value of s is 1.01 to 10. The above-mentioned number average value of s is an average value calculated from the number average molecular weight of the compound represented by the general formula (6). Examples of the alkyl group having 1 to 4 carbon atoms include the same ones as the alkyl group having 1 to 4 carbon atoms exemplified as the bifunctional polytetramethylene ether glycol derivative of the polyol component (ap). . In the general formula (6), b is preferably an integer of 25-60. In the general formula (6), the average value of s is preferably 1.01-5. As the urethane prepolymer (b), it is also preferable that the number average molecular weight of the part _{of (CHR-CHR-CHR-CHR-O) b in the above general formula (6) is 1,400-5,100, and more} Preferably, it is a compound of 2,000 to 3,000.

From the viewpoint of the strength and adhesive force of the resulting urethane adhesive sheet, when the polyol component (ap) and the polyisocyanate component (bp) are reacted in the urethane prepolymer having an isocyanate group (b) The ratio of (bp) isocyanate group equivalent to (ap) active hydrogen-containing group equivalent (isocyanate group equivalent/active hydrogen-containing group equivalent) is preferably 1.1-2.0, and more preferably 1.2-1.8, especially It is 1.3 to 1.7. In addition, from the viewpoint of the strength and adhesive force of the resulting urethane adhesive sheet, the weight average molecular weight of the urethane prepolymer (b) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 4,000 to 30,000. The weight average molecular weight of the urethane prepolymer (b) can be measured by the method described later. The urethane prepolymer (b) is preferably bifunctional (that is, the urethane prepolymer (b) is a compound in which 1 mol of isocyanate group has 2 mols). The above-mentioned urethane prepolymer (b) preferably has an isocyanate group content based on the weight of the urethane prepolymer (b) of 0.1 to 12% by weight, and more preferably 0.3 to 1.5% by weight. The above-mentioned isocyanate group content can be measured in accordance with JISK7301-1995, 6.3 isocyanate group content rate.

The urethane prepolymer (b) having isocyanate groups of the present invention can be obtained by reacting the polyol component (ap) with the polyisocyanate component (bp) in a general method. As the method for producing the urethane prepolymer (b) in the present invention, for example, there can be mentioned: in the solvent (toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone, methyl ethyl A method of reacting the polyol component (ap) with the polyisocyanate component (bp) in the presence or absence of ketones, tetrahydrofuran, etc.). This can be done by reducing the ratio of the equivalent of the active hydrogen-containing group of (ap) to the equivalent of the isocyanate of (bp) (preferably the ratio of the equivalent of the isocyanate group of (bp) above to the equivalent of the active hydrogen-containing group of (ap) Adjust the range) to produce a urethane prepolymer (b) with an isocyanate group at the end. In addition, the above reaction can also be carried out in the presence of an antigelling agent (the same compound as the hardening retarder described later can be used).

A known reaction device (a mixing tank equipped with a stirrer, a static mixer, etc.) can be used for the reaction. From the viewpoint of reactivity and suppression of thermal degradation, the reaction temperature is preferably 10 to 160°C, more preferably 25 to 120°C, From the viewpoint of stability, it is preferable to replace the gas phase portion with nitrogen.

The urethane resin (P) having a hydroxyl group, which constitutes the main agent of the 2-component curing urethane adhesive of the present invention, can be prepolymerized with the above-mentioned polyol component (a) and the above-mentioned urethane having an isocyanate group by a general method The substance (b) is obtained by reaction.

From the viewpoint of the strength and adhesion of the resulting urethane adhesive sheet, the urethane prepolymer (b) when the polyol component (a) is reacted with the urethane prepolymer having an isocyanate group (b) The ratio of isocyanate group equivalent to active hydrogen-containing group equivalent of polyol component (a) (isocyanate group equivalent/active hydrogen-containing group equivalent) is 0.05 to 0.7, preferably 0.1 to 0.5, and more preferably 0.15 to 0.4.

The urethane resin (P) preferably contains a compound represented by the following general formula (7).

In the general formula (7), K is a 2-10 valent group obtained by removing two or more OH groups from the compound of the polyol component (a), and U, R, and L are the same as above. In the general formula (7), b is an integer of 20-70, preferably an integer of 25-60. In the general formula (7), the average number of s is 1.01-10, preferably 1.01-5. In the general formula (7), t is an integer of 1 or more, preferably an integer of 1-10. When t is 2 or more, the block bond represented by [K-U-[L-U-(CHR-CHR-CHR-CHR-O) _b －U] _s －L－U] _{t forms a straight chain} shape. In the general formula (7), when K is a trivalent or higher group, the K to which the hydroxyl group at the end of the general formula (7) is bonded may further have the U shown in the general formula (7) One or more amine ester bonds (that is, the above K may have more than two amine ester bonds). In addition, when the above K has one or more amine ester bonds other than U represented by the general formula (7), K may also have [K-U-[L-U-(CHR) through the amine ester bond other than U －CHR－CHR－CHR－O) _b －U] _s －L－U] The block represented by _t. When K has the above-mentioned block through an amine-ester bond other than U, the compound represented by the general formula (7) has a branched structure with a plurality of the above-mentioned blocks starting from K.

Regarding the weight ratio of the compound represented by the general formula (7) contained in the urethane resin (P), from the viewpoint of reducing the peeling force and improving the cutting properties of the cured product, the weight of the urethane resin (P) is preferred. It is 30% by weight or more, more preferably 50% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

Regarding the weight average molecular weight of the urethane resin (P), from the viewpoint of the breaking strength, breaking elongation, cutting properties, and curability of the cured product, it is preferably 10,000 to 500,000, and more preferably 120,000 to 500,000.

The weight average molecular weight of the urethane prepolymer (b) and the urethane resin (P) in the present invention can be measured by gel permeation chromatography, for example, under the following conditions. In addition, when measuring the case of the urethane prepolymer (b), the weight average molecular weight is measured for the reaction of all the isocyanate groups of the urethane prepolymer (b) with methanol. Furthermore, the weight derived from methanol is calculated from the isocyanate group content, and the value obtained by subtracting it from the measured weight average molecular weight is used as the weight average molecular weight of the urethane prepolymer (b). Device: "HLC-8120GPC" [manufactured by Tosoh Corporation] Guard column: "Guardcolumn　HXL-H" [manufactured by Tosoh Corporation] Column: "TSKgel GMHXL" [manufactured by Tosoh Corporation] Sample solution: 0.125 wt% dimethylformamide (containing LiBr 0.01M) solution Solution injection volume: 100μl Flow rate: 1ml/min Measuring temperature: 40℃ Detection device: refractive index detector Reference material: standard polystyrene

As the method for producing the urethane resin (P) having a hydroxyl group in the present invention, known methods for producing urethane resins can be used, for example: solvents (toluene, xylene, ethyl acetate, butyl acetate, two In the presence or absence of methylformamide, acetone, methyl ethyl ketone, tetrahydrofuran, etc.), a method of reacting the polyol component (a) with the urethane prepolymer (b) having an isocyanate group. The ratio of the active hydrogen-containing group equivalent of the polyol component (a) to the isocyanate equivalent of the urethane prepolymer (b) can be increased (preferably the ratio of the isocyanate equivalent of the urethane prepolymer (b) above Adjust the ratio range of the active hydrogen-containing group equivalent of the polyol component (a)) to produce a urethane resin (P) having a hydroxyl group at the end. In addition, the above reaction can also be carried out in the presence of an antigelling agent (the same compound as the hardening retarder described later can be used). By using an anti-gelling agent, high molecular weight can be achieved without gelling the urethane resin (P), so cutting performance or breaking elongation can be improved.

A known reaction device (a mixing tank equipped with a stirrer, a static mixer, etc.) can be used for the reaction. From the viewpoint of reactivity and suppression of thermal degradation, the reaction temperature is preferably 10 to 160°C, more preferably 25 to 120°C, From the viewpoint of stability, it is preferable to replace the gas phase portion with nitrogen.

The two-component curable urethane adhesive of the present invention contains a main agent and a hardener, the main agent contains the above-mentioned urethane resin (P), and the hardener contains a crosslinking agent (D) having an isocyanate group.

As a crosslinking agent (D) which has an isocyanate group, the polyisocyanate etc. exemplified as a polyisocyanate component (bp) are mentioned.

From the viewpoint of curability, the average number of functional groups of the crosslinking agent (D) is preferably 2-6 or more, more preferably 2-5, and particularly preferably 3-4.

When manufacturing the 2-component curing type urethane adhesive, the hardened product of the 2-component curing type urethane adhesive and the adhesive sheet using the 2-component curing type urethane adhesive of the present invention, the degree of application and curing requirements can be determined , Use amine esterification catalyst.

Examples of the amine esterification catalyst include metal catalysts and amine catalysts. Examples of metal catalysts include tin-based catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate ( stannous octoate) and dibutyl tin maleate, etc.); lead-based catalysts (lead oleate, lead 2-ethylhexanoate, lead naphthenate and lead octenate, etc.); bismuth-based catalysts (bismuth carboxylate, Bismuth alkoxides and compounds with dicarbonyl groups and bismuth chelating compounds, etc.); titanium-based catalysts (isopropoxytriN-ethylamine ethylamine (aminato) titanium, tetrabutyl titanate and tetraiso Propoxy dioctyl titanium phosphite, etc.); zinc-based catalysts (organic zinc complexes, etc.); zirconium-based catalysts (tetraacetyl zirconium pyruvate and tributoxy acetyl zirconium pyruvate, etc.) ; Aluminum-based catalysts (aluminum complexes, etc.); iron-based catalysts [iron carboxylate compounds (iron lactate and iron ricinoleate, etc.), ferrocene compounds (ferrocene and acetylene Iron, etc.) and iron phthalocyanine, etc.] and other metal catalysts (metal naphthenates such as cobalt naphthenate and phenylmercuric propionate, etc.).

基（aziridinyl））乙胺、4－（1－哌啶基）－2－己胺等]以及N－甲基及N－乙基嗎福林等。Examples of amine catalysts include: triethylenediamine, tetramethylethylenediamine, diazedbicycloalkene [1,8-diazedbicyclo[5.4.0]undecene-7[DBU (San-Apro Co., Ltd.) Co., Ltd., registered trademark)], etc.], dialkyl (carbon number 1 to 3) amine alkyl (carbon number 2 to 4) amine (dimethylaminoethylamine, dimethylaminopropylamine, two Ethylaminopropylamine and dipropylaminopropylamine, etc.), heterocyclic amine alkyl (carbon number 2-6) amine [2-(1- acridine)

(Aziridinyl) ethylamine, 4-(1-piperidinyl)-2-hexylamine, etc.] and N-methyl and N-ethyl mopholin.

Among these, the preferred ones are diazebicyclic olefins, bismuth-based catalysts, tin-based catalysts and zinc-based catalysts, and particularly preferred ones are DBU, bismuth carboxylate, dibutyltin dilaurate and organozinc complex Things.

Although the amount of amine esterification catalyst varies depending on the application, when high fast curing properties are required, based on the weight of the two-part hardening urethane adhesive, it is preferably 3,000 ppm or less, and more preferably It is 1 to 2,000 ppm, particularly preferably 10 to 1,000 ppm. The amine esterification catalyst may be used alone or in combination of two or more.

The 2-component curable urethane adhesive of the present invention may further contain solvents, antioxidants, curing retarders, ultraviolet absorbers, and plastics as exemplified in the production method of the above-mentioned urethane resin (P) within a range that does not hinder the effects of the present invention. Additives such as chemical agents, tackifiers, fillers and pigments. The additive may be added to either the main agent or the hardening agent, and may be added when the main agent and the hardening agent are blended, but it is preferably added to the main agent in advance.

Examples of antioxidants include: hindered phenol compounds [triethylene glycol-bis[3-(3-tertiarybutyl-5-methyl-4-hydroxyphenyl) propionate], new Pentaerythrityl (pentaerythrityl)-four [3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate] and 2,2-thio-diethylene bis [3-(3,5-Di-tertiary butyl-4-hydroxyphenyl) propionate] etc.] and phosphite compounds [see (2,4-Di-tertiary butylphenyl) phosphorous acid Esters, 2,2-methylene bis(4,6-di-tertiary butylphenyl) octyl phosphite, bis(2,6-di-tertiary butylphenyl) neopentaerythritol- Di-phosphite and Si (2,4-di-tertiary butyl phenyl) 4,4'-biphenylene-di-phosphonite (phosphonite) etc.] etc. These antioxidants may be used singly, or two or more of them may be used in combination. From the viewpoint of anti-oxidation effect and adhesion, the amount of antioxidant is based on the weight of the two-part hardening urethane adhesive, preferably 5% by weight or less, and more preferably 0.05 to 1% by weight.

Examples of hardening retarders include 2,4-pentanedione (acetyl acetone), 3-methyl-2,4-pentanedione, 2,4-hexanedione, 2,2- Dimethyl-3,5-Hexanedione, 2,4-Heptanedione, 3,5-Heptanedione, 2,2,6,6-Tetramethyl-3,5-Heptanedione , 2,4-octanedione, 2,2,7-trimethyl-3,5-octanedione, 2,4-nonanedione, 3-methyl-2,4-nonanedione, 2- Methyl-4,6-nonanedione, 1-phenyl-1,3-butanedione (benzyl acetone), dibenzoyl methane and 2-furyl benzoyl Β-diketones such as acetylmethane; methyl acetylacetate, ethyl acetylacetate, propyl acetylacetate, butyl acetylacetate, methyl propylacetate, ethyl propylacetate, propylacetate, Isopropyl acrylate, butyl acrylate, methyl butyl acetate, ethyl butyl acetate, propyl butyl acetate, methyl hexyl acetate, ethyl hexyl acetate, propyl hexyl acetate and hexyl acetate Β-ketoesters such as butyl acetate; dimethyl malonate, diethyl malonate, ethyl methyl malonate, diisopropyl malonate and dibutyl malonate, etc. Alkyl esters; N,N-dimethyl acetamide and N-ethyl acetamide and other acetamide. These hardening retarders may be used singly, or two or more of them may be used in combination. From the viewpoint of the curing delay effect and the adhesive force, the amount of the curing delay agent is based on the weight of the two-component curing urethane adhesive, and is preferably 5% by weight or less, and more preferably 0.01 to 3% by weight.

Examples of ultraviolet absorbers include salicylic acid derivatives (salic acid-p-octyl phenyl ester, salicylic acid-p-tertiary butyl phenyl ester, etc.), and diphenyl ketone compounds [2,4- Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4 '-Dimethoxybenzophenone, 2,2'-Dihydroxy-4,4'-Dimethoxy-5-sulfonic acid benzophenone, 2-hydroxy-4-methoxy-2 '-Carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone trihydrate, 2-hydroxy-4-n-octoxy (n-octoxy) benzophenone , 2-Hydroxy-4-octadecyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-(2-hydroxy-3-methacryloxy group) propoxy benzophenone and bis(2-methoxy-4-hydroxy-5-benzylbenzene) Group) methane, etc.], benzotriazole compound {2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di- Tertiary butyl-phenyl) benzotriazole, 2-(2'-hydroxy-3'-tertiary butyl-5'-methyl-phenyl)-5-chlorobenzotriazole, 2-( 2'-hydroxy-3',5'-di-tertiary butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-4'-n-octyloxyphenyl)benzo Triazole, 2-(2'-hydroxy-5'-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary pentylphenyl)benzene Triazole, 2-[2'-hydroxy-3'-(3”,4”,5”,6”-tetrahydrophthaliminomethyl)-5'-methylphenyl]benzotriazole And 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol] etc.}; cyanoacrylate Compounds (2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, etc.) and the like. The ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of ultraviolet absorbing effect and adhesion, the amount of ultraviolet absorber is based on the weight of the two-part hardening urethane adhesive, and is preferably 5% by weight or less, and more preferably 0.1 to 1% by weight.

Examples of plasticizers include hydrocarbons [process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, chlorinated paraffin, paraffin, ethylene and α -Copolymerization of olefin (carbon number 3-20) (weight ratio 0.1/99.9-99.9/0.1) oligomer (weight average molecular weight 5,000-100,000) and copolymerization of propylene and α-olefin (carbon number 4-20) (weight Ratio 0.1/99.9～99.9/0.1) oligomer (weight average molecular weight 5,000～100,000)]; chlorinated paraffin; ester [phthalate [diethyl phthalate (DEP), dibutyl phthalate (DBP), Di-2-ethylhexyl phthalate (DOP), didecyl phthalate, dilauryl phthalate, di(octadecyl) phthalate and diisononyl phthalate, etc.], adipate[ Di(2-ethylhexyl) adipate (DOA) and dioctyl adipate, etc.] and sebacate (dioctyl sebacate, etc.), fatty acid esters (butane octadecanoate, etc.) Ester, 2-ethylhexyl hexadecanoate, 2-ethylhexyl octadecanoate, monoglyceryl behenate, cetyl 2-ethylhexanoate, isopropyl hexadecanoate, isooctadecanoate Cholesteryl acid, coconut oil methyl ester, methyl laurate, methyl oleate, methyl octadecanoate, isopropyl myristate, octyl dodecyl myristate, myristyl myristate, ten Stearyl octadecanoate, 2-ethylhexyl octadecanoate, isotridecyl octadecanoate, triglyceride 2-ethylhexanoate, butyl laurate and octyl oleate, etc.), poly(methyl) ) Acrylic esters (polybutyl acrylate, 2-ethylhexyl acrylate, etc.)]; animal and vegetable fats and oils (linoleic acid and hypolinoleic acid, etc.); and those with hydrogenated unsaturated double bonds among these Hydride and so on. A plasticizer may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of the cohesive force of the adhesive, the amount of the plasticizer is based on the weight of the two-part hardening urethane adhesive, preferably 100% by weight or less, more preferably 1-50% by weight, and particularly preferably 3-40% by weight %, particularly preferably 5 to 35% by weight, most preferably 10 to 30% by weight.

The weight average molecular weight of the plasticizer can be measured by gel permeation chromatography, for example, under the following conditions. Device: "HLC-8120GPC" [manufactured by Tosoh Corporation] Column: "Guardcolumn HXL-H" (1 piece), "TSKgel GMHXL" (2 pieces) [all manufactured by Tosoh Corporation] Sample solution: 0.25% by weight tetrahydrofuran solution Solution injection volume: 100μl Flow rate: 1ml/min Measuring temperature: 40℃ Detection device: refractive index detector Reference material: standard polystyrene

As the tackifier, for example, terpene resin, terpene phenol resin, phenol resin, aromatic hydrocarbon modified terpene resin, rosin resin, modified rosin resin, synthetic petroleum resin (aliphatic, aromatic or alicyclic Formula synthetic petroleum resins, etc.), lavender-indene resins, xylene resins, styrene resins, fencyclopentadiene resins, and hydrogenated products of those having unsaturated double bonds that can be hydrogenated. One type of tackifier may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of adhesion, those having polarity are preferred, rosin resin, phenol resin, terpene phenol resin, xylene resin, and hydrogenated products thereof are more preferred, and terpene phenol resin is particularly preferred. And its hydride. From the viewpoint of adhesion and heat resistance, the amount of tackifier is based on the weight of the two-part hardening urethane adhesive, preferably 100% by weight or less, more preferably 1-50% by weight, and particularly preferably 3-40 The weight% is particularly preferably 5 to 35% by weight, and most preferably 10 to 30% by weight.

Examples of fillers include carbonates (magnesium carbonate and calcium carbonate, etc.), sulfates (aluminum sulfate, calcium sulfate, barium sulfate, etc.), sulfites (calcium sulfite, etc.), molybdenum disulfide, silicate ( Aluminum silicate and calcium silicate, etc.), diatomaceous earth, silica powder, talc, silica and zeolite. The filler is preferably fine particles with a volume average particle diameter of about 0.01 to 5 μm, and may be used singly or in combination of two or more. From the viewpoint of the cohesive force of the adhesive, the amount of the filler is based on the weight of the two-part hardening urethane adhesive, preferably 250% by weight or less, and more preferably 0.5-100% 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, lead monoxide, lithopone, barite, cadmium red, cadmium mercury red, hematite oxide, molybdenum red, red lead, chrome yellow, cadmium yellow, barium yellow, strontium yellow, titan yellow , Titanium black, chrome oxide green, cobalt oxide, cobalt green, cobalt/chrome green, ultramarine blue, iron blue, cobalt blue, cerulean blue, manganese violet and cobalt violet, etc.) and organic pigments (shellac, insoluble azo Pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue and dyeing lakes, etc.). The above-mentioned pigments are preferably fine particles having a volume average particle diameter of about 0.01 to 5 μm, and they may be used singly or in combination of two or more. From the viewpoint of the cohesive force of the adhesive, the amount of the pigment is based on the weight of the two-component hardening urethane adhesive, preferably 250% by weight or less, and more preferably 0.1-50% by weight.

The NCO/OH ratio (isocyanate equivalent to hydroxyl equivalent) when mixing the main agent and the hardener is preferably 0.3 to 2.0, and more preferably 0.5 to the viewpoint of the film strength and adhesion of the adhesive sheet obtained. 1.5, particularly preferably 0.7 to 1.3.

The use of the two-component curable urethane adhesive of the present invention is not particularly limited. For example, the main agent and the curing agent can be mixed, and then coated on a base film such as a polyester film and a polyolefin film, and cured to obtain an adhesive sheet , And then bonded to optical components, used in surface protection films, etc. A cured product obtained by curing the 2-component curing type urethane adhesive of the present invention and a urethane adhesive sheet using the 2-component curing type urethane adhesive of the present invention are also included in the present invention.

As an optical component using 2-component hardening urethane adhesive and urethane adhesive sheet, examples include: polarizing plates, phase difference plates, and light diffusion plates used in liquid crystal displays, organic EL displays, plasma displays, field emission displays, etc. , Anti-reflection film, electromagnetic wave shielding film and glass substrate, etc.

As a specific example of the method of forming a urethane adhesive sheet, the following methods etc. are mentioned. For coating the substrate film with a 2-component curing urethane adhesive, you can use a gravure coater, reverse roll coater, comma coater, spin coater, Curtain coater, slot coater, bar coater, die coater, knife coater, etc. The coating amount (solid content) of the adhesive during coating is preferably 0.5 to 300 g/m ² , more preferably 1 to 200 g/m ² , and particularly preferably 10 to 100 g/m ² .

The coating temperature of the adhesive when applied to the substrate film is preferably 10 to 160°C, and more preferably 25 to 130°C, from the viewpoint of coatability and suppression of thermal degradation. The viscosity of the adhesive at the coating temperature From the viewpoints of formability (it is possible to coat thickly, without warpage and sink marks after curing) and coatability, it is preferably 0.01 to 100 Pa·s, and more preferably 0.02 to 50 Pa·s, particularly preferred It is 0.03～10Pa·s. The viscosity of the present invention can be measured by a B-type rotary viscometer. For lamination, a generally used dry lamination machine or extrusion lamination machine can be used. After lamination, the adhesive is cured completely by curing at 10-50°C for 20-150 hours.

The concentration of the urethane group of the cured product and the urethane adhesive sheet of the two-component curing urethane adhesive of the present invention is based on the urethane resin (P) with hydroxyl in the main agent from the viewpoint of adhesion to the substrate The total weight with the crosslinking agent (D) in the hardener is preferably 3 to 25% by weight. [Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples.

[Production of polyoxyalkylene polyol] ＜Manufacturing example 1＞ A stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line, and an exhaust line is filled with 100 parts by weight of sorbitol and 4.0 parts by weight of potassium hydroxide, and then the raw materials are supplied The pipeline continuously injected 3,200 parts by weight of PO into the liquid phase for 12 hours, and at the same time controlled the reaction temperature to maintain 90-100°C. After aging at 100°C for 3 hours, 30 parts by weight of synthetic silicate {"Kyoward 600" made by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water were added, and the mixture was treated at 60°C for 3 hours. It was taken out from the autoclave, filtered with a filter with a pore size of 1 micron, and dehydrated to obtain polyoxyalkylene polyol (a11-1). (A11-1) The hydroxyl value is 66mgKOH/g, the viscosity is 700mPa·s/25℃, and the first-order rate is 2%. In addition, in the general formula (1) of (a11-1), p is 0 and q is approximately 14.

＜Manufacturing example 2＞ A stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line, and an exhaust line is charged with 1,000 parts by weight of polyoxyalkylene polyol (a11-1) and TPB. After .09 parts by weight, stirring was started, and the pressure in the autoclave and coagulation equipment was reduced to 0.005 MPa. 50 parts by weight of PO was continuously poured into the liquid phase through the raw material supply line for 12 hours, and at the same time, the reaction temperature was controlled to be maintained at 70-80°C. In order to condense and recover PO in the condensing equipment, the -30℃ refrigerant is circulated. Then, after aging at 70°C for 4 hours, 200 parts by weight of water was added and heated at 130-140°C for 1 hour. After heating for 1 hour, the water was distilled off under normal pressure for 2 hours, and then steam was introduced while maintaining the pressure at 0.04～0.07MPa, and the remaining water and by-product low boiling point compounds were decompressed for 3 hours Distilled to remove. Then add 30 parts by weight of synthetic silicate {Kyoward600 made by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water, stir at 60°C for 3 hours, remove from the autoclave, and filter with a filter with a pore size of 1 micron After that, dehydration is performed to obtain polyoxyalkylene polyol (a11-2). (A11-2) The hydroxyl value is 65mgKOH/g, the viscosity is 800mPa·s/25℃, and the first order rate is 40%. In addition, in the general formula (1) of (a11-2), p is 0 and q is approximately 14.

＜Manufacturing example 3＞ The polyoxyalkylene polyol (a11-3) was obtained in the same manner as in Production Example 2 except that the input amount of PO in Production Example 2 was changed to 180 parts by weight. (A11-3) The hydroxyl value is 62mgKOH/g, the viscosity is 980mPa·s/25℃, and the first-order rate is 60%. In addition, in the general formula (1) of (a11-3), p is 0 and q is approximately 15.

＜Manufacturing example 4＞ A stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensing device, a raw material supply line, and an exhaust line is filled with 100 parts by weight of neopentylerythritol and 0.09 parts by weight of TPB, and then the stirring is started , The pressure in the autoclave and coagulation equipment is reduced to 0.005MPa. 2248 parts by weight of PO was continuously poured into the liquid phase through the raw material supply line for 12 hours, while controlling the reaction temperature to be maintained at 70-80°C. In order to condense and recover PO in the condensing equipment, the -30℃ refrigerant is circulated. Then, after aging at 70°C for 4 hours, 200 parts by weight of water was added and heated at 130-140°C for 1 hour. After heating for 1 hour, the water was distilled off under normal pressure for 2 hours, then steam was introduced while maintaining the pressure at 0.04～0.07MPa, and the remaining water and by-product low boiling point compounds were distilled under reduced pressure for 3 hours Remove. Then add 30 parts by weight of synthetic silicate {Kyoward600 made by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water, stir at 60°C for 3 hours, remove from the autoclave, and filter with a filter with a pore size of 1 micron After that, dehydration is performed to obtain polyoxyalkylene polyol (a11-4). (A11-4) The hydroxyl value is 43mgKOH/g, the viscosity is 940mPa·s/25℃, and the first-order rate is 70%. In addition, in the general formula (1) of (a11-4), p is 0 and q is approximately 25.

＜Manufacturing example 5＞ Using sorbitol as a base agent and reacting PO in the presence of a KOH catalyst, polyoxypropylene glycol (first-order ratio 2%, hydroxyl value 490mgKOH/g) was prepared, and 100 parts by weight of the Polyoxypropylene glycol is placed in a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line, and an exhaust line. After loading 0.09 parts by weight of TPB, the stirring is started, and the autoclave The pressure inside the condensing equipment is reduced to 0.005MPa. 365 parts by weight of PO was continuously poured into the liquid phase through the raw material supply line for 12 hours, and at the same time, the reaction temperature was controlled to be maintained at 70-80°C. In order to condense and recover PO in the condensing equipment, the -30℃ refrigerant is circulated. Then, after aging at 70°C for 4 hours, 200 parts by weight of water was added and heated at 130-140°C for 1 hour. After heating for 1 hour, the water was distilled off under normal pressure for 2 hours, then steam was introduced while maintaining the pressure at 0.04～0.07MPa, and the remaining water and by-product low boiling point compounds were distilled under reduced pressure for 3 hours Remove. Then add 30 parts by weight of synthetic silicate {Kyoward600 made by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water, stir at 60°C for 3 hours, remove from the autoclave, and filter with a filter with a pore size of 1 micron After that, dehydration is performed to obtain polyoxyalkylene polyol (a11-5). (A11-5) The hydroxyl value is 105mgKOH/g, the viscosity is 690mPa·s/25℃, and the first-order rate is 66%. In addition, in the general formula (1) of (a11-5), p is 0 and q is approximately 8.

＜Manufacturing Example 6＞ Using sucrose as a base, PO was reacted in the presence of KOH catalyst to prepare polyoxypropylene glycol (first order rate 2%, hydroxyl value 35mgKOH/g, p in general formula (1) is 0, q About 27.), the 100 parts by weight of the polyoxypropylene glycol is placed in a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation device, a raw material supply line, and an exhaust line, and hydrogen is charged After 4.0 parts by weight of potassium oxide, 25 parts by weight of EO was continuously poured into the liquid phase through the raw material supply line for 12 hours, and at the same time, the reaction temperature was controlled to maintain 90-100°C. After aging at 100°C for 3 hours, 30 parts by weight of synthetic silicate {"Kyoward 600" made by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water were added, and the mixture was treated at 60°C for 3 hours. It was taken out from the autoclave, filtered with a filter with a pore size of 1 micron, and dehydrated to obtain the polyoxyalkylene polyol ethylene oxide adduct (a12-1). The hydroxyl value of (a12-1) is 28mgKOH/g, the viscosity is 1,660mPa·s/25℃, and the a in general formula (2) or (3) is about 9.

[Synthesis of urethane prepolymer with isocyanate group] ＜Synthesis example 1＞ Put PTMG3000{2-functional polytetramethylene ether glycol into a 4-necked flask equipped with reflux cooling tube, stirring rod and thermometer, hydroxyl value 39mgKOH/g, b value in general formula (6) is about 40, Mitsubishi Chemical Co., Ltd. {100 parts by weight, HDI (hexamethylene diisocyanate) 9.6 parts by weight, 47 parts by weight of ethyl acetate as a solvent, Neostann U-600 as an amine esterification catalyst {Nitto Chemical Co., Ltd. Prepare 0.03 parts by weight and 0.05 parts by weight of diethyl malonate as an antigelling agent, and react at 78°C for 6 hours to obtain a solution of urethane prepolymer (b-1) with isocyanate groups. (B-1) The isocyanate group content of the solution is 1.1%, the concentration is 70% by weight, and the viscosity is 30,000mPa·s/25°C.

＜Synthesis example 2～8＞ Except for changing the charging amount to the value described in Table 1, in the same manner as in Synthesis Example 1, solutions of urethane prepolymers (b-2) to (b-8) having isocyanate groups were obtained. Table 1 shows the isocyanate group content, concentration and viscosity of the solutions of (b-2) to (b-8). In addition, "PTG-L2000" in Table 1 represents a bifunctional polytetramethylene ether glycol derivative {hydroxy value 56mgKOH/g, manufactured by Hodogaya Chemical Industry Co., Ltd., random copolymerization of tetrahydrofuran and 3-methyltetrahydrofuran物}, "IPDI" stands for isophorone diisocyanate.

[Table 1] Synthesis example 1 2 3 4 5 6 7 8 Urethane prepolymer with isocyanate group (b) (B-1) (B-2) (B-3) (B-4) (B-5) (B-6) (B-7) (B-8) Polyol component (ap) PTMG3000 100 100 100 100 - 100 100 - PTG-L2000 - - - - 100 - - 100 Polyisocyanate component (bp) HDI (type quantity = 168.2) 9.6 - - - 12.6 - - - IPDI (type quantity = 222.3) - 12.7 10.8 10.0 - 9.2 15.6 17.6 Solvent Ethyl acetate 47 48 110 110 48 164 77 78 Amine esterification catalyst Neostann U-600 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Antigelling agent Diethyl malonate 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 The value of s in the general formula (6) 1.67 1.67 2.86 4.00 2.50 6.67 1.02 1.54 Isocyanate group content of urethane prepolymer solution (%) 1.1 1.1 0.46 0.33 1.1 0.16 1.5 1.5 Concentration of urethane prepolymer solution (wt%) 70 70 50 50 70 40 60 60 Viscosity of urethane prepolymer solution (mPa·s/25℃) 30,000 22,000 9,200 33,000 16,000 11,000 8,600 6,600

[Synthesis of urethane resin with hydroxyl group] ＜Synthesis example 9＞ Put 15 parts by weight of polyoxyalkylene polyol (a11-1) and urethane prepolymer (b-1) with isocyanate group into a 4-necked flask equipped with reflux cooling tube, stir bar and thermometer. 16 Parts by weight and 34.5 parts by weight of ethyl acetate as a solvent were reacted at 78°C for 10 hours to obtain a solution of a urethane resin (P-1) having a hydroxyl group. The solution of (P-1) has a hydroxyl value of 11.2mgKOH/g, a concentration of 40% by weight, a viscosity of 6,200mPa·s/25°C, and a weight average molecular weight of 131,000.

<Synthesis examples 10-24, comparative synthesis examples 1-2> Except that the loading amount was changed to the value described in Table 2, the rest was the same as in Synthesis Example 9 to obtain urethane resins having hydroxyl groups (P-2) to (P-16), (P'-1) to (P'-2) solution. Table 2 shows the hydroxyl value, concentration, viscosity, and weight average molecular weight of the solutions of (P-2)～(P-16) and (P’-1)～(P’-2). In addition, (a2-1) in Table 2 represents SANNIX GH-5000{3-functional polypropylene glycol, with a hydroxyl value of 33mgKOH/g, manufactured by Sanyo Chemical Co., Ltd.}, (a2-2) represents SANNIX SP-750{6-functional Polypropylene glycol, hydroxyl value 490mgKOH/g, manufactured by Sanyo Chemical Industry Co., Ltd.}.

[Table 2] Synthesis example Comparative synthesis example 9 10 11 12 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four 1 2 Urethane resin with hydroxyl group (P) (P-1) (P-2) (P-3) (P-4) (P-5) (P-6) (P-7) (P-8) (P-9) (P-10) (P-11) (P-12) (P-13) (P-14) (P-15) (P-16) (P'-1) (P'-2) Polyol component (a) (a11-1) 15 15 - - - - 15 - - - 25 - - - - - - - (a11-2) - - 15 - - - - - - - - - - - - - - - (a11-3) - - - 15 10 8 - 10 16 32 - - - - 15 16 - - (a11-4) - - - - - - - - - - - - - 15 - - - - (a11-5) - - - - - - - - - - - - 15 - - - - - (a12-1) - - - - - - - - - - - 25 - - - - - - (a2-1) - - - - - - - - - - - - - - - - 15 - (a2-2) - - - - - - - - - - - - - - - - - 10 Solution of urethane prepolymer (b) with isocyanate group (b-1) solution 16 - - - - - - - - - - - 26 - - - 17 65 (b-2) solution - 17 17 16 - - - - - - - - - 13 - - - - (b-3) solution - - - - 25 - - - - - - - - - - - - - (b-4) solution - - - - - 38 - - - - - - - - - - - - (b-5) solution - - - - - - 17 - - - - - - 16 - - - (b-6) solution - - - - - - - 58 - - - - - - - - - - (b-7) solution - - - - - - - - 15 29 twenty four 7.1 - - - - - - (b-8) solution - - - - - - - - - - - - - - - 14 - - Solvent Ethyl acetate 34.5 34.9 35.0 34.2 21.1 18.9 34.6 15.0 31.4 21.4 16.7 41.0 41.8 31.8 33.9 31.2 35.5 15.0 The total number of groups represented by general formula (2) relative to the total number of groups represented by general formula (2) and the number of groups represented by general formula (3) possessed by polyol (a1) The proportion of the number (%) 2 2 40 60 60 60 2 60 60 60 2 2 66 70 60 60 2 2 Hydroxyl value of urethane resin solution (mgKOH/g) 11.2 11.1 11.2 10.7 8.3 6.8 11.2 6.0 11.1 18.0 18.3 7.7 17.8 6.8 10.5 11.5 3.8 1.6 Concentration of urethane resin solution (wt%) 40 40 40 40 40 40 40 40 40 60 60 40 40 40 40 40 40 40 Viscosity of urethane resin solution (mPa·s/25℃) 6,200 5,000 5,700 37,000 45,000 55,000 8,900 13,000 20,000 21,000 37,000 45,000 11,000 5,400 9,800 15,000 5,500 14,700 Weight average molecular weight of urethane resin (P) 131,000 64,500 64,700 110,000 93,900 106,000 116,000 175,000 304,000 124,000 144,000 442,000 132,000 88,300 122,000 236,000 135,000 49,600

<Examples 1 to 16 and Comparative Examples 1 to 2> Mix the solution of urethane resin (P-1)～(P-16) or the solution of (P'-1)～(P'-2) with hydroxyl as the main agent in the parts by weight listed in Table 3 , Desmodur XP2675 (D-1) {HDI trimeric isocyanate, manufactured by Covestro Corporation} or Duranate TFD-90B (D-2) {HDI trimeric isocyanate, manufactured by Asahi Kasei Co., Ltd.} as a hardener, ethyl acetate as a solvent Ester and dibutyl tin dilaurate or Borchi Kat22 {manufactured by Borchers Corporation} as a catalyst for amine esterification are centrifuged to defoam to obtain an adhesive solution. Use a bar coater to coat a 38μm thick polyethylene terephthalate film so that the film thickness after drying and curing is 30μm. After drying it at 130°C for 3 minutes, a release film was attached and cured at 50°C for 2 days to obtain an adhesive sheet. Using the obtained adhesive sheet, the initial adhesive strength, the adhesive strength after the heat resistance test, the cutting property, and the adhesion to the substrate were evaluated by the following evaluation methods. The results are shown in Table 3. Also, using a cured adhesive obtained by changing the polyethylene terephthalate film to a 100μm OPP (stretched polypropylene) film and changing the film thickness after drying and curing to 100μm, the breaking strength was evaluated by the following method , Elongation at break, yield and gel fraction. The results are shown in Table 3.

(1) Measuring method of initial adhesion The adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 to 2 were each cut into a size of 100mm×25mm, and the peeling film was peeled off and attached to a glass plate. Using a tensile testing machine, it was pulled at 23°C. The 180° peel strength (unit: N/25mm) was measured at an extension speed of 300mm/min as the initial adhesion. The measurement system was performed on 5 samples, and the average value is shown in Table 3. When used in the case of a surface protection sheet, the peel strength is preferably in the range of 0.01-0.03N/25mm from the viewpoint that it does not peel off and can be easily peeled off.

(2) Measuring method of adhesion after heat resistance test The adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 to 2 were each cut into a size of 100mm×25mm, the peeling film was peeled off and attached to a glass plate, and then placed in a thermostat at 85°C for 7 days . Then, after 4 hours of temperature adjustment in a temperature-controlled room at 50%RH and 23°C, use a tensile testing machine to measure the 180° peel strength at 23°C at a tensile speed of 300mm/min (unit: N/25mm) Used as adhesion after heat resistance test. The measurement system was performed on 5 samples, and the average value is shown in Table 3. The peel strength after the heat resistance test is preferably in the range of 0.01 to 0.05 N/25 mm, and more preferably in the range of 0.01 to 0.04 N/25 mm. In addition, the peel strength after the heat resistance test is preferably 0.025N/25mm or less compared to the change in the initial adhesion.

(3) Measuring method of cutting property The peeling film was peeled off from the adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 to 2, and the blade of the cutter was pressed against the adhesive surface to quickly cut out the notches. The cut surface after cutting was visually observed through a magnifying glass, and the cutting property was evaluated based on the following criteria. The results are shown in Table 3. Since the chips during processing will contaminate the adherend and reduce the performance, it is preferable not to generate chips. <Evaluation criteria> ◎ ：The cut surface is smooth and no chips are generated. ○: Although the cut surface is not smooth, no chips are generated. △: The cut surface is not smooth, and chips are generated. ×: The cut surface is not smooth, and chips are scattered around.

(4) Evaluation method of substrate adhesion Peel off the release film from the adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 to 2, and rub each adhesive surface ten times with nails, and visually confirm whether the surface of the adhesive layer is from the polyterephthalic acid of the base material. The peeling of the ethylene glycol film was evaluated based on the following criteria. The results are shown in Table 3. <Evaluation criteria> ◎ ：No whitening or peeling. ○: Although it has not peeled off, it is whitish. △: If rubbed 6-10 times, it will peel off. ×: Rub it 1 to 5 times and it will peel off.

(5) Measuring method of breaking strength and breaking elongation Peel off the release film and OPP film from the cured adhesives obtained in Examples 1 to 16 and Comparative Examples 1 to 2, and make a dumbbell-shaped No. 3 test piece. Use a tensile testing machine at 23°C, 50%RH Measure the breaking strength and breaking elongation of the test piece under the condition of a tensile speed of 100mm/min. The measurement system was performed on 5 test pieces, the average value was calculated, and the breaking strength and breaking elongation were evaluated based on the following criteria. The results are shown in Table 3. <Evaluation criteria for breaking strength> ◎ ：Above 2.0MPa. ○: Above 1.0MPa but less than 2.0MPa. △: Above 0.5MPa but less than 1.0MPa. ×: Less than 0.5MPa. <Evaluation criteria for elongation at break> ◎ ：Above 100%. ○: Above 75%, but less than 100%. △: Above 50%, but less than 75%. ×: Less than 50%.

(6) Evaluation method of yield The adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 to 2 were each cut into a size of 100 mm × 25 mm, and a test piece was prepared. After peeling off the peeling film, one end of the test piece 5 mm × 25 mm was bonded to the glass The board should be fixed so that it does not peel off. Next, the portion of 95 mm×25 mm that was not bonded to the glass plate was vertically suspended from the glass plate on the short side of the test piece. Next, the suspended test piece was released, and the time until the entire test piece was in close contact with the surface of the glass plate was measured. The measurement system was performed on 5 test pieces, the average value was calculated, and the yield was evaluated based on the following criteria. The results are shown in Table 3. The shorter the time to close adhesion, the more difficult it is for air bubbles to be mixed during bonding, and the better the yield. <Evaluation criteria> ◎: Less than 2.0 seconds. ○: More than 2.0 seconds but less than 4.0 seconds. △: More than 4.0 seconds, but less than 8.0 seconds. ×: More than 8.0 seconds.

(7) Evaluation method of gel fraction The cured adhesives obtained in Examples 1 to 16 and Comparative Examples 1 to 2 were cut into a size of about 70 mm × about 70 mm, and after peeling off the release film and OPP film, they were folded in 4 to make a size of about 35 mm × About 35mm test piece. In addition, cut the SUS grid with an aperture of 77μm into 150mm×150mm, and shape it into a beam bag shape, and fix the opening with a metal wire to make a packaging material. After measuring the weight of the packaging material (W1), open the wire, put the test piece in, measure the weight again (W2), put it in a glass bottle, and soak in 100 mL of ethyl acetate. After standing at 25°C for 24 hours, it was taken out from ethyl acetate and heated and dried in a dryer at 130°C for 90 minutes. The weight (W3) was measured, and the gel fraction calculated by the following formula (1) was evaluated using the following criteria: Rate. The results are shown in Table 3. The higher the gel fraction, the more the adhesive can be cured to a practical level in a short time. Gel fraction (weight%)=(W3-W1)/(W2-W1)×100　(1) <Evaluation criteria> ◎ ：More than 90%. ○: More than 70%, but less than 90%. △: Above 50%, but less than 70%. ×: Less than 50%.

[table 3] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1 2 Main agent (P-1) 100 - - - - - - - - - - - - - - - - - (P-2) - 100 - - - - - - - - - - - - - - - - (P-3) - - 100 - - - - - - - - - - - - - - - (P-4) - - - 100 - - - - - - - - - - - - - - (P-5) - - - - 100 - - - - - - - - - - - - - (P-6) - - - - - 100 - - - - - - - - - - - - (P-7) - - - - - - 100 - - - - - - - - - - - (P-8) - - - - - - - 100 - - - - - - - - - - (P-9) - - - - - - - - 100 - - - - - - - - - (P-10) - - - - - - - - - 100 - - - - - - - - (P-11) - - - - - - - - - - 100 - - - - - - - (P-12) - - - - - - - - - - - 100 - - - - - - (P-13) - - - - - - - - - - - - 100 - - - - - (P-14) - - - - - - - - - - - - - 100 - - - - (P-15) - - - - - - - - - - - - - - 100 - - - (P-16) - - - - - - - - - - - - - - - 100 - - (P'-1) - - - - - - - - - - - - - - - - 100 - (P'-2) - - - - - - - - - - - - - - - - - 100 hardener (D-1) 5.1 5.0 5.1 4.9 3.7 3.1 5.1 - - - - - 8.1 3.1 4.8 - 2.7 - (D-2) - - - - - - - 3.2 5.8 9.5 9.7 4.1 - - - 6.0 - 0.85 Solvent Ethyl acetate 40 40 40 40 40 40 40 64 98 66 66 98 52 40 40 98 40 35 Amine esterification catalyst Dibutyl tin dilaurate 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 - - 0.008 0.008 0.008 0.008 0.008 0.008 0.008 Borchi Kat22 - - - - - - - - - 0.30 0.30 - - - - - - - Isocyanate group equivalent/hydroxyl equivalent 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Initial adhesion (N/25mm) 0.017 0.021 0.015 0.020 0.014 0.011 0.018 0.024 0.016 0.013 0.018 0.017 0.019 0.036 0.019 0.019 0.051 0.012 Adhesion after heat resistance test (N/25mm) 0.039 0.039 0.036 0.038 0.015 0.016 0.037 0.027 0.023 0.034 0.032 0.037 0.042 0.051 0.035 0.028 0.078 0.034 Change in adhesion after heat resistance test (N/25mm) 0.022 0.018 0.021 0.018 0.001 0.005 0.019 0.003 0.007 0.021 0.014 0.020 0.023 0.015 0.016 0.009 0.027 0.022 Cutability ◎ ○ ○ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ △ △ Substrate adhesion ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ ◎ △ △ Breaking strength ○ ○ ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ △ ○ Elongation at break ◎ ◎ ◎ ◎ ○ ○ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ X Yield ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ ◎ ○ X Gel fraction ◎ ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎ ○ △ [Industrial availability]

The main agent for the 2-component curing type urethane adhesive of the present invention and the 2-component curing type urethane adhesive using the same can be used for the protection of optical members in the manufacturing process of image display devices such as polarizing plates or the attachment of optical members to each other It is extremely useful for a wide range of purposes.

without

without

Claims (8)

A two-component hardening type urethane adhesive, containing a main agent and a hardening agent, the main agent containing a polyol component (a) and an isocyanate group (isocyanate group) urethane prepolymer (b) reacted to form a Hydroxyl urethane resin (P), the polyol component (a) uses polyoxyalkylene polyol (a1) with a hydroxyl value of 10 to 350 mgKOH/g as an essential component. The alkylene polyol (a1) is a polyoxyalkylene polyol (a11) having a hydroxypropyl group at the molecular end represented by the general formula (1) and/or its ethylene oxide adduct (a12), The hardener contains a crosslinking agent (D) with isocyanate groups,

[In the general formula (1), X is an m-valent residue obtained by removing all active hydrogen atoms from a compound having m active hydrogen atoms; A is a carbon number of 2～ which can be substituted by phenyl, halophenyl or halogen atoms The alkylene of 12; Z is propylidene; m is an integer of 4 to 10; p is an integer of 0 to 199, q is an integer of 1 to 200, and satisfies 1≦p+q≦200]. Such as the 2-component curing type urethane adhesive of claim 1, wherein the urethane prepolymer (b) is a compound represented by the general formula (6),

[In the general formula (6), L is a divalent group obtained by removing isocyanate groups from the polyisocyanate component (bp), U represents a urethane bond, and R is each independently a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, b It is an integer of 20 to 70, and the average value of s is 1.01 to 10]. According to claim 1 or 2 of the 2-liquid hardening urethane adhesive, wherein the urethane prepolymer (b) is bifunctional, and the isocyanate group content based on the weight of the urethane prepolymer (b) is 0.1 to 12% by weight. The 2-component curing type urethane adhesive according to any one of claims 1 to 3, wherein the polyfunctional polyoxyalkylene polyol (a1) has a group represented by the general formula (2) at the molecular end and / Or the polyol of the group represented by the general formula (3), the ratio of the number of the group represented by the general formula (2) possessed by the polyfunctional polyoxyalkylene polyol (a1) is expressed by the multifunctional polyoxyalkylene The number of groups represented by the general formula (2) and the number of groups represented by the general formula (3) of the alkyl polyol (a1) are 40% or more based on the total number,

[In general formulas (2) and (3), a is each independently an integer of 0 or more]. The 2-component curing urethane adhesive according to any one of claims 1 to 4, wherein the polyfunctional polyoxyalkylene polyol (a1) is an alkylene oxide adduct of sorbitol, The alkylene oxide contains propylene oxide, and the addition molar number of the propylene oxide is 50-200. The 2-component curing type urethane adhesive according to any one of claims 1 to 5, wherein the weight average molecular weight of the urethane resin (P) is 10,000-500,000. A hardened product of a two-component hardening urethane adhesive, the two-component hardening urethane adhesive being a two-component hardening urethane adhesive according to any one of claims 1 to 6. A urethane adhesive sheet is formed by using the 2-component hardening urethane adhesive of any one of claims 1 to 6.