KR20220062406A - 2-component curing type urethane adhesive, cured product of 2-component curing type urethane adhesive and urethane adhesive sheet - Google Patents

Abstract

[일반식 (1) 중, X 는 m 개의 활성 수소 원자를 갖는 화합물로부터 모든 활성 수소 원자를 제외한 m 가의 잔기 ; A 는 페닐기, 할로페닐기 또는 할로겐 원자로 치환되어 있어도 되는 탄소수 2 ∼ 12 의 알킬렌기 ; Z 는 프로필렌기 ; m 은 4 ∼ 10 의 정수 ; p 는 0 ∼ 199 의 정수, q 는 1 ∼ 200 의 정수로서, 1 ≤ p ＋ q ≤ 200 을 만족한다.]An object of the present invention is to provide a two-component curable urethane pressure-sensitive adhesive that exhibits excellent cured film physical properties, can be peeled with very small force, and can obtain a pressure-sensitive adhesive sheet having a small change in adhesive strength before and after a heat resistance test. The present invention contains a main agent and a curing agent, wherein the main agent is a polyol component (a) containing as an essential component a polyfunctional polyoxyalkylene polyol (a1) having a hydroxyl group of 10 to 350 mgKOH/g, and a urethane-free having an isocyanate group A urethane resin (P) having a hydroxyl group formed by reacting a polymer (b) is contained, and the polyfunctional polyoxyalkylene polyol (a1) has a hydroxypropyl group at the molecular terminal represented by the general formula (1). It is an alkylene polyol (a11) and/or its ethylene oxide adduct (a12), The said hardening|curing agent is a two-component curable urethane adhesive containing the crosslinking agent (D) which has an isocyanate group.

[In the general formula (1), X is an m-valent residue obtained by excluding all active hydrogen atoms from a compound having m active hydrogen atoms; A is a phenyl group, a halophenyl group, or an alkylene group having 2 to 12 carbon atoms which may be substituted with a halogen atom; Z is a propylene group; m is an integer of 4 to 10; p is an integer from 0 to 199, q is an integer from 1 to 200, satisfying 1 ≤ p + q ≤ 200.]

Description

2-component curing type urethane adhesive, cured product of 2-component curing type urethane adhesive and urethane adhesive sheet

The present invention relates to a two-component curable urethane adhesive, a cured product of a two-component curable urethane adhesive, and a urethane adhesive sheet.

The optical member sheet|seat laminated|stacked the adhesive on the base material (polyester, polyethylene, polypropylene, glass, etc.) is used. The optical member sheet|seat is used for surface protection at the time of shipping an optical member in manufacturers of optical members, such as a polarizing plate. Moreover, in manufacturers of image display apparatuses, such as a liquid crystal display, it is used for the protection use of the optical member in the manufacturing process of a display apparatus (liquid crystal module), pasting of optical members, etc.

Although an acrylic adhesive is mainly used for these optical member sheets, the followability with respect to a to-be-adhered body is favorable, and the urethane adhesive is also examined for reasons, such as being excellent in 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 lot of curing agent, increase the crosslinking point, or increase the urethane group concentration, and the flexibility is inferior, and the cured film of the obtained adhesive is weak. There was a problem such as the change in adhesion strength before and after the heat resistance test was large. Moreover, since the adhesive force of an adhesive sheet did not become low enough, when peeling a sheet|seat from an optical member, large force was needed, and there existed a problem that workability|operativity was inferior.

Japanese Laid-Open Patent Publication No. 2006-182795

An object of the present invention is to provide a two-component curable urethane pressure-sensitive adhesive that exhibits excellent cured film physical properties, can peel with very small force, and can obtain an adhesive sheet with a small change in adhesive strength before and after the heat resistance test.

MEANS TO SOLVE THE PROBLEM The present inventors arrived at this invention, as a result of earnestly examining in order to solve the said subject.

That is, the present invention contains a main agent and a curing agent, wherein the main agent has a polyol component (a) containing as an essential component a polyfunctional polyoxyalkylene polyol (a1) having a hydroxyl group of 10 to 350 mgKOH/g, and an isocyanate group Contains a urethane resin (P) having a hydroxyl group formed by reacting a urethane-free polymer (b), wherein the polyfunctional polyoxyalkylene polyol (a1) has a hydroxypropyl group at the molecular terminal represented by the general formula (1) It is a polyoxyalkylene polyol (a11) and/or its ethylene oxide adduct (a12), The said hardening|curing agent is a two-component curable urethane adhesive containing the crosslinking agent (D) which has an isocyanate group; Hardened|cured material of the said two-component curable urethane adhesive; It is a urethane adhesive sheet formed using the said two-component curable urethane adhesive.

[Formula 1]

[In the general formula (1), X is an m-valent residue obtained by excluding all active hydrogen atoms from a compound having m active hydrogen atoms; A is a phenyl group, a halophenyl group, or an alkylene group having 2 to 12 carbon atoms which may be substituted with a halogen atom; Z is a propylene group; m is an integer of 4 to 10; p is an integer from 0 to 199, q is an integer from 1 to 200, satisfying 1 ≤ p + q ≤ 200.]

The two-component curable urethane pressure-sensitive adhesive of the present invention exhibits excellent cured film physical properties, can be peeled off with a very small force, and a two-component curable urethane pressure-sensitive adhesive sheet with a small change in adhesive strength before and after the heat resistance test can be obtained.

In the two-component curable urethane pressure-sensitive adhesive of the present invention, the main agent contains a urethane resin (P) having a hydroxyl group formed by reacting a polyol component (a) and a urethane-free polymer (b) having an isocyanate group.

The polyol component (a) in this invention makes the polyfunctional polyoxyalkylene polyol (a1) whose hydroxyl group 10-350 mgKOH/g an essential component.

The polyoxyalkylene polyol (a11) having a hydroxypropyl group at the molecular terminal represented by the general formula (1) and/or an ethylene oxide adduct (a12) thereof is essential for the polyfunctional polyoxyalkylene polyol (a1) as an ingredient

[Formula 2]

[In the general formula (1), X is an m-valent residue obtained by excluding all active hydrogen atoms from a compound having m active hydrogen atoms; A is a phenyl group, a halophenyl group, or an alkylene group having 2 to 12 carbon atoms which may be substituted with a halogen atom; Z is a propylene group; m is an integer of 4 to 10; p is an integer from 0 to 199, q is an integer from 1 to 200, satisfying 1 ≤ p + q ≤ 200.]

X in General formula (1) is a residue of m valence except all active hydrogen atoms from the compound which has m number of active hydrogen atoms, and m is an integer of 4-10.

When m is less than 4, the peeling force of the adhesive obtained rises, a cured film becomes brittle, or adhesive force does not become low enough.

When m exceeds 10, the viscosity of the polyfunctional polyoxyalkylene polyol (a1) increases, the viscosity at the time of coating the mixed solution of the main agent and the curing agent increases, and the cut property of the cured product also decreases. In addition, when the hardened|cured material of the said hardened|cured material is cut|disconnected with the blade of a cutter etc. with the cut property of said hardened|cured material, it is a property which can suppress generation|occurrence|production of chips. Moreover, it is preferable that a cut surface is smooth. Generally, the cut property of hardened|cured material is a property opposite to reduction of peeling force.

It is preferable that it is 5-8, and, as for m, it is preferable that it is 5-8 from a viewpoint of adhesiveness with a base material, peeling force reduction, and the cut property improvement of hardened|cured material, and it is more preferable.

Examples of the compound having m active hydrogen atoms constituting the residue X include a hydroxyl group-containing compound, an amino group-containing compound, a carboxy group-containing compound, and a group selected from a hydroxyl group, a primary or secondary amino group, a carboxy group and a mercapto group, such as thiol The compound etc. which have are mentioned.

As said hydroxyl-containing compound, polyhydric alcohol (pentaerythritol, sorbitol, xylitol, mannitol, etc.); These intermolecular or intramolecular dehydration products (For example, dipentaerythritol, sorbitan, etc.); polyglycerol (degree of polymerization 2 to 8); saccharides and derivatives thereof (eg, glucose, sucrose, fructose, α-methylglucoside and glycoside) and the like; Polymer or oligomer having a number average molecular weight of 2,000 or less which has m hydroxyl groups {Polyalkadiene (C4-10) polyol (For example, polybutadiene polyol and its hydrogenated substance); (co)polymer of hydroxyalkyl (C2-4) (meth)acrylate; polyvinyl alcohol (saponification degree 60% or more) etc.}; and mixtures of two or more thereof.

In addition, the number average molecular weight in this invention can be measured by gel permeation chromatography on condition of the following, for example.

Device: 「Waters Alliance 2695」 [manufactured by Waters]

Column: “Guardcolumn Super H-L” (1 pc.), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected by one each”

Sample solution: 0.25 wt% tetrahydrofuran solution

Solution injection volume: 10 μl

Flow rate: 0.6 ml/min

Measuring temperature: 40℃

Detection device: refractive index detector

Reference material: standard polyethylene glycol

As the amino group-containing compound, polyamines having 4 to 10 active hydrogen atoms [aliphatic diamines having 2 to 12 carbon atoms or more; alkylenediamines having 2 to 12 carbon atoms (eg, ethylenediamine, propylenediamine, hexamethylenediamine, etc.) ), an alicyclic diamine having 6 to 15 carbon atoms (1,4-diaminocyclohexane, isophoronediamine and 4,4'-diaminocyclohexylmethane, etc.)}, an aromatic diamine having 6 to 15 carbon atoms {m- or p -phenylenediamine, tolylenediamine, diethyltoluenediamine, 4,4'-diaminophenylmethane and 2,2-bis(4,4'-diaminophenyl)propane}, aromatic aliphatic having 8 to 15 carbon atoms Diamine (m- or p-xylylenediamine, etc.), heterocyclic polyamine having 4 to 10 carbon atoms {piperazine, aminoalkyl (2 to 4 carbon atoms) piperazine (eg aminoethylpiperazine), aminoalkyl (carbon number 2 to 4) imidazole, etc.}, polyalkylene polyamines having 2 to 4 carbon atoms in the alkylene group {diethylenetriamine, dipropylenetriamine, triethylenetetramine, polyethyleneimine having a number average molecular weight of 2,000 or less, and mono-; di- or tri-alkyl (C1-C4) polyalkylene polyamine (eg, dimethyltriethylenetetramine etc.)} etc.]; mono- or di-alkanol (C2-4) amines (such as N,N-bis(2-hydroxyethyl)ethylenediamine) of a hydroxyalkyl group (C2-4); Polymers or oligomers having one or two or more amino groups and having a number average molecular weight of 2,000 or less [aminoalkyl (C2 to C4) (meth)acrylate (co)polymers, etc.]; and mixtures of two or more thereof.

Examples of the carboxyl group-containing compound include aromatic polycarboxylic acids having 8 to 30 carbon atoms (eg, naphthalenetetracarboxylic acid and pyromellitic acid), unsaturated carboxylic acid polymers [(meth)acrylic acid having a number average molecular weight of 2,000 or less (meth)acrylic acid ( co) polymer, etc.] and mixtures of two or more thereof.

As a thiol, a C2-C6 or more polythiol (For example, pentaerythritol tetrakis(3-mercaptobutyrate) etc.) etc. are mentioned.

Among these, from the viewpoint of curability, hydroxyl group-containing compounds and amino group-containing compounds are preferable, and 4- to 10-hydric polyhydric alcohols {pentaerythritol, sorbitol, xylitol, mannitol, etc.} are more preferable; These intermolecular or intramolecular dehydrates (eg, dipentaerythritol and sorbitan; polyglycerin (degree of polymerization 2 to 8); saccharides and derivatives thereof (eg, glucose, fructose, sucrose, α-methylglucoside) and glycosides, etc.).

A in general formula (1) is a phenyl group, a halophenyl group, or a C2-C12 alkylene group which may be substituted with a halogen atom, A C2-C12 linear or branched alkylene group, C6-C10 cyclo and those in which at least a part of the alkylene group and the hydrogen atoms it has are substituted with a phenyl group, a halophenyl group, or a halogen atom (such as Cl and Br).

Specific examples of A include an ethylene group, a 1,2- or 1,3-propylene group, a 1,2-, 2,3-, 1,3- or 1,4-butylene group, and 1 having 5 to 12 carbon atoms. ,2-alkylene group (1,2-dodecylene group, etc.), 1,2-cyclohexylene group, chloropropylene group, bromopropylene group, phenylethylene group and chlorophenylethylene group.

(A-O) in the general formula (1) is a moiety derived from AO obtained by adding an alkylene oxide (hereinafter, abbreviated as AO) to a compound having m active hydrogen atoms constituting the residue X. As AO used, 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 having 5 to 12 carbon atoms, epihalohydrin (epichlorohydrin, epibromohydrin, etc.), styrene oxide , chlorostyrene oxide, 1,2-cyclohexene oxide, and combinations of two or more thereof, and when p (A-O) is composed of two or more oxyalkylene groups, the bonding mode is either block or random. okay Among these, PO and 1,2-BO are preferable from the viewpoint of the flexibility of the cured product.

Z in the general formula (1) is a propylene group, specifically, a 1,2- or 1,3-propylene group.

In general formula (1), p is an integer of 0-199, q is an integer of 1-200, and 1≤p+q≤200 is satisfied. It is preferable that it is 50 or less from an adhesive viewpoint with a base material, and, as for the value of p+q, it is more preferable that it is 30 or less.

Moreover, it is preferable that said polyfunctional polyoxyalkylene polyol (a1) is a polyol which has a group represented by general formula (2) and/or group represented by general formula (3) at a molecular terminal.

[Formula 3]

[Formula 4]

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 terminal of the polyoxyalkylenepolyol (a11), and when a is 1 or more, the general formulas (2) and (3) are polyoxyalkylene The molecular terminus of the ethylene oxide adduct (a12) of the polyol (a11) is shown.

In addition, the ratio of the total number of groups represented by the general formula (2) which the polyfunctional polyoxyalkylene polyol (a1) has is, from the viewpoints of the breaking strength and cutability of the cured product, the polyfunctional polyoxyalkylene polyol (a1) It is preferably 40% or more, more preferably 60% or more, based on the sum of the number of groups represented by the general formula (2) and the number of groups represented by the general formula (3).

Confirmation that the polyoxyalkylene polyol (a11) has a hydroxypropyl group at the molecular terminal can be performed, for example, by ¹ H-NMR method. The hydroxypropyl group includes a primary hydroxyl group (hydroxyl group bonded to primary carbon)-containing group represented by the following formula (4) and a secondary hydroxyl group (hydroxyl group bonded to secondary carbon)-containing group represented by the following general formula (4'). Primary hydroxyl group content (hereinafter abbreviated as primary conversion rate) which is the ratio of the number of primary hydroxyl group-containing groups to the total number of primary hydroxyl group-containing groups and secondary hydroxyl group-containing groups in the polyoxyalkylene polyol (a11) is , from the viewpoint of adhesive strength, preferably 40% or more, more preferably 60% or more.

[Formula 5]

[Formula 6]

After pre-processing (esterification) a sample in advance, the primary chemical conversion rate can be measured and calculated|required by < ¹ >H-NMR method.

The details of the ¹ H-NMR method will be described below.

<Sample preparation method>

About 30 mg of the measurement sample is weighed into a sample tube for NMR with a diameter of 5 mm, and about 0.5 ml of a deuterated solvent is added and dissolved. After that, about 0.1 ml of trifluoroacetic anhydride is added to prepare a sample for analysis. As the deuterated solvent, a solvent capable of dissolving the sample is appropriately selected from, for example, deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, and the like.

<NMR measurement>

¹ H-NMR measurement is performed under normal conditions.

＜Calculation method of the primary fire rate＞

By the method of the pretreatment mentioned above, the hydroxyl group at the terminal of polyoxyalkylene polyol reacts with the added trifluoroacetic anhydride, and turns into trifluoroacetic acid ester. As a result, the signal derived from the methylene group to which the primary hydroxyl group is bonded is observed at around 4.3 ppm, and the signal derived from the methine group to which the secondary hydroxyl group is bonded is observed at around 5.2 ppm. The primary fire rate is calculated by the following formula.

Primary rate (%) = [x/(x + 2 × y)] × 100

[However, x is the integral value of the signal derived from the methylene group bonded to the primary hydroxyl group around 4.3 ppm, and y is the integral value of the signal derived from the methine group bonded to the secondary hydroxyl group around 5.2 ppm.]

In other words, it is preferable that the said polyfunctional polyoxyalkylene polyol (a1) satisfy|fills the following conditions.

When the polyfunctional polyoxyalkylene polyol (a1) is only the polyoxyalkylene polyol (a11), it is preferable that the primary hydroxyl group content of the polyoxyalkylene polyol (a11) is at least 40%. When the polyoxyalkylene polyol (a11) is two or more types, it is preferable that the primary hydroxyl group content of the mixture is at least 40%.

Moreover, when the said polyfunctional polyoxyalkylene polyol (a1) is only the said ethylene oxide adduct (a12), it is preferable that the primary hydroxyl group content rate of (a11) before ethylene oxide addition is at least 40 %. When (a11) before ethylene oxide addition is 2 or more types, it is preferable that the primary hydroxyl group content rate of the mixture is at least 40 %.

In the case where the polyfunctional polyoxyalkylene polyol (a1) is a mixture of the polyoxyalkylene polyol (a11) and the ethylene oxide adduct (a12), (a11) before the ethylene oxide addition of (a12) and , assuming that the mixture of (a11) contained in the polyfunctional polyoxyalkylene polyol (a1) exists, it is preferable that the primary hydroxyl group content of the mixture is at least 40%.

In addition, the ratio of the total number of groups represented by General formula (2) which polyfunctional polyoxyalkylene polyol (a1) has is a polyfunctional polyoxyalkylene polyol (a1) from a viewpoint of the breaking strength and cutability improvement of hardened|cured material. ) is more preferably 60% or more on the basis of the sum of the number of groups represented by the general formula (2) and the number of groups represented by the general formula (3).

The polyoxyalkylene polyol (a11) can be produced, for example, by the method described in JP-A-2000-344881. Preferred examples of the polyoxyalkylene polyol (a11) include an active hydrogen-containing compound (a0) represented by the following general formula (5) in the presence of a tris(pentafluorophenyl)borane catalyst (hereinafter abbreviated as TPB), The thing obtained by ring-opening addition polymerization of PO, etc. are mentioned. When PO ring-opening addition polymerization is carried out using TPB as a catalyst, PO addition tends to proceed so that the terminal hydroxyl group is selectively a group of the formula (4).

[Formula 7]

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

Specific examples of the active hydrogen-containing compound (a0) include the same compounds as those exemplified as compounds having m active hydrogen atoms constituting the residue of the general formula (1) when p is 0.

In the present specification, the compound obtained by adding PO to the compound having p in the general formula (5) is 0 and q is 1 or more in the general formula (1).

The active hydrogen-containing compound (a0) when p is 1 or more is a polyol obtained by (co)addition of AO to a compound constituting the residue X using a conventionally known catalyst (such as an alkali metal hydroxide). Preferred examples are the PO adduct or PO/1,2-BO co-adduct of pentaerythritol (block or random), the PO adduct of dipentaerythritol or the PO/1,2-BO co-adduct (block or random) random), PO adduct or PO/1,2-BO adduct of polyglycerin (block or random), PO adduct or PO/1,2-BO adduct of sorbitol (block or random), sucrose PO adducts or PO/1,2-BO co-adducts (block or random); and the like.

Although there is no particular limitation on the amount of TPB used in the production of the polyfunctional polyoxyalkylene polyol (a1) by ring-opening addition polymerization of PO to the active hydrogen-containing compound (a0), the weight of the polyfunctional polyoxyalkylene polyol (a1) Based on the above, preferably 0.00005 to 10% by weight, more preferably 0.0001 to 1% by weight.

The number of moles added of PO is 1 to 200 moles, preferably 2 to 100 moles, more preferably 3 to 30 moles per active hydrogen atom of the active hydrogen-containing compound (a0). The number of added moles of the total AO (the sum of AO in the first step and PO in the second step) per active hydrogen atom of the compound constituting the residue X is from 1 to 200 moles, preferably from 3 to 100 moles. When the number of added moles exceeds 200 moles, the viscosity of the polyfunctional polyoxyalkylene polyol (a1) increases, the viscosity of the mixed solution of the main agent and the curing agent increases, and the cut property of the cured product also decreases.

Therefore, q in General formula (1) is 1-200, Preferably it is 2-100, More preferably, it is 3-30. Moreover, p+q in General formula (1) is 1-200, Preferably it is 3-100.

The reaction temperature at the time of ring-opening addition polymerization of PO becomes like this. Preferably it is 0-250 degreeC, More preferably, it is 20-180 degreeC. From the viewpoint of controlling the reaction temperature, a method in which PO is added dropwise to a mixture of the active hydrogen-containing compound (a0) and TPB or a mixture of PO and TPB is added dropwise to the active hydrogen-containing compound (a0) is preferred.

Since the prepared addition polymer contains TPB, it is preferable to perform adsorption removal treatment using an adsorbent such as synthetic silicate (magnesium silicate and aluminum silicate, etc.) and activated clay.

The EO adduct (a12) of the polyoxyalkylene polyol (a11) can be obtained by adding EO to the polyoxyalkylene polyol (a11) by a commonly used method. The amount of the oxyethylene group added is 40 wt% or less, preferably 30 wt% or less, particularly preferably 10 wt% or less, based on the total weight of oxyalkylene groups in the EO adduct (a12).

The content of the total of the polyoxyalkylene polyol (a11) and/or the EO adduct (a12) in the polyol component (a) in the present invention is preferably 50% by weight based on the weight of the polyol component (a). or more, more preferably 70 wt% or more. If it is less than 50 weight%, the effect of this invention may be hard to be acquired.

The hydroxyl value of polyfunctional polyoxyalkylene polyol (a1) is 10-350 mgKOH/g. When a hydroxyl value is less than 10 mgKOH/g, the cut property of hardened|cured material deteriorates. When a hydroxyl value exceeds 350 mgKOH/g, peeling force will rise, and the adhesive performance of an adhesive and to-be-adhered body will deteriorate (yield by generation|occurrence|production of a bubble deteriorates).

From the viewpoint of improving the cutability 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.

A hydroxyl value can be measured by the method of JISK1557-1.

A polyoxyalkylene polyol (a11) and its EO adduct (a12) may use together 2 or more types, respectively. As an aspect of the combined use, for example, a base agent [a compound having m active hydrogen atoms constituting the residue X in the general formula (1)] of a different type [for example, a polyhydric alcohol (sorbitol, etc.) is used as a base and those based on polyamines (triethylenetetramine, etc.) and those based on the number of functional groups [m in the general formula (1)] and a compound based on a 5- to 10-functional compound (dipentaerythritol, sorbitol, sucrose, etc.)], a hydroxyl value or AO added mole number [p+q in the general formula (1)] different [hydroxyl value 300 mgKOH/ g or more and less than 300 mgKOH/g (preferably 30 mgKOH/g or more and less than 300 mgKOH/g)] can be used in combination.

Preferred specific examples of the polyfunctional polyoxyalkylene polyol (a1) constituting the polyol component (a) in the present invention include a PO adduct of pentaerythritol and a PO/1,2-BO adduct (block ), PO adduct of dipentaerythritol and PO/1,2-BO adduct (block), PO adduct and PO/1,2-BO adduct of polyglycerol (block), PO adduct of sorbitol water and a PO/1,2-BO conjugate (block), a PO adduct of sucrose, and a PO/1,2-BO conjugate (block). Among these, the PO adduct of sorbitol and the PO/1,2-BO covalent adduct (block) are more preferable from the viewpoint of the film strength of the pressure-sensitive adhesive, no lifting and peeling, and easy peeling when peeling, particularly preferably is a PO 50 to 200 molar adduct of sorbitol.

The polyol component (a) in this invention can contain other polyol (a2) other than the said polyfunctional polyoxyalkylene polyol (a1).

As another polyol (a2), it is a thing other than polyfunctional polyoxyalkylene polyol (a1), A polyether polyol, polyester polyol, polyolefin polyol, polyalkadiene polyol, acrylic polyol, etc. are mentioned.

Examples of the polyether polyol include polyethylene glycol, polytetramethylene ether glycol, poly-3-methyltetramethylene ether glycol, copolymerized polyoxyalkylenediol [EO/PO copolymerized diol not having a hydroxypropyl group at the terminal, THF/EO copolymerized diol, THF/3-methyltetrahydrofuran copolymerized diol, etc. (weight ratio is 1/9 - 9/1, for example)] and an AO adduct of a bisphenol-based compound that does not have a hydroxypropyl group at the terminal; Trifunctional or higher polyether polyols containing hydroxyalkyl groups other than hydroxypropyl groups at the terminal, for example, AO adducts of trihydric or higher polyhydric alcohols [AO adducts of glycerin, AO adducts of trimethylolpropane, etc. ] ; And what couple|coupled 1 or more types of these by methylene dichloride, etc. are mentioned.

Examples of the polyester polyol include castor oil fatty acid ester polyol (eg, castor oil, partially dehydrated castor oil, and castor oil fatty acid ester);

poly (n = 2 to 3 or more) carboxylic acids [aliphatic saturated or unsaturated polycarboxylic acids having 2 to 40 carbon atoms, such as oxalic acid, adipic acid, azelaic acid, dodecanoic acid, maleic acid, fumaric acid, it Conic acid and dimerized linoleic acid), aromatic ring-containing polycarboxylic acids (8 to 15 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid) and alicyclic polycarboxylic acids (7 carbon atoms) to 15, for example 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid) and polyols [for example, the hydroxyl group-containing compound, polyfunctional polyoxyalkylene polyol (a1) ) and other polyols (a2), etc.] a linear or branched polyester polyol;

A polylactone polyol [for example, one or a mixture of two or more of the above hydroxyl group-containing compounds (2 to trivalent) is used as a base agent, and (substituted) caprolactone (6 to 10 carbon atoms, for example ε-caprolactone, A polyol obtained by addition polymerization of α-methyl-ε-caprolactone and ε-methyl-ε-caprolactone in the presence of a catalyst (organometallic compound, metal chelate compound, fatty acid metal acyl compound, etc.) (e.g. polycaprolactone polyol) )] ; A polyether ester polyol obtained by addition polymerization of AO (EO and PO, etc.) to a polyester having a carboxyl group and/or a hydroxyl group at the terminal, neither of the polyoxyalkylene polyol (a11) nor the EO adduct (a12) thing ;

Polycarbonate polyol etc. are mentioned.

As polyolefin polyol, polyisobutene polyol etc. are mentioned.

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 (meth) acrylate (alkyl having 1 to 30 carbon atoms) ester [butyl (meth) acrylate, etc.] and a hydroxyl group-containing acrylic monomer [hydroxyethyl (meth) acrylate, etc.] can

When using another polyol (a2), 0.1 to 5 weight% of the content is preferable based on the total weight of a polyol component (a).

It is preferable that the hydroxyl equivalent (number average molecular weight per hydroxyl group) of the polyol component (a) in this invention is 500 or more.

The urethane-free polymer (b) which has an isocyanate group in this invention is a urethane-free polymer which has an isocyanate group which consists of a polyol component (ap) and a polyisocyanate component (bp).

As the polyol component (ap), polyether polyol, polyester polyol, polyolefin polyol, polyalkadiene polyol, acrylic polyol, and the like can be used. Among these, from the viewpoint of reducing the strength and peeling force of the resulting urethane pressure-sensitive adhesive sheet, preferably polyether polyol, polyester polyol, and acrylic polyol, more preferably bifunctional polyether polyol, particularly preferably bifunctional polyol propylene glycol and bifunctional polytetramethylene ether glycol or derivatives thereof (such as a compound in which a hydrogen atom in a methylene group is substituted with an alkyl group having 1 to 4 carbon atoms). A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group etc. are mentioned as said C1-C4 alkyl group.

Moreover, it is preferable from a viewpoint of the cut property improvement of hardened|cured material, and reduction of peeling force, bifunctional polytetramethylene ether glycol or its derivative(s).

The polyisocyanate component (bp) in the present invention includes those having 2 to 3 or more isocyanate groups, for example, a chain aliphatic polyisocyanate having 4 to 22 carbon atoms (bp1), 8 to 18 carbon atoms and alicyclic polyisocyanate (bp2), aromatic polyisocyanate (bp3) having 8 to 26 carbon atoms, aromatic polyisocyanate (bp4) having 10 to 18 carbon atoms, and modified products (bp5) of these polyisocyanates.

A polyisocyanate component (bp) may be used individually by 1 type, and may use 2 or more types together.

Examples of the chain aliphatic polyisocyanate (bp1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11 -Undecanetriisocyanate, 2,2,4-trimethylhexamethylenediisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis(2-isocyanatoethyl)fumarate, bis(2-iso Cyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc. are mentioned.

Examples of the alicyclic polyisocyanate (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, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate and the like.

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-tolylene diisocyanate (hereinafter abbreviated as TDI); Crude TDI, 4,4'- or 2,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI, polyallyl polyisocyanate, 4,4'-diisocyanatobiphenyl, 3 , 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4"-triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, etc. are mentioned.

Examples of the aromatic aliphatic polyisocyanate (bp4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α,α,α′,α′-tetramethylxylylene diisocyanate.

As the modified product (bp5) of the polyisocyanate of (bp1) to (bp4), imine group, isocyanurate group, or oxazolidone group-containing modified product; free isocyanate group content of 8 to 33% by weight, preferably 10 to 30% by weight, particularly 12 to 29% by weight), for example, modified Modified products of polyisocyanates such as MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI can be heard

Among these polyisocyanate components (bp), from the viewpoint of the strength and adhesive force of the resulting urethane pressure-sensitive adhesive sheet, preferably a C4-C22 chain aliphatic polyisocyanate (bp1) and a C8-C18 alicyclic polyisocyanate (bp2) and more preferably HDI and IPDI.

As a urethane-free polymer (b), it is preferable that it is a compound represented by General formula (6).

[Formula 8]

In the general formula (6), L is a divalent group excluding an isocyanate group from the polyisocyanate component (bp), U represents a urethane bond, R is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and b is The integer of 20-70 and the number average value of s are 1.01-10. The 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).

As said C1-C4 alkyl group, the thing similar to the C1-C4 alkyl group illustrated with respect to the derivative of the said polyol component (ap) of bifunctional polytetramethylene ether glycol is mentioned.

In general formula (6), it is preferable that b is an integer of 25-60.

In general formula (6), it is preferable that the number average value of s is 1.01-5.

As the urethane-free polymer (b), a compound having a number average molecular weight of the portion of (CHR-CHR-CHR-CHR-O) _b in the general formula (6) is 1,400 to 5,100, and 2,000 to 3,000. A phosphorus compound is more preferred.

In the urethane-free polymer (b) having an isocyanate group, the equivalent of the isocyanate group in (bp) to the equivalent of the active hydrogen-containing group in (ap) in the case of reacting the polyol component (ap) and the polyisocyanate component (bp) The ratio (equivalent of isocyanate group/equivalent of active hydrogen-containing group) is preferably 1.1 to 2.0, more preferably 1.2 to 1.8, particularly preferably 1.3 to 1.7, from the viewpoints of the strength and adhesive force of the resulting urethane pressure-sensitive adhesive sheet. am.

The weight average molecular weight of the urethane-free polymer (b) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 4,000 to 30,000 from the viewpoints of the strength and adhesive force of the urethane pressure-sensitive adhesive sheet to be obtained. The weight average molecular weight of a urethane-free polymer (b) can be measured by the method mentioned later.

It is preferable that the said urethane-free polymer (b) is bifunctional (that is, the compound whose isocyanate group which 1 mol of urethane-free polymer (b) has is 2 mol).

It is preferable that the isocyanate group content based on the weight of the said urethane-free polymer (b) is 0.1 to 12 weight%, and, as for the said urethane-free polymer (b), it is more preferable that it is 0.3 to 1.5 weight%.

Said isocyanate group content is measured based on JISK7301-1995, 6.3 isocyanate group content rate.

The urethane-free polymer (b) which has an isocyanate group of this invention can be obtained by making a polyol component (ap) and a polyisocyanate component (bp) react by a general method.

In the method for producing the urethane-free polymer (b) in the present invention, for example, the presence of a solvent (toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide, acetone, methyl ethyl ketone, tetrahydrofuran, etc.) A method in which the polyol component (ap) and the polyisocyanate component (bp) are reacted in the presence or absence is mentioned. To decrease the ratio of the equivalent of the active hydrogen-containing group of (ap) to the equivalent of the isocyanate of (bp) (preferably the equivalent of the isocyanate group of (bp) to the equivalent of the active hydrogen-containing group of (ap) above) ), the urethane-free polymer (b) having an isocyanate group at the terminal can be produced.

In addition, you may carry out said reaction in presence of gelatinization inhibitor (The compound similar to the hardening retarder mentioned later can be used).

A well-known reaction apparatus (a mixing tank provided with a stirrer, a static mixer, etc.) can be used for reaction, The reaction temperature becomes like this from a viewpoint of reactivity and thermal deterioration suppression. Preferably it is 10-160 degreeC, More preferably, 25- It is 120 degreeC, and from a viewpoint of stability, it is preferable to replace a gaseous-phase part with nitrogen.

The urethane resin (P) having a hydroxyl group constituting the main component of the two-component curable urethane pressure-sensitive adhesive of the present invention can be obtained by reacting the polyol component (a) with the urethane-free polymer (b) having an isocyanate group by a general method. .

The ratio of the equivalent of the isocyanate group of the urethane-free polymer (b) to the equivalent of the active hydrogen-containing group of the polyol component (a) in the case of reacting the polyol component (a) with the urethane-free polymer (b) having an isocyanate group (isocyanate group) The equivalent/equivalent of an active hydrogen-containing group) is 0.05 to 0.7, preferably 0.1 to 0.5, more preferably 0.15 to 0.4, from the viewpoints of the strength and adhesive force of the urethane pressure-sensitive adhesive sheet to be obtained.

It is preferable that the urethane resin (P) contains the compound represented by the following general formula (7).

[Formula 9]

In the general formula (7), K is a divalent to divalent group excluding two or more OH groups from the compound of the polyol component (a), and U, R, and L are the same as above.

In general formula (7), b is an integer of 20-70, and it is preferable that it is an integer of 25-60.

In general formula (7), the number average value of s is 1.01-10, and it is preferable that it is 1.01-5.

In general formula (7), t is an integer of 1 or more, and it is preferable that it is an integer of 1-10. When t is 2 or more, the blocks represented by [KU-[LU-(CHR-CHR-CHR-CHR-O) _b -U] _s -LU] _t are linearly bonded.

In the general formula (7), when K is a trivalent or higher group, K to which the hydroxy group at the terminal of the general formula (7) is bonded is, in addition to U shown in the general formula (7), one or more urethane bonds You may have (that is, said K may have 2 or more urethane bond).

In addition, when K has one or more urethane bonds other than U shown in the general formula (7), K is [KU-[LU-(CHR-CHR-CHR-CHR-O) _b -U] _s -LU] You may have a block represented by _t . When K has the block via a urethane bond other than U, the compound represented by the general formula (7) has a branched structure in which a plurality of blocks have K as a starting point.

The weight ratio of the compound represented by the general formula (7) contained in the urethane resin (P) is 30% by weight or more based on the weight of the urethane resin (P) from the viewpoint of reducing peeling force and improving cutability of the cured product. It is preferable that it is 50 weight% or more, more preferably, it is 80 weight% or more, It is especially preferable that it is 80 weight% or more, and it is most preferable that it is 90 weight% or more.

It is preferable that it is 10,000-500,000, and, as for the weight average molecular weight of said urethane resin (P), the viewpoint of the breaking strength of hardened|cured material, breaking elongation, cut property, and sclerosis|hardenability, it is still more preferable that it is 120,000-500,000.

The weight average molecular weight of the urethane free polymer (b) and the urethane resin (P) in this invention can be measured by gel permeation chromatography on the following conditions, for example. In addition, when measuring a urethane-free polymer (b), a weight average molecular weight is measured with respect to what made all the isocyanate groups which a urethane-free polymer (b) have react with methanol. In addition, let the value which subtracted this from the weight average molecular weight measured by calculating the weight derived from methanol from isocyanate group content as the weight average molecular weight of a urethane free polymer (b).

Device: 「HLC-8120GPC」 [manufactured by Toso Co., Ltd.]

Guard column: 「Guardcolumn HXL-H」 [manufactured by Tosoh Corporation]

Column: "TSKgel GMHXL" [manufactured by Tosoh Corporation]

Sample solution: 0.125% by weight of dimethylformamide (containing 0.01 M LiBr) solution

Solution injection volume: 100 μl

Flow rate: 1 ml/min

Measuring temperature: 40℃

Detection device: refractive index detector

Reference material: standard polystyrene

As a manufacturing method of the urethane resin (P) which has a hydroxyl group in this invention, a known manufacturing method of a urethane resin can be used, For example, solvent (toluene, xylene, ethyl acetate, butyl acetate, dimethylformamide) , acetone, methyl ethyl ketone, tetrahydrofuran, etc.) in the presence or absence of the polyol component (a) and a method of reacting the urethane-free polymer (b) having an isocyanate group is mentioned. To increase the ratio of the equivalent of the active hydrogen-containing group of the polyol component (a) to the equivalent of the isocyanate of the urethane-free polymer (b) (preferably urethane with respect to the equivalent of the active hydrogen-containing group of the polyol component (a) above) It is adjusted in the ratio range of the equivalent of the isocyanate group of a free polymer (b)), and the urethane resin (P) which has a hydroxyl group at the terminal can be manufactured.

In addition, you may carry out said reaction in presence of a gelatinization inhibitor (The compound similar to the hardening retarder mentioned later can be used). Since high molecular weight can be made without gelatinizing a urethane resin (P) by using a gelatinization inhibitor, cut property and breaking elongation can be improved.

A well-known reaction apparatus (a mixing tank provided with a stirrer, a static mixer, etc.) can be used for reaction, The reaction temperature becomes like this from a viewpoint of reactivity and thermal deterioration suppression. Preferably it is 10-160 degreeC, More preferably, 25- It is 120 degreeC, and from a viewpoint of stability, it is preferable to replace a gaseous-phase part with nitrogen.

The two-component curable urethane adhesive of this invention contains the hardening|curing agent containing the main body containing the said urethane resin (P), and the crosslinking agent (D) which has an isocyanate group.

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

From a hardenable viewpoint, it is preferable that the average functional group number of a crosslinking agent (D) is 2-6 or more, More preferably, it is 2-5, Especially preferably, it is 3-4.

When producing the pressure-sensitive adhesive sheet using the two-component curable urethane pressure-sensitive adhesive, the cured product of the two-component curable urethane pressure-sensitive adhesive, and the two-component curable urethane pressure-sensitive adhesive according to the present invention, depending on the use and curability requirements, a urethanization catalyst can be used there is.

As a urethanation catalyst, a metal catalyst, an amine catalyst, etc. are mentioned. Examples of the metal catalyst include tin-based catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltindilaurate, dibutyltindiacetate, dibutyltindilaurate, stannus octoate, dibutyltin maleate, and the like); lead catalysts (lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octhenate, etc.); bismuth catalysts (such as bismuth carboxylate, bismuth alkoxide, and a chelate compound of a compound having a dicarbonyl group and bismuth); titanium-based catalysts (such as isopropoxytriN-ethylaminoethylaminate titanium, tetrabutyl titanate and tetraisopropoxybisdioctylphosphite titanium); zinc-based catalysts (organic zinc complexes, etc.); zirconium-based catalysts (such as zirconium tetraacetylacetonate and zirconium tributoxyacetylacetonate); aluminum-based catalysts (such as aluminum complexes); Iron-based catalysts [such as iron carboxylate compounds (iron lactate and iron ricinolate), ferrocene-based compounds (ferrocene and acetylferrocene, etc.) and iron phthalocyanine, etc.] and other metal catalysts (naphthenic acid metal salts such as cobalt naphthenate, and phenyl and mercury propionate).

Examples of the amine catalyst include triethylenediamine, tetramethylethylenediamine, diazabicycloalkene [1,8-diazabicyclo[5.4.0]undecene-7 [DBU (manufactured by San Apro Co., Ltd., registered trademark)], etc. ], dialkyl (1 to 3 carbon atoms) aminoalkyl (2 to 4 carbon atoms) amine (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine and dipropylaminopropylamine, etc.), heterocyclic aminoalkyl ( C2-6) amine [2-(1-aziridinyl)ethylamine, 4-(1-piperidinyl)-2-hexylamine, etc.], N-methyl, N-ethylmorpholine, etc. are mentioned. .

Among these, diazabicycloalkenes, bismuth-based catalysts, tin-based catalysts and zinc-based catalysts are preferable, and DBU, bismuth carboxylate, dibutyltindilaurate and organic zinc complexes are particularly preferable.

The amount of the urethanization catalyst used varies depending on the application, but when high fast curing is required, preferably 3,000 ppm or less, more preferably 1 to 2,000 ppm, particularly preferably based on the weight of the two-component curing type urethane pressure-sensitive adhesive. 10 to 1,000 ppm. A urethanation catalyst may be used individually by 1 type, and may use 2 or more types together.

The two-component curable urethane pressure-sensitive adhesive of the present invention is further exemplified by the method for producing the urethane resin (P), an antioxidant, a curing retardant, a ultraviolet absorber, a plasticizer, It may contain additives such as tackifiers, fillers and pigments. The additive may be added to any of the main agent and the curing agent, or may be added at the time of mixing the main agent and the curing agent, but it is preferable to add the additive to the main agent in advance.

Antioxidants include hindered phenol compounds [triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetrakis[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate] and 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl) ) propionate] and the like] and a phosphorous acid ester compound [tris(2,4-di-t-butylphenyl)phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, Bis(2,6-di-t-butylphenyl)pentaerythritol-di-phosphite and tetrakis(2,4-di-t-butylphenyl) 4,4'-biphenylene-di-phosphonite etc.] and the like. These antioxidants may be used individually by 1 type, and may use 2 or more types together. Based on the weight of the two-component curing type urethane pressure-sensitive adhesive, the amount of the antioxidant used is preferably 5% by weight or less, and more preferably 0.05 to 1% by weight from the viewpoint of the antioxidant effect and adhesive strength.

As a curing retardant, 2,4-pentanedione (acetylacetone), 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 (benzoylacetone), dibenzoylmethane and 2 β-diketones such as -furoylbenzoylmethane; Methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl propionyl acetate, ethyl propionyl acetate, propyl propionyl acetate, isopropyl propionyl acetate, butyl propionyl acetate, methyl butyryl acetate, butyryl acetate β-ketoesters such as ethyl, propyl butyryl acetate, methyl caproyl acetate, ethyl caproyl acetate, propyl caproyl acetate, and butyl caproyl acetate; malonic acid dialkyl esters such as dimethyl malonate, diethyl malonate, methyl ethyl malonate, diisopropyl malonate, and dibutyl malonate; and acetoacetamides such as N,N-dimethylacetoacetamide and N-ethylacetoacetamide. These curing retarders may be used individually by 1 type, and may use 2 or more types together. The amount of the curing retarder to be used is preferably 5% by weight or less, and more preferably 0.01 to 3% by weight from the viewpoint of the curing delay effect and adhesive strength based on the weight of the two-component curable urethane pressure-sensitive adhesive.

Examples of the ultraviolet absorber include salicylic acid derivatives (phenyl salicylate, salicylic acid-p-octylphenyl and salicylic acid-p-tert butylphenyl, etc.), benzophenone 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-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2- Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxy hydroxybenzophenone, 2-hydroxy-4-(2-hydroxy-3-methacryloxy)propoxybenzophenone and bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane], benzo Triazole compound {2-(2'-hydroxyl-5'-methyl-phenyl)benzotriazole, 2-(2'-hydroxyl-3',5'-di-t-butyl-phenyl)benzotriazole , 2-(2'-hydroxyl-3'-t-butyl-5'-methyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-3',5'-di-t -Butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-4'-n-octoxyphenyl)benzotriazole, 2-(2'-hydroxyl-5'-t-butyl Phenyl)benzotriazole, 2-(2'-hydroxyl-3',5'-di-t-amylphenyl)benzotriazole, 2-[2'-hydroxyl-3'-(3",4" ,5",6"-tetrahydrophthalimidemethyl)-5'-methylphenyl]benzotriazole and 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6- (2H-benzotriazol-2-yl)phenol] etc.}; and cyanoacrylate compounds (such as 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate). A ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together. The amount of the ultraviolet absorber to be used is preferably 5% by weight or less, and more preferably 0.1 to 1% by weight from the viewpoint of the ultraviolet absorption effect and adhesive strength based on the weight of the two-component curable urethane pressure-sensitive adhesive.

As the plasticizer, hydrocarbons [process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, chlorinated paraffin, paraffin wax, ethylene and α-olefin (3 to 20 carbon atoms) copolymerization (weight ratio 0.1/99.9) to 99.9/0.1) oligomer (weight average molecular weight 5,000 to 100,000) and copolymerization of propylene and α-olefin (C4 to 20) (weight ratio 0.1/99.9 to 99.9/0.1) oligomer (weight average molecular weight 5,000 to 100,000)]; chlorinated paraffin; Esters [phthalic acid esters [diethyl phthalate (DEP), dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), didecyl phthalate, dilauryl phthalate, distearyl phthalate, diisononyl phthalate, etc.], Adipic acid esters [di(2-ethylhexyl)adipate (DOA) and dioctyl adipate, etc.] and sebacate esters (dioctyl sebacate, etc.), fatty acid esters (butyl stearate, palmitic acid 2- Ethylhexyl, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, isopropyl palmitate, cholesteryl isostearate, methyl palm fatty acid, methyl laurate, methyl oleate, stearate Methyl acid, isopropyl myristate, octyldodecyl myristate, myristyl myristyl, stearyl stearate, 2-ethylhexyl stearate, isotridecyl stearate, 2-ethylhexanoic acid triglyceride, lauric acid butyl acid and octyl oleate), poly(meth)acrylic acid esters (such as butyl polyacrylate and 2-ethylhexyl polyacrylate)]; Animal and plant oils and fats (linoleic acid and linolenic acid, etc.); And among these, the hydrogenated substance etc. of what has an unsaturated double bond which can be hydrogenated are mentioned. A plasticizer may be used individually by 1 type, and may use 2 or more types together. The amount of the plasticizer used is preferably 100% by weight or less, more preferably 1 to 50% by weight, particularly preferably 3 to 40% by weight, from the viewpoint of cohesive force of the pressure-sensitive adhesive based on the weight of the two-component curable urethane pressure-sensitive adhesive; Especially preferably, it is 5 to 35 weight%, Most preferably, it is 10 to 30 weight%.

The weight average molecular weight of a plasticizer can be measured by gel permeation chromatography on condition of the following, for example.

Device: 「HLC-8120GPC」 [manufactured by Toso Co., Ltd.]

Column: "Guardcolumn HXL-H" (1 piece), "TSKgel GMHXL" (2 pieces) [all manufactured by Tosoh Corporation]

Sample solution: 0.25 wt% tetrahydrofuran solution

Solution injection volume: 100 μl

Flow rate: 1 ml/min

Measuring temperature: 40℃

Detection device: refractive index detector

Reference material: standard polystyrene

Examples of the tackifier 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 synthetic petroleum resins, etc.), coumarone- Indene resin, xylene resin, styrene resin, dicyclopentadiene resin, the hydrogenated substance etc. of what has an unsaturated double bond which can be hydrogenated among these are mentioned. A tackifier may be used individually by 1 type, or may use 2 or more types together.

Among these, those having polarity from the viewpoint of adhesive strength are preferable, rosin resins, phenol resins, terpene phenol resins, xylene resins, and hydrogenated substances thereof are more preferable, and terpene phenol resins and hydrogenated substances thereof are particularly preferable. The amount of the tackifier to be used is preferably 100% by weight or less, more preferably 1 to 50% by weight, particularly preferably 3 to 40% by weight from the viewpoint of adhesive strength and heat resistance, based on the weight of the two-component curable urethane pressure-sensitive adhesive. %, particularly preferably from 5 to 35% by weight, most preferably from 10 to 30% by weight.

As fillers, carbonates (such as magnesium carbonate and calcium carbonate), sulfates (such as aluminum sulfate, calcium sulfate and barium sulfate), sulfites (such as calcium sulfite), molybdenum disulfide, silicates (such as aluminum silicate and calcium silicate), diatomaceous earth, silicate powder, talc, silica, zeolite, and the like. The said filler becomes like this. Preferably they are microparticles|fine-particles whose volume average particle diameter is about 0.01-5 micrometers, and may be used individually by 1 type, or may use 2 or more types together. Based on the weight of a two-component curable urethane pressure-sensitive adhesive, the amount of the filler to be used is preferably 250 wt% or less from the viewpoint of the cohesive force of the pressure-sensitive adhesive, and more preferably 0.5 to 100 wt%.

As pigments, inorganic pigments (alumina white, graphite, titanium oxide, ultrafine titanium oxide, zinc oxide, black iron oxide, mica-like iron oxide, light white, white carbon, molybdenum white, carbon black, lisage, lithopone, barite, cadmium red , Cadmium Mercury Red, Bengal, Molybdenum Red, Podium, Yellow Lead, Cadmium Sulfur, Barium Sulfur, Strontium Sulfur, Titanium Sulfur, Titanium Black, Chromium Oxide Rust, Cobalt Oxide, Cobalt Rust, Cobalt Chrome Rust, Ultramarine Blue, Wire Blue, Cobalt Blue , cerulean blue, manganese violet, cobalt violet, etc.) and organic pigments (shellac, insoluble azo pigment, soluble azo pigment, condensed azo pigment, phthalocyanine blue, dyed lake, etc.). The said pigment becomes like this. Preferably they are microparticles|fine-particles whose volume average particle diameter is about 0.01-5 micrometers, and may be used individually by 1 type, or may use 2 or more types together. Based on the weight of a two-component curable urethane adhesive, the usage-amount of a pigment becomes like this from a viewpoint of the cohesive force of an adhesive, Preferably it is 250 weight% or less, More preferably, it is 0.1 to 50 weight%.

The NCO/OH ratio (equivalent of the isocyanate group to the equivalent of the hydroxyl group) at the time of mixing the main agent and the curing agent is preferably 0.3 to 2.0, more preferably 0.5 to 1.5, Especially preferably, it is 0.7-1.3.

The use of the two-component curable urethane pressure-sensitive adhesive of the present invention is not particularly limited, but for example, after mixing the main agent and the curing agent, it is applied to a base film such as a polyester film and a polyolefin film and cured to obtain an adhesive sheet, and an optical member It can be bonded together and used for a surface protection film etc.

The hardened|cured material formed by hardening|curing the two-component curable urethane adhesive of this invention, and the urethane adhesive sheet formed using the two-component curable urethane adhesive of this invention are also included in this invention.

As an optical member to which the two-component curable urethane adhesive and urethane adhesive sheet are applied, a polarizing plate, a retardation plate, a light diffusion plate, an antireflection film, an electromagnetic wave shield film used for liquid crystal displays, organic EL displays, plasma displays, field emission displays, etc. and a glass substrate.

The following method etc. are mentioned as a specific example of the method of forming a urethane adhesive sheet.

A gravure coater, a reverse roll coater, a comma coater, a spin coater, a curtain coater, a slot coater, a bar coater, a comma coater, a die coater, or a knife coater may be used for coating the two-component curable urethane adhesive on the base film. The application amount (solid content) of the pressure-sensitive adhesive at the time of 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 .

Preferably the coating temperature of the adhesive at the time of applying to a base film is 10-160 degreeC, More preferably, it is 25-130 degreeC from a viewpoint of coatability and thermal deterioration suppression, The viscosity of the adhesive in coating temperature is shaping|molding From the viewpoints of properties (which can be applied thickly and which do not have appearance defects such as warpage and dents after curing) and coatability, preferably 0.01 to 100 Pa·s, more preferably 0.02 to 50 Pa·s, particularly preferably 0.03 to 10 Pa·s. The viscosity in this invention is measured with a B-type rotational viscometer.

For the laminate, a dry laminator or an extrusion laminator which is generally used is used. After lamination, an adhesive completely hardens by curing at 10-50 degreeC for 20-150 hours.

The urethane group concentration of the cured product of the two-component curable urethane pressure-sensitive adhesive of the present invention and the urethane pressure-sensitive adhesive sheet is the total weight of the urethane resin having a hydroxyl group in the main agent (P) and the crosslinking agent (D) in the curing agent from the viewpoint of adhesive strength with the adherend 3 to 25% by weight is preferable based on the

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

[Production of polyoxyalkylene polyol]

<Production Example 1>

100 parts by weight of sorbitol and 4.0 parts by weight of potassium hydroxide were injected into a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation facility, a raw material supply line and an exhaust line, and then 3,200 parts by weight of PO through the raw material supply line The part was continuously poured into the liquid phase over 12 hours while controlling the reaction temperature to be maintained at 90 to 100°C. After aging at 100°C for 3 hours, 30 parts by weight of a synthetic silicate {"Kyowad 600" manufactured by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water were added, followed by treatment at 60°C for 3 hours. After taking out from the autoclave and filtering with a filter with a pore diameter of 1 micron, it dehydrated and obtained polyoxyalkylene polyol (a11-1). The hydroxyl value of (a11-1) was 66 mgKOH/g, the viscosity was 700 mPa*s/25 degreeC, and the primary conversion rate was 2 %. In addition, p in General formula (1) of (a11-1) was 0, and q was about 14.

<Production Example 2>

After injecting 1,000 parts by weight of polyoxyalkylene polyol (a11-1) and 0.09 parts by weight of TPB into a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation facility, a raw material supply line and an exhaust line, Stirring was started, and the inside of an autoclave and a condensation installation was pressure-reduced to 0.005 MPa. Through the raw material supply line, 50 parts by weight of PO was continuously added to the liquid phase over 12 hours while controlling the reaction temperature to be maintained at 70 to 80°C. A refrigerant at -30 ℃ was circulated to condense and recover PO by a condensing facility. Subsequently, after aging at 70°C for 4 hours, 200 parts by weight of water was added, followed by heating at 130 to 140°C for 1 hour. After heating for 1 hour, water was distilled off under atmospheric pressure over 2 hours, then the pressure was maintained at 0.04 to 0.07 MPa while continuously introducing steam, and the remaining water and by-product low boiling point compounds were distilled off under reduced pressure over 3 hours. Thereafter, 30 parts by weight of a synthetic silicate {"Kyowad 600" manufactured by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water were added, stirred at 60° C. for 3 hours, taken out from the autoclave, and the pore diameter was 1 micron After filtering with a filter, it dehydrated and obtained polyoxyalkylene polyol (a11-2). The hydroxyl value of (a11-2) was 65 mgKOH/g, the viscosity was 800 mPa*s/25 degreeC, and the primary conversion rate was 40 %. Moreover, p in General formula (1) of (a11-2) was 0, and q was about 14.

<Production Example 3>

A polyoxyalkylene polyol (a11-3) was obtained in the same manner as in Production Example 2 except that the amount of PO added in Production Example 2 was replaced with 180 parts by weight. The hydroxyl value of (a11-3) was 62 mgKOH/g, the viscosity was 980 mPa*s/25 degreeC, and the primary conversion rate was 60 %. Moreover, p in General formula (1) of (a11-3) was 0, and q was about 15.

<Production Example 4>

100 parts by weight of pentaerythritol and 0.09 parts by weight of TPB were injected into a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation facility, a raw material supply line and an exhaust line, and then stirring was started, the autoclave and the inside of the condensing facility were pressure-reduced to 0.005 MPa. 2248 parts by weight of PO was continuously added to the liquid phase over 12 hours while controlling the reaction temperature to be maintained at 70 to 80°C through the raw material supply line. A refrigerant at -30 ℃ was circulated to condense and recover PO by a condensing facility. Subsequently, after aging at 70°C for 4 hours, 200 parts by weight of water was added, followed by heating at 130 to 140°C for 1 hour. After heating for 1 hour, water was distilled off under atmospheric pressure over 2 hours, then the pressure was maintained at 0.04 to 0.07 MPa while continuously introducing steam, and the remaining water and by-product low boiling point compounds were distilled off under reduced pressure over 3 hours. Thereafter, 30 parts by weight of a synthetic silicate {"Kyowad 600" manufactured by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water were added, stirred at 60° C. for 3 hours, taken out from the autoclave, and the pore diameter was 1 micron After filtering with a filter, it dehydrated and obtained polyoxyalkylene polyol (a11-4). The hydroxyl value of (a11-4) was 43 mgKOH/g, the viscosity was 940 mPa*s/25 degreeC, and the primary conversion rate was 70 %. Moreover, p in General formula (1) of (a11-4) was 0, and q was about 25.

<Production Example 5>

100 parts by weight of polyoxypropylene glycol (2% primary conversion rate, 490 mgKOH/g hydroxyl value) prepared by reacting PO in the presence of a KOH catalyst with sorbitol as a base agent, a heat exchanger as a stirring device, a temperature control device, and a condensation facility; After putting in a stainless steel autoclave equipped with a raw material supply line and an exhaust line, and injecting 0.09 weight part of TPB, stirring was started, and the inside of an autoclave and a condensation facility was pressure-reduced to 0.005 MPa. 365 parts by weight of PO was continuously added to the liquid phase over 12 hours while controlling the reaction temperature to be maintained at 70 to 80° C. through the raw material supply line. A refrigerant at -30 ℃ was circulated to condense and recover PO by a condensing facility. Subsequently, after aging at 70°C for 4 hours, 200 parts by weight of water was added, followed by heating at 130 to 140°C for 1 hour. After heating for 1 hour, water was distilled off under atmospheric pressure over 2 hours, then the pressure was maintained at 0.04 to 0.07 MPa while continuously introducing steam, and the remaining water and by-product low boiling point compounds were distilled off under reduced pressure over 3 hours. Thereafter, 30 parts by weight of a synthetic silicate {"Kyowad 600" manufactured by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water were added, stirred at 60° C. for 3 hours, taken out from the autoclave, and the pore diameter was 1 micron After filtration with a filter, it dehydrated and obtained polyoxyalkylene polyol (a11-5). The hydroxyl value of (a11-5) was 105 mgKOH/g, the viscosity was 690 mPa*s/25 degreeC, and the primary conversion rate was 66 %. Moreover, p in General formula (1) of (a11-5) was 0, and q was about 8.

<Production Example 6>

Polyoxypropylene glycol produced by using sucrose as a base agent and reacting PO in the presence of a KOH catalyst (primary rate of 2%, hydroxyl value of 35 mgKOH/g, p in the general formula (1) is 0, q is about 27 ) 100 parts by weight were put into a stainless steel autoclave equipped with a stirring device, a temperature control device, a heat exchanger as a condensation facility, a raw material supply line and an exhaust line, and 4.0 parts by weight of potassium hydroxide was injected, and then EO 25 through the raw material supply line A weight part was continuously injected|thrown-in to the liquid phase over 12 hours while controlling the reaction temperature to maintain 90-100 degreeC. After aging at 100°C for 3 hours, 30 parts by weight of a synthetic silicate {"Kyowad 600" manufactured by Kyowa Chemical Industry Co., Ltd.} and 40 parts by weight of water were added, followed by treatment at 60°C for 3 hours. It took out from the autoclave, and after filtering with the filter whose pore diameter is 1 micron, it dehydrated and obtained the polyoxyalkylene polyol ethylene oxide adduct (a12-1). The hydroxyl value of (a12-1) was 28 mgKOH/g, the viscosity was 1,660 mPa*s/25 degreeC, and a in General formula (2) or (3) was about 9.

[Synthesis of urethane-free polymer having an isocyanate group]

<Synthesis Example 1>

PTMG3000 {bifunctional polytetramethylene ether glycol, hydroxyl value of 39 mgKOH/g, and the value of b in the general formula (6) is about 40, Mitsubishi Chemical (Mitsubishi Chemical) Co., Ltd. production} 100 parts by weight, 9.6 parts by weight of HDI (hexamethylene diisocyanate), 47 parts by weight of ethyl acetate as a solvent, Neostan U-600 (manufactured by Nitto Chemical Co., Ltd.) 0.03 parts by weight and an anti-gelling agent as a urethanization catalyst 0.05 parts by weight of diethyl malonate as a compound was added and reacted at 78°C for 6 hours to obtain a solution of a urethane-free polymer (b-1) having an isocyanate group. The isocyanate group content of the solution of (b-1) was 1.1 %, the density|concentration was 70 weight%, and the viscosity was 30,000 mPa*s/25 degreeC.

<Synthesis Examples 2 to 8>

Except changing the injection amount to the value shown in Table 1, it carried out similarly to the synthesis example 1, and obtained the solution of the urethane-free polymer (b-2) - (b-8) which have an isocyanate group. 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 is a bifunctional polytetramethylene ether glycol derivative {a hydroxyl value of 56 mgKOH/g, manufactured by Hodogaya Chemical Co., Ltd., random air of tetrahydrofuran and 3-methyltetrahydrofuran coalesce}, "IPDI" represents isophorone diisocyanate.

[Synthesis of urethane resin having a hydroxyl group]

<Synthesis Example 9>

15 parts by weight of polyoxyalkylene polyol (a11-1), 16 parts by weight of a solution of a urethane-free polymer (b-1) having an isocyanate group, and ethyl acetate as a solvent in a four-neck flask equipped with a reflux cooling tube, a stirring bar and a thermometer 34.5 weight part was thrown in, it was made to react at 78 degreeC for 10 hours, and the solution of the urethane resin (P-1) which has a hydroxyl group was obtained. The hydroxyl value of the solution of (P-1) was 11.2 mgKOH/g, the density|concentration was 40 weight%, the viscosity was 6,200 mPa*s/25 degreeC, and the weight average molecular weight was 131,000.

<Synthesis Examples 10-24, Comparative Synthesis Examples 1-2>

Except for changing the injection amount to the value shown in Table 2, in the same manner as in Synthesis Example 9, urethane resins having a hydroxyl group (P-2) to (P-16), (P'-1) to (P'-2) a solution was obtained. (P-2) - (P-16), (P'-1) - The hydroxyl value of the solution of (P'-2) shows a density|concentration, a viscosity, and a weight average molecular weight in Table 2. In addition, (a2-1) in Table 2 is Sannix GH-5000 {trifunctional polypropylene glycol, hydroxyl value is 33 mgKOH/g, Sanyo Chemical Industry Co., Ltd. product}, (a2-2) is Sannix SP-750 {6-functional polypropylene glycol, hydroxyl value of 490 mgKOH/g, manufactured by Sanyo Chemical Industry Co., Ltd.} is shown.

<Examples 1 to 16 and Comparative Examples 1 to 2>

A solution of (P-1) to (P-16) or a solution of (P'-1) to (P'-2) having a hydroxyl group as a main agent, Desmodur XP2675(D-1) {HDI as a curing agent Isocyanurate, manufactured by Covestro} or Duranate TFD-90B (D-2) {HDI isocyanurate, manufactured by Asahi Chemical Co., Ltd.}, ethyl acetate as a solvent, and dibutyltin dilaurate as a urethanation catalyst Alternatively, Borchi Kat22 {manufactured by Borchers} was mixed with the number of parts by weight shown in Table 3, followed by centrifugal defoaming to obtain a pressure-sensitive adhesive solution. It was applied to a 38 µm thick polyethylene terephthalate film using a bar coater so that the film thickness after drying and curing was set to 30 µm. After drying at 130 degreeC for 3 minutes, the peeling film was bonded together, it cured at 50 degreeC for 2 days, and the adhesive sheet was obtained. The following evaluation methods evaluated the initial adhesive force, the adhesive force after a heat resistance test, cut property, and base material adhesiveness using the obtained adhesive sheet. A result is shown in Table 3. In addition, using the adhesive cured product obtained by changing the polyethylene terephthalate film to an OPP (stretched polypropylene) film of 100 µm and changing the film thickness after drying and curing to 100 µm, the breaking strength and elongation at break in the following manner , yield and gel fraction were evaluated. A result is shown in Table 3.

(1) Measuring method of initial adhesive force

Each of the pressure-sensitive adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 to 2 is cut to a size of 100 mm × 25 mm, the release film is peeled off and bonded to a glass plate, and using a tensile tester, a tensile rate of 300 at 23°C 180° peel strength (unit: N/25 mm) was measured under the conditions of mm/min, and it was set as initial stage adhesive force. The measurement was performed about 5 samples, and the average value is shown in Table 3. When using for a surface protection sheet, the range of 0.01-0.03 N/25 mm of peeling strength is preferable from a viewpoint that there is no floating peeling and can peel easily.

(2) Method of measuring adhesive strength after heat resistance test

After cutting out the adhesive sheet obtained in Examples 1-16 and Comparative Examples 1-2 to a size of 100 mm x 25 mm, respectively, peeling a peeling film and bonding it to a glass plate, it is left still in an 85 degreeC thermostat for 7 days. ) was done. Thereafter, after 4 hours of temperature control in a temperature control room at 50%RH and 23°C, 180° peel strength (unit: N/25 mm) was measured using a tensile tester at 23°C at a tensile rate of 300 mm/min. Thus, it was set as the adhesive force after the heat resistance test. The measurement was performed about 5 samples, and the average value is shown in Table 3. It is preferable that it is the range of 0.01-0.05 N/25 mm, and, as for the peeling strength after a heat resistance test, it is more preferable that it is the range of 0.01-0.04 N/25 mm. Moreover, it is preferable that the amount of change of peeling strength after a heat resistance test compared with initial stage adhesive force is 0.025 N/25 mm or less.

(3) Measuring method of cut property

The peeling film was peeled from the adhesive sheet obtained in Examples 1-16 and Comparative Examples 1-2, the blade of a cutter was put on the adhesive surface, and it cut quickly. The cut surface after cutting was visually observed through the loupe, and the following references|standards evaluated cut property. The results are shown in Table 3. Since chips during processing contaminate an adherend and deteriorate performance, it is preferable that chips are not generated.

<Evaluation criteria>

(double-circle): The cut surface was smooth, and chips did not generate|occur|produce.

(circle): Although a cut surface was not smooth, the chippings did not generate|occur|produce.

(triangle|delta): A cut surface is not smooth, and chips have generate|occur|produced.

x: The cut surface is not smooth, and chips generate|occur|produce and are scattered around.

(4) Evaluation method of substrate adhesion

Peel the release film from the pressure-sensitive adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 and 2, and visually check whether the surface of the pressure-sensitive adhesive layer is peeled from the polyethylene terephthalate film of the substrate by rubbing the pressure-sensitive adhesive surface with a nail 10 times, respectively. and evaluated according to the following criteria. The results are shown in Table 3.

<Evaluation criteria>

(double-circle) : It does not become white and does not peel.

(circle): Although it does not peel, it becomes cloudy white.

(triangle|delta): When it rubs 6-10 times, it peels.

x: When it rubs 1-5 times, it peels.

(5) Method for measuring breaking strength and elongation at break

The release film and the OPP film were peeled off from the adhesive cured product obtained in Examples 1 to 16 and Comparative Examples 1 to 2 to prepare a dumbbell-shaped No. 3 test piece, and a tensile tester was used to pull it under an environment of 23°C and 50%RH. The breaking strength and breaking elongation of the test piece were measured under the condition of a speed of 100 mm/min. The measurement was performed with respect to five test pieces, the average value was computed, and the following criteria evaluated the breaking strength and breaking elongation. The results are shown in Table 3.

<Evaluation criteria for breaking strength>

(double-circle): It is 2.0 MPa or more.

○: 1.0 MPa or more and less than 2.0 MPa.

(triangle|delta): 0.5 Mpa or more and less than 1.0 Mpa.

x: It is less than 0.5 MPa.

<Elongation at break evaluation criteria>

(double-circle): It is 100 % or more.

(circle): 75 % or more and less than 100 %.

(triangle|delta): 50 % or more and less than 75 %.

x: It is less than 50 %.

(6) Evaluation method of yield

Each of the pressure-sensitive adhesive sheets obtained in Examples 1 to 16 and Comparative Examples 1 to 2 was cut to a size of 100 mm × 25 mm to prepare a test piece, and after peeling the release film, 5 mm × 25 mm of one end of the test piece was placed on a glass plate It was attached and fixed so that it might not peel. Next, the short side part of the test piece was hung up vertically from the glass plate and the 95 mm x 25 mm part which is not bonded together. Next, the suspended test piece was released, and time until the whole test piece closely_contact|adhered to the surface of a glass plate was measured. The measurement was performed with respect to five test pieces, the average value was computed, and the following reference|standard evaluated the yield. The results are shown in Table 3. It means that bubbles etc. are hard to mix at the time of bonding, so that the time until close_contact|adherence is short, and a yield is favorable.

<Evaluation criteria>

◎: less than 2.0 seconds.

○: 2.0 seconds or more and less than 4.0 seconds.

(triangle|delta): 4.0 second or more and less than 8.0 second.

×: 8.0 seconds or longer.

(7) Evaluation method of gel fraction

The adhesive cured product obtained in Examples 1 to 16 and Comparative Examples 1 to 2 was cut to a size of about 70 mm × about 70 mm, and after peeling the release film and the OPP film, fold it into 4 pieces to have a size of about 35 mm × about 35 mm It was set as the test piece. Separately, a SUS mesh having a grid interval of 77 µm was cut to 150 mm x 150 mm, molded in a drawstring purse shape, and the mouth was closed with a wire to provide a packaging material. After measuring the weight (W1) of the packaging material, the wire was opened, the test piece was put, and the weight (W2) was measured again, put into a glass bottle, and immersed in 100 mL of ethyl acetate. After standing at 25°C for 24 hours, taking out from ethyl acetate, drying by heating at 130°C for 90 minutes in a dryer, measuring the weight (W3), and evaluating the gel fraction calculated by the following formula (1) based on the following criteria did The results are shown in Table 3. As the gel fraction is higher, it means that the adhesive is cured to a practical level with a short curing time.

Gel fraction (wt%) = (W3 - W1)/(W2 - W1) × 100 (1)

<Evaluation criteria>

(double-circle) : 90 % or more.

○: 70% or more and less than 90%.

(triangle|delta): 50 % or more and less than 70 %.

x: less than 50%.

The main agent for two-component curing type urethane adhesive of the present invention and two-component curing type urethane pressure-sensitive adhesive using the same can be used in a wide range of applications, such as for protection of optical members in the manufacturing process of image display devices, such as polarizing plates, and for sticking between optical members yes, it is very useful

Claims (8)

containing a main agent and a hardener,
The above subject has a hydroxyl group formed by reacting a polyol component (a) containing as an essential component a polyfunctional polyoxyalkylene polyol (a1) having a hydroxyl group of 10 to 350 mgKOH/g and a urethane-free polymer (b) having an isocyanate group containing a urethane resin (P),
The polyfunctional polyoxyalkylene polyol (a1) is a polyoxyalkylene polyol (a11) having a hydroxypropyl group at the molecular terminal represented by the general formula (1) and/or an ethylene oxide adduct (a12) thereof;
The said hardening|curing agent contains the crosslinking agent (D) which has an isocyanate group, The two-component curable urethane adhesive.

[In the general formula (1), X is an m-valent residue obtained by excluding all active hydrogen atoms from a compound having m active hydrogen atoms; A is a phenyl group, a halophenyl group, or an alkylene group having 2 to 12 carbon atoms which may be substituted with a halogen atom; Z is a propylene group; m is an integer of 4 to 10; p is an integer from 0 to 199, q is an integer from 1 to 200, satisfying 1 ≤ p + q ≤ 200.] The method of claim 1,
The two-component curable urethane pressure-sensitive adhesive wherein the urethane-free polymer (b) is a compound represented by the general formula (6).

[In the general formula (6), L is a divalent group excluding an isocyanate group from the polyisocyanate component (bp), U represents a urethane bond, R is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and b is An integer of 20 to 70, and the number average value of s is 1.01 to 10.] 3. The method according to claim 1 or 2,
The said urethane-free polymer (b) is bifunctional, and the isocyanate group content based on the weight of the said urethane-free polymer (b) is 0.1 to 12 weight% of two-component curable urethane adhesive. 4. The method according to any one of claims 1 to 3,
The polyfunctional polyoxyalkylene polyol (a1) is 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, and the polyfunctional polyoxyalkylene polyol (a1) is The sum of the number of groups represented by the number of groups represented by the general formula (2) and the number of groups represented by the general formula (3) that the polyfunctional polyoxyalkylene polyol (a1) has in the ratio of the number of groups represented by the general formula (2) Two-component curing type urethane adhesive with 40% or more based on

[In the general formulas (2) and (3), a is each independently an integer of 0 or more.] 5. The method according to any one of claims 1 to 4,
The polyfunctional polyoxyalkylene polyol (a1) is an alkylene oxide adduct of sorbitol, the alkylene oxide contains propylene oxide, and the added mole number of the propylene oxide is 50 to 200, a two-component curable urethane pressure-sensitive adhesive. 6. The method according to any one of claims 1 to 5,
The two-component curable urethane adhesive whose weight average molecular weights of the said urethane resin (P) are 10,000-500,000. Hardened|cured material of the two-component curable urethane adhesive in any one of Claims 1-6. The urethane adhesive sheet formed using the two-component curing type urethane adhesive in any one of Claims 1-6.