TW202202540A - Pressure-sensitive adhesive, and pressure-sensitive adhesive sheet - Google Patents

Abstract

The present invention provides an adhesive that exhibits excellent initial curability, can suppress an increase in adhesive force even when exposed to a hot environment and particularly to a hot, humid environment, and can form an adhesive layer having excellent re-peeling properties. Also provided is an adhesive sheet in which said adhesive is used. The adhesive of the present invention comprises: a hydroxyl group-terminated urethane prepolymer (UPH) that is a reaction product between one or more active hydrogen group-containing compounds (H) having a plurality of active hydrogen groups per molecule, and one or more polyisocyanates (N); and a polyfunctional isocyanate compound (I). The hydrogen group-terminated urethane prepolymer (UHP) is a urethane-based adhesive having a degree of branching of 0.2-0.8 as measured by the GPC-MALS method.

Description

Adhesives and Adhesive Sheets

This application claims priority based on Japanese Patent Application No. 2020-112855 for which it applied on June 30, 2020, and the entire content of the disclosure is incorporated into this application. The present invention relates to an adhesive and an adhesive sheet.

Conventionally, as a surface protection sheet for various members, an adhesive sheet having an adhesive layer formed on a base sheet has been widely used. As the adhesive, there are acrylic adhesives, silicone adhesives, urethane adhesives, and the like. Acrylic adhesives have excellent adhesive strength, but because of their high adhesive strength, the re-peelability after being attached to an adherend is poor. Regarding silicone-based adhesives, there are also concerns that the adherends are prone to contamination, and silicone resins with relatively low molecular weights are volatilized and adsorbed on the surfaces of electronic components and other equipment, causing problems. On the other hand, the urethane-based adhesive has good adhesiveness with respect to the adherend, is excellent in re-peelability, and is not easily volatile. In this specification, unless otherwise specified, “adhesive” refers to a releasable adhesive (removable adhesive), and “adhesive sheet” refers to a releasable adhesive (removable adhesive) .

As a method for producing a urethane-based adhesive, there is a method of using a hydroxyl-terminated urethane prepolymer and a polyfunctional isocyanate compound as a reaction product of an active hydrogen group-containing compound such as a polyol and a polyisocyanate. and a method of reacting a polyol and a polyfunctional isocyanate compound in one shot (one shot method) without using a hydroxyl-terminated urethane prepolymer.

A general method of manufacturing an adhesive sheet includes: a coating step of applying an adhesive on a substrate sheet; a heating step of subjecting the formed coating layer to heat and drying treatment to form an adhesive layer of a cured product containing the adhesive; roll In the winding step, the obtained adhesive sheet is wound on the core to form the form of the adhesive sheet roll; and the curing step is for curing the adhesive sheet roll.

Flat panel displays such as liquid crystal displays (LCDs) and organic electroluminescence displays (OELDs), as well as touch panel displays combining the flat panel displays and touch panels, are widely used in televisions (television). , TV), personal computer (PC), mobile phone, and portable information terminals and other electronic equipment. Urethane-based adhesive sheets can be preferably used as flat panel displays and touch panel displays, as well as substrates (glass substrates, and indium tin oxide ( indium tin oxide, ITO) film, ITO/glass substrate, etc.) and surface protection sheet for optical components, etc. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-256124 [Patent Document 2] International Publication No. 2015/141380 [Patent Document 3] Japanese Patent Laid-Open No. 2017-193601 [Patent Document 4] International Publication No. 2015/141379

[The problem to be solved by the invention]

Urethane-based adhesives are hardened shortly after production. If the initial curability of the urethane-based adhesive is too low, the re-peelability of the adhesive layer decreases, and the components of the adhesive layer tend to adhere to fingers, adherends, etc. that are in contact with the adhesive layer. In this case, after the adhesive sheet is peeled off from the fingers and the adherend, so-called "residual glue" (also known as "adhesive contamination") is likely to occur in which the components of the adhesive layer remain on the fingers and the adherend. ”). The urethane-based adhesive preferably has good initial hardening properties.

When the adhesive sheet is exposed to a heat environment, especially a humid heat environment, the anchoring property between the adherend and the adhesive layer becomes high, and as a result, the adhesive force of the adhesive layer increases and the re-peelability tends to decrease. The adhesive sheet preferably has good re-peelability even when exposed to a heat environment, especially a humid-heat environment, and no adhesive layer components remain on the surface of the adherend after re-peeling.

Patent Documents 1 to 4 can be cited as the related technologies of the present invention. Patent Document 1 discloses a re-peelable water-dispersible pressure-sensitive adhesive (acrylic adhesive) containing as a main component a (meth)acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms as a main component. An aqueous dispersion of a polymer of monomers having a weight average molecular weight of 2.5 million or more and a polymer having a molecular weight of 5 million having a number of branches per molecule of 5 or less (first invention).

Patent Document 2 discloses an adhesive composition for polarizing plates (acrylic adhesive), which contains: (A) A (meth)acrylic copolymer obtained by copolymerizing a monomer component containing an alkyl (meth)acrylate having 4 to 18 carbon atoms in an alkyl group and a carboxyl group-containing monomer, and using a gel The branching degree measured by permeation chromatography/multi-angle laser light scattering detector (GPC-MALS (gel permeation chromatography-multi angle laser light scattering)) is below 0.55, and the acid value 0.1 mgKOH/g～7.8 mgKOH/g; (B1) isocyanate compounds; and (B2) Metal chelate compound (first invention).

Patent Document 3 discloses a photocurable adhesive precursor composition comprising an ethylenically unsaturated monomer, a prepolymer having a monomer unit derived from a hydrogen-donating monomer, and a hydrogen abstraction type photoinitiator agent (first invention). The ethylenically unsaturated monomer is preferably a (meth)acrylate (paragraph 0021). The hydrogen-donating monomer preferably has an ethylenically unsaturated double bond and is at least one selected from the group consisting of an amine group, an amide group, a hydroxyl group, a thiol group, a heterocyclic ring, and an alkylene oxide chain (No. two inventions). Patent Document 3 discloses a photocurable adhesive comprising a random branched (co)polymer having a branching degree of 0.25 or more and 0.44 or less (fifth invention). In Examples 1 to 3 of Patent Document 3, acrylic adhesives were produced.

Patent Document 4 discloses an adhesive composition for polarizing plates (acrylic adhesive) comprising: (A) a (meth)acrylic copolymer in which (methyl) having an alkyl group having 4 to 18 carbon atoms is added. It is obtained by copolymerizing monomer components of alkyl acrylate and a hydroxyl group-containing monomer, and the branching degree measured by gel permeation chromatography/multi-angle laser light scattering detector (GPC-MALS) is 0.55 or less; and (B) Isocyanate compound (1st invention). The symbols of the respective components described in Patent Documents 1 to 4 are the symbols described in these documents, and have no relation to the symbols used for the respective components of the present invention.

Patent Documents 1 to 4 describe the number of branches or the degree of branching of the acrylic (co)polymer. These patent documents all relate to acrylic adhesives, not urethane adhesives. For urethane-based adhesives, there is no document describing the degree of branching of the prepolymer or its raw material.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive and an adhesive sheet using the same, which have good initial hardening properties and can be formed even when exposed to a heat environment, especially a humid heat environment In the case of the adhesive layer, the increase in the adhesive force is suppressed and the re-peelability is good. [Means of Solving Problems]

The adhesive of the present invention comprises: Hydroxy-terminated urethane prepolymer (UPH), the hydroxyl-terminated urethane prepolymer (UPH) is one or more active hydrogen group-containing compounds having a plurality of active hydrogen groups in one molecule ( H), reaction products with more than one polyisocyanate (N); and polyfunctional isocyanate compound (I), The adhesive is a urethane-based adhesive with a branching degree of 0.2-0.8 measured by GPC-MALS method in a hydroxyl-terminated urethane prepolymer (UPH).

In the adhesive of the first embodiment of the present invention, One or more active hydrogen group-containing compounds (H) contain 50% by mass or more of active hydrogen group-containing compounds (HX) having a branching degree measured by GPC-MALS method of 0.5 or less, The branching degree measured by the GPC-MALS method in the hydroxyl-terminated urethane prepolymer (UPH) was 0.2 to 0.6.

In the adhesive of the second embodiment of the present invention, One or more active hydrogen group-containing compounds (H) containing 50% by mass or more of active hydrogen group-containing compounds (HY) having a branching degree of more than 0.5 as measured by GPC-MALS method, In the hydroxyl-terminated urethane prepolymer (UPH), the branching degree measured by the GPC-MALS method exceeded 0.6 and was 0.8 or less.

The adhesive sheet of the present invention includes a base material sheet and an adhesive layer containing a cured product of the adhesive of the present invention. [Effect of invention]

According to the present invention, it is possible to provide an adhesive and an adhesive sheet using the adhesive, the adhesive having good initial hardening properties and capable of suppressing an increase in adhesive force even when exposed to a heat environment, particularly a humid heat environment , and the adhesive layer with good re-peelability. According to the first aspect of the present invention, there can be provided an adhesive and an adhesive sheet using the adhesive, the initial hardenability of the adhesive, and the re-peelability when exposed to a heat environment, particularly a humid heat environment (suppression of adhesion) can be provided. The effect of increasing the force) is good, and it is possible to form an adhesive layer with good substrate adhesion, scratch resistance, and curved surface adhesion. According to the second aspect of the present invention, there can be provided an adhesive and an adhesive sheet using the same, the initial hardenability of the adhesive and the re-peelability when exposed to a heat environment, especially a humid heat environment (suppression of adhesion) can be provided. The effect of increasing the force) is good, and it is possible to form an adhesive layer with good folding resistance, cutting properties, and heat resistance.

[adhesive] The adhesive of the present invention comprises: Hydroxy-terminated urethane prepolymer (UPH) (also referred to as "prepolymer"), the hydroxyl-terminated urethane prepolymer (UPH) is a molecule with multiple active hydrogen groups. The reaction product of one or more active hydrogen group-containing compounds (H) and one or more polyisocyanates (N); and polyfunctional isocyanate compound (I), The adhesive is a re-peelable urethane with a branching degree α (also referred to as "branching degree α") measured by GPC-MALS method in a hydroxyl-terminated urethane prepolymer (UPH) of 0.2 to 0.8. Ester based adhesive. The pressure-sensitive adhesive sheet of the present invention is a urethane-based pressure-sensitive adhesive sheet including a base material sheet and an adhesive layer including a cured product of the pressure-sensitive adhesive of the present invention.

"Branching degree α" is a device that combines a multi-angle light scattering detector (MALS) with a viscosity detector (VISCO) and a gel permeation chromatography (GPC) (also known as "GPC-MALS" or "GPC"). -MALS-VISCO"), and measured by a known method. Regarding the measurement of the branching degree α by GPC-MALS, please refer to Patent Documents 1 to 4 listed in the section [Prior Art].

The GPC method is a method of measuring the molecular weight according to the elution time by passing a solution of a sample whose molecular weight is to be measured through a column filled with a porous material such as silica. The smaller the molecular size, the more the sample passes through the deeper part in the pores of the porous material, so the elution time becomes longer. The molecular weight of the sample is determined by comparing a standard substance of known molecular weight with the dissolution time. The length of the dissolution time of the sample in the GPC method corresponds to the size of the molecular size, but the size of the molecular size is not strictly related to the size of the molecular weight. Since the molecular size varies according to the affinity with the chaotropic liquid, the molecular weight cannot be accurately determined depending on the polarity of the sample. The molecular size also varies according to the branching state of the molecule. Even with the same molecular weight, the more branches, the smaller the molecular size. There are cases where the actual molecular weight (absolute molecular weight) differs depending on the polarity or the branched state of the molecule even in samples with the same elution time. However, in the GPC method, the measured molecular weights are the same in samples with the same elution time.

In GPC-MALS, in addition to normal GPC measurement, a sample solution is irradiated with laser light of a specific wavelength, and the scattered light intensity by Rayleigh scattering is measured. The scattered light intensity varies depending on the molecular size and branching state. For example, in the case of a sample with a small molecular size and no branches, there is only one scattering point, and the scattered light intensity becomes low. In the case of a sample with a large molecular size and many branches, there are many scattering points, and the scattered light intensity becomes high. In GPC-MALS, VISCO was also used to determine the intrinsic viscosity of the samples. The absolute molecular weight can also be determined by GPC-MALS.

The relationship between the intrinsic viscosity, density, weight average molecular weight (Mw), and branching degree α is represented by the calculation formula (the following formula) of Mark-Houwink-Sakurada. [Number 1] log[η]=logK+αlogMw In the formula, log[η] represents the intrinsic viscosity, logK represents the density, Mw represents the weight average molecular weight, and α represents the degree of branching. In (pre-)polymer molecules, the smaller the α value, the more branches (high branching), forming a spherical or nearly spherical shape (approximately in the range of α < 0.5), and the larger the α value, the less branching (low branching). branch), forming a rod-like or nearly rod-like shape (approximately in the range of α>0.8).

For example, as shown in FIG. 3 , when 3 molecules of relatively high branched polyol (PO1), 5 molecules of relatively low branched polyol (PO2), and 7 molecules of relatively low branched polyisocyanate (PI1) are reacted In this case, it is possible to generate a relatively high branched prepolymer (PP1), a relatively low branched prepolymer (PP2), or a prepolymer in an intermediate branched state of these. Prepolymer (PP1) and prepolymer (PP2) have the same molecular weight, but different branching states, different molecular sizes and molecular shapes. 3 is an image diagram of a reaction example. As explained in the section [Problems to be Solved by the Invention], in the case of urethane-based adhesives, there is no document describing the degree of branching α of the prepolymer or its raw material. In the present invention, the branching degree α of the prepolymer or its raw material is optimized, and the properties of the adhesive are optimized. The branching degree α of the prepolymer can be adjusted according to the branching degree α of the various raw materials used, the combination of the various raw materials used, the amount ratio of the various raw materials used, the reaction conditions, and the reaction procedure.

The branching degree α of the hydroxyl-terminated urethane prepolymer (UPH) contained in the adhesive of the present invention is 0.2 to 0.8. When the branching degree α is less than 0.2, the prepolymer molecule has many branches (high branching), and has a spherical or nearly spherical shape. During the reaction between the hydroxyl-terminated urethane prepolymer (UPH) and the hardener, the intramolecular reaction of the adhesive containing the hyperbranched hydroxyl-terminated urethane prepolymer (UPH) is excessive, and the intermolecular reaction is inhibited. As the crosslinking reaction proceeds, the initial curability tends to decrease. Furthermore, the re-peelability of the adhesive layer is reduced centered on the portion with a low degree of intermolecular cross-linking, and after the adhesive sheet is peeled off from the finger and the adherend, the components that are likely to generate an adhesive layer remain on the finger, the adherend, etc. the so-called "residual glue" (also known as "sticky contamination"). In addition, when exposed to a heat environment, especially a humid heat environment, the increase in the adhesive force becomes large, and the re-peelability tends to decrease.

When the branching degree α exceeds 0.8, the prepolymer molecule has few branches (low branching), and has a rod-like or nearly rod-like shape. In adhesives containing a low-branched hydroxyl-terminated urethane prepolymer (UPH), it is difficult to form a high density because the hydroxyl-terminated urethane prepolymer (UPH) has a rod-like or nearly rod-like shape The cross-linked structure is easy to reduce the initial hardenability. Furthermore, the cross-linked structure becomes insufficient, and as a result, the re-peelability of the adhesive layer is lowered, and after the adhesive sheet is peeled off from the fingers, the adherend, etc., the components of the adhesive layer are likely to remain on the fingers, the adherend, etc., so-called so-called. "Glue residue" (contaminated with sticky substances). In addition, when exposed to a heat environment, especially a humid heat environment, the increase in the adhesive force becomes large, and the re-peelability tends to decrease.

By using a hydroxyl-terminated urethane prepolymer (UPH) with a branching degree α in the range of 0.2 to 0.8, when the hydroxyl-terminated urethane prepolymer (UPH) reacts with a curing agent, the molecular The internal reaction and the intermolecular cross-linking reaction proceed moderately, and a high-density cross-linked structure is formed in the early stage, so the following adhesives can be provided. An adhesive layer having good re-peelability while suppressing the increase in adhesive force even in the case.

(first embodiment) In the adhesive according to the first embodiment of the present invention, one or more active hydrogen group-containing compounds (H) contain 50% by mass or more of active hydrogen group-containing compounds having a branching degree α measured by GPC-MALS method of 0.5 or less. In compound (HX), the branching degree α measured by GPC-MALS method in the hydroxyl-terminated urethane prepolymer (UPH) is 0.2 to 0.6. In the adhesive of the first embodiment, since the intramolecular crosslinking reaction proceeds early and advantageously while maintaining the progress of the intermolecular crosslinking reaction, the initial hardenability and exposure to a heat environment, especially a humid heat environment The re-peelability (the effect of suppressing the increase in adhesive force) during the Adhesive layer with good properties and surface adhesion.

In the adhesive of the first embodiment, the branching degree α measured by the GPC-MALS method in the hydroxyl-terminated urethane prepolymer (UPH) is preferably 0.3 in order to effectively obtain the above-mentioned effects. to 0.6, more preferably 0.4 to 0.6.

In the adhesive of the first embodiment, in order to effectively obtain the above-mentioned effects, it is preferable that one or more active hydrogen group-containing compounds (H) contain 50% by mass or more and less than 100% by mass of the active-hydrogen group-containing compound (H). Active hydrogen group-containing compounds (HX) having a branching degree α measured by GPC-MALS method of 0.5 or less, including more than 0 mass % and less than 50 mass % of active hydrogen group-containing compounds having a branching degree α measured by GPC-MALS method exceeding 0.5 Hydrogen-based compounds (HY). When the active hydrogen group-containing compound (H) satisfies the above-mentioned requirements, the contrast between the sparse part and the dense part in the generated urethane bond is stronger, so that the performance of the sea-island structure can be effectively improved. the effect.

In the adhesive of the first embodiment, it is preferable that one or more active hydrogen group-containing compounds (H) contain a branching degree α of 0.3 as measured by the GPC-MALS method in order to effectively obtain the above-mentioned effects. The following active hydrogen group-containing compound (HX-S) is more preferably an active hydrogen group-containing compound having a branching degree α of 0.2 or less.

It is more preferable that the adhesive of 1st Embodiment contains 70 mass % or more of 1 or more types of active hydrogen group-containing compounds (HX) whose branching degree α is 0.5 or less. The adhesive of the first embodiment is more preferably more than 0 mass % and less than 30 mass % containing one or more active hydrogen group-containing compounds (HY) having a branching degree α of more than 0.5, particularly preferably more than 10 mass % and less than 30 mass %. When the active hydrogen group-containing compound (H) satisfies the above-mentioned requirements, a denser urethane bond is formed, and the above-mentioned effect due to the expression of the sea-island structure is effectively enhanced.

(Second Embodiment) In the adhesive according to the second aspect of the present invention, the one or more active hydrogen group-containing compounds (H) contain 50% by mass or more of an active hydrogen group-containing compound whose branching degree α measured by GPC-MALS method exceeds 0.5 (HY), the branching degree α measured by the GPC-MALS method in the hydroxyl-terminated urethane prepolymer (UPH) exceeds 0.6 and is 0.8 or less. In the adhesive of the second embodiment, since a cross-linked structure is formed at an early stage due to an appropriate branching structure contained in the hydroxyl-terminated urethane prepolymer (UPH), initial hardenability and exposure can be formed. Adhesive layer with good re-peelability (the effect of suppressing the increase in adhesive force) in a hot environment, especially in a humid and hot environment. Moreover, in the adhesive agent of 2nd Embodiment, since the structure which has a comparatively sparse crosslinking density is formed, it becomes possible to form an adhesive layer with good folding resistance, cutting property, and heat resistance.

In the adhesive of the second embodiment, the hydroxyl-terminated urethane prepolymer (UPH) is more preferably a GPC- The degree of branching α measured by the MALS method was 0.7 to 0.8.

In the adhesive of the second embodiment, it is preferable that one or more active hydrogen group-containing compounds (H) are contained in an amount of 50% by mass in terms of forming a uniform and moderate cross-linked structure and effectively obtaining the above-mentioned effects. More than and less than 100 mass % of active hydrogen group-containing compounds (HY) whose branching degree α measured by GPC-MALS method exceeds 0.5, including more than 0 mass % and less than 50 mass % measured by GPC-MALS method An active hydrogen group-containing compound (HX) having a branching degree α of 0.5 or less.

In the adhesive of the second embodiment, it is preferable that one or more active hydrogen group-containing compounds (H) are contained in an amount of 50% by mass in terms of forming a uniform and moderate cross-linked structure and effectively obtaining the above-mentioned effects. The above active hydrogen group-containing compound (HY-L) whose branching degree α measured by the GPC-MALS method exceeds 0.6.

In the adhesive of the second embodiment, the branching degree α of the active hydrogen group-containing compound (HY) is more preferably 0.8 or more. The adhesive of the second embodiment more preferably contains 70% by mass or more of one or more active hydrogen group-containing compounds (HY). The adhesive of the second embodiment is more preferably more than 0 mass % and less than 30 mass % containing one or more active hydrogen group-containing compounds (HX) having a branching degree α of 0.5 or less, particularly preferably 10 mass % or more And less than 30 mass %.

(Hydroxy-terminated urethane prepolymer (UPH)) The hydroxyl-terminated urethane prepolymer (UPH) is a reaction product obtained by copolymerizing one or more active hydrogen group-containing compounds (H) and one or more polyisocyanates (N). The copolymerization reaction may be carried out in the presence of one or more catalysts as needed. In the copolymerization reaction, if necessary, one or more solvents may be used. In the present invention, the branching degree α of each of the various raw materials used, the combination of the various raw materials used, the amount ratio of the various raw materials used, the reaction conditions, and the reaction procedure are adjusted to obtain a hydroxyl-terminated urethane prepolymer. The branching degree α of (UPH) is in the range of 0.2 to 0.8.

In the adhesive of the first embodiment, the weight average molecular weight (Mw) of the hydroxyl-terminated urethane prepolymer (UPH) is preferably 40,000 or more, more preferably 60,000 or more, and particularly preferably 80,000 or more . When Mw is more than the said lower limit, initial stage hardenability and re-peelability become favorable.

In the adhesive of the second embodiment, the weight average molecular weight (Mw) of the hydroxyl-terminated urethane prepolymer (UPH) is preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more . When Mw is more than the said lower limit, initial stage hardenability, re-peelability, and heat resistance become favorable.

<Active hydrogen group-containing compound (H)> The active hydrogen group-containing compound (H) is a compound having a plurality of active hydrogen groups in one molecule. As an active hydrogen group, a hydroxyl group (hydroxyl group), a mercapto group, and an amine group (in this specification, unless otherwise specified, an amine group includes an imine group) etc. are mentioned. Examples of the active hydrogen group-containing compound (H) include polyols having a plurality of hydroxyl groups in one molecule, polyamines having a plurality of amino groups in one molecule, amino alcohols having an amino group and a hydroxyl group in one molecule, and polythiols having multiple mercapto groups in one molecule. These active hydrogen group-containing compounds (H) may be non-polymers or polymers. One or two or more of these can be used. Among them, polyhydric alcohols are preferred. Since polyamines and polythiols have high reactivity with polyisocyanates and have a short pot life, when these are used, they are preferably used in combination with polyols.

Examples of polyols that can be used as the active hydrogen group-containing compound (H) include polyester polyols, polyether polyols, polyacrylic acid polyols, polycaprolactone polyols, polycarbonate polyols, and castor polyols. Sesame oil-based polyols, etc. Among them, polyester polyols, polyether polyols, and combinations thereof are preferred in terms of moderate flexibility, better adhesion of the adhesive layer, folding resistance, and curved surface adhesion. Furthermore, it is particularly preferable that the one or more active hydrogen group-containing compounds (H) contain a polyether polyol in terms of better hydrolysis resistance.

As the polyester polyol which can be used as the active hydrogen group-containing compound (H), a known one can be used. As a polyester polyol, the compound (esterified product) obtained by the esterification reaction of one or more polyol components and one or more acid components is mentioned, for example.

The polyol component of the raw material includes ethylene glycol (EG), propylene glycol (PG), diethylene glycol, 1,3-butanediol, 1,4-butanediol, new Pentanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1 ,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1 , 8-octanediol, 1,8-decanediol, octadecanediol, glycerol, trimethylolpropane, and pentaerythritol, etc.

Examples of the acid component of the raw material include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-decanedioic acid Tetraalkanedioic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid Formic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, acid anhydrides thereof, and the like.

As the polyether polyol which can be used as the active hydrogen group-containing compound (H), a known one can be used. Examples of the polyether polyol include compounds obtained by addition-polymerizing one or more oxirane compounds using an active hydrogen group-containing compound having a plurality of active hydrogen groups in one molecule as an initiator (addition-polymerization). into polymers).

As a starting agent, a hydroxyl group-containing compound, amines, etc. are mentioned. Specifically, ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol, neopentyl glycol, butylethylpentanediol, N-aminoethylethanolamine, isophor Difunctional initiators such as ketone diamine and xylylenediamine; trifunctional initiators such as glycerol, trimethylolpropane, and triethanolamine; tetrafunctional initiators such as pentaerythritol, ethylenediamine, and aromatic diamines Functional initiators, etc. Examples of the oxirane compound include alkylene oxides such as ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). AO); tetrahydrofuran (tetrahydrofuran, THF) and so on.

The polyether polyol is preferably an alkylene oxide adduct of an active hydrogen group-containing compound (also referred to as polyoxyalkylene polyol). Among them, polyethylene glycol (PEG), polypropylene glycol (PPG), PPG with ethylene oxide (EO) added to the end (PPG-EO), and polytetramethylene are preferred. Difunctional polyether polyols such as polyalkylene glycols such as diols; trifunctional polyether polyols such as alkylene oxide adducts of glycerin, etc.

Examples of polyamines that can be used as the active hydrogen group-containing compound (H) include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-propanediamine, and 1,2-propanediamine. 5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12- Dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, hexamethylenediamine, trimethylhexamethylenediamine, iminobispropylamine , methyliminobispropylamine, 1,5-diamino-2-methylpentane, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexyl Amino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine, norbornane skeleton dimethylamine, meta-xylylene diamine, MXDA), hexamethylenediamine carbamate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine and other aliphatic polyamines; 3,3'-dichloro- 4,4'-Diaminodiphenylmethane (3,3'-dichloro-4,4'-diaminodiphenylmethane, MOCA), 4,4'-diaminodiphenylmethane, 2,4'-diamine diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 3,3'-diamine Biphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-toluenediamine, 2,4-toluene Aromatic polyamines such as diamine, 2,5-toluenediamine, 2,6-toluenediamine, 3,4-toluenediamine, and diethyltoluenediamine, and the like.

Examples of the amino alcohol that can be used as the active hydrogen group-containing compound (H) include monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, and tris(hydroxymethyl)amino Monoamines having hydroxyl groups such as methane and 2-amino-2-ethyl-1,3-propanediol; diamines having hydroxyl groups such as N-(2-hydroxypropyl)ethanolamine, and the like.

As the polythiol which can be used as the active hydrogen group-containing compound (H), methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, Butanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol Thiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol Alcohol, 1,3-propanedithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,5-naphthalenedithiol, 1,2-dithiol Benzenedimethanethiol, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4'-thiodiphenylthiol, 2,5-dimercapto-1,3,4 - Thiadiazole, 1,8-dimercapto-3,6-dioxoctane, 1,5-dimercapto-3-thiapentane, 2-di-n-butylamino-4,6-di mercapto-s-triazine, and thiol-terminated polymers (polysulfide polymers, etc.), etc.

One or more active hydrogen group-containing compounds (H) may include a difunctional active hydrogen group-containing compound and/or a trifunctional or more active hydrogen group-containing compound. In general, the bifunctional active hydrogen group-containing compound has two-dimensional crosslinking properties and can impart moderate flexibility to the adhesive layer. The trifunctional or higher active hydrogen group-containing compound has three-dimensional crosslinking properties, and can impart moderate hardness to the adhesive layer. By selecting the number of functional groups (the number of active hydrogen groups) of each active hydrogen group-containing compound (H), the properties of the urethane-based adhesive such as adhesion, cohesion, and releasability can be adjusted. The number of functional groups of various materials can be selected according to the application, etc., so that the properties such as adhesive force, cohesion force, and re-peelability are in a preferable range. The one or more active hydrogen group-containing compounds (H) preferably contain a bifunctional active hydrogen group-containing compound and a trifunctional or more active hydrogen group-containing compound in view of easy compatibility of adhesive force and releasability.

The active hydrogen group-containing compound (H) preferably contains an active hydrogen group-containing compound (HX) having a branching degree α measured by GPC-MALS method of 0.5 or less, and a branching degree α measured by GPC-MALS method exceeding 0.5 The active hydrogen-containing compound (HY). The branching degree α of the active hydrogen group-containing compound (H) can be adjusted according to the structures of the various raw materials used, the amount ratio of the various raw materials used, the combination of the various raw materials used, the reaction conditions, and the reaction procedure. Furthermore, even if the raw material composition is the same, when the molecular weight of the active hydrogen group-containing compound (H) changes, the branching degree α thereof changes. Even if the molecular weight of the active hydrogen group-containing compound (H) is the same, if the branching structure is changed, the branching degree α also changes. When the branched structure of the active hydrogen group-containing compound (H) is changed, the number of functional groups may change depending on the composition.

The number of functional groups of the active hydrogen group-containing compound (H) is not particularly limited. It is preferable that the number of functional groups of the active hydrogen group-containing compound (HX) having a branching degree α of 0.5 or less is trifunctional or more, in terms of easily obtaining a highly branched structure. The number of functional groups of the active hydrogen group-containing compound (HY) having a branching degree α of more than 0.5 is preferably not more than bifunctional in terms of easily obtaining a low-branched structure.

The number average molecular weight (Mn) of the active hydrogen group-containing compound (H) is not particularly limited. The Mn of the active hydrogen group-containing compound (H) is preferably from 50 to 20,000, more preferably from 100 to 15,000, and particularly preferably from 400 to 10,000, so that the adhesive force and wettability of the adhesive layer become better. Mn of the active hydrogen group-containing compound (H) affects the branching degree α. However, as described above, the branching degree α is also influenced by factors other than Mn.

The active hydrogen group-containing compound (H) preferably contains an active hydrogen group-containing compound having a primary hydroxyl group. In this case, the initial hardenability of the adhesive can be improved.

＜Polyisocyanate (N)＞ As polyisocyanate (N), a well-known thing can be used, and an aromatic polyisocyanate, an aliphatic polyisocyanate, an alicyclic polyisocyanate, etc. are mentioned.

As aromatic polyisocyanate, 1, 3- phenylene diisocyanate, 4, 4'- diphenyl diisocyanate, 1, 4- phenylene diisocyanate, 4, 4'- diphenylmethane diisocyanate can be mentioned. Isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, Lianda Anisidine diisocyanate, 4,4'-diphenylether diisocyanate, and 4,4',4''-triphenylmethane triisocyanate, ω,ω'-diisocyanate-1,3-dimethylbenzene , ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylenediisocyanate, and 1,3-Tetramethylxylylene diisocyanate, etc.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate Isocyanates, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexane Diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), and 1,4-bis (Isocyanate methyl) cyclohexane and the like.

Moreover, as polyisocyanate, the trimethylolpropane adduct, biuret (biuret) body, allophanate (allophanate) body, and trimer (this trimer contains isocyanurate ring), etc.

A preferable raw material formulation example of the hydroxyl-terminated urethane prepolymer (UPH) is as follows. Preferably, the ratio of the molar number of isocyanate groups (NCO) possessed by the polyisocyanate (N) to the total molar number of active hydrogen groups (H) possessed by a plurality of active hydrogen group-containing compounds (H) ( The raw material mixing ratio is determined so that the NCO/H ratio) becomes 0.20 to 0.95, preferably 0.40 to 0.85. There is a tendency that the closer the NCO/H ratio is to 1, the easier it is to gel when synthesizing a hydroxyl-terminated urethane prepolymer (UPH). When the NCO/H ratio is 0.95 or less, gelation at the time of synthesizing a hydroxyl-terminated urethane prepolymer (UPH) can be effectively suppressed.

＜Catalyst＞ In the polymerization of the hydroxyl-terminated urethane prepolymer (UPH), if necessary, one or more catalysts may be used. As a catalyst, a well-known thing can be used, and a tertiary amine compound, an organometallic compound, etc. are mentioned. Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7(1,8-diazabicyclo( 5,4,0)-undecene-7, DBU) etc. As an organometallic compound, a tin type compound, a non-tin type compound, etc. are mentioned. Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, and dibutyltin dilaurate. dilaurate, DBTDL), dibutyltin diacetate, dioctyltin dilaurate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyl tin ethoxide , tributyl tin ethoxide (tributyl tin ethoxide), dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate, and tin 2-ethylhexanoate, etc. Examples of non-tin-based compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead oleate, lead 2-ethylhexanoate, and lead benzoate , and lead series such as lead naphthenate; iron series such as iron 2-ethylhexanoate and iron acetoacetate; cobalt series such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate and 2-ethyl acetate Zinc series such as zinc hexanoate; zirconium series such as zirconium naphthenate. The type and addition amount of the catalyst can be appropriately designed within a range in which the reaction proceeds well.

When a plurality of active hydrogen group-containing compounds (H) having different reactivity are used in combination, due to the difference in reactivity of these compounds, poor polymerization stability or cloudiness of the reaction solution is likely to occur in a single catalyst system. worry. In this case, by using two or more kinds of catalysts, it becomes easy to control the reaction (for example, reaction rate, etc.), and the said problem can be solved. In a system in which a plurality of active hydrogen group-containing compounds (H) having different reactivity are used in combination, it is preferable to use two or more kinds of catalysts. The combination of two or more catalysts is not particularly limited, and examples thereof include tertiary amine/organometallic, tin/non-tin, and tin/tin. Preferably it is tin-based/tin-based, more preferably dioctyltin dilaurate and tin 2-ethylhexanoate. The mass ratio of tin 2-ethylhexanoate to dioctyltin dilaurate (tin 2-ethylhexanoate/dioctyltin dilaurate) is not particularly limited, preferably more than 0 and less than 1, More preferably, it is 0.2-0.8. If the mass ratio is less than 1, the balance of the catalytic activity is good, the gelation and cloudiness of the reaction solution are effectively suppressed, and the polymerization stability is further improved.

The usage amount of one or more catalysts is not particularly limited, but is preferably 0.01% by mass to 1.0% by mass relative to the total amount of one or more active hydrogen group-containing compounds (H) and one or more polyisocyanates (N). .

＜Solvent＞ In the polymerization of the hydroxyl-terminated urethane prepolymer (UPH), if necessary, one or more solvents may be used. As a solvent, a well-known thing can be used, and methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned. In terms of the solubility of the hydroxyl-terminated urethane prepolymer (UPH), the boiling point of the solvent, and the like, ethyl acetate, toluene, and the like are particularly preferred.

<Polymerization method of hydroxyl-terminated urethane prepolymer (UPH)> The polymerization method of the hydroxyl-terminated urethane prepolymer (UPH) is not particularly limited, and known polymerization methods such as a bulk polymerization method and a solution polymerization method can be applied. As the polymerization procedure of the hydroxyl-terminated urethane prepolymer (UPH), one can cite: Procedure 1) One or more active hydrogen group-containing compounds (H), one or more polyisocyanates (N), one or more catalysts as needed, and one or more solvents as needed are all put into a flask program of; Procedure 2) One or more active hydrogen group-containing compounds (H), one or more catalysts as needed, and one or more solvents as needed are put into a flask, and one or more polymers are added dropwise thereto. Procedures for isocyanates (N), etc. In the polymerization method of the procedure 1), there is a possibility that a part of the reaction proceeds rapidly, and a polymer with a low branching degree is formed as a main component, or a gel is formed. On the other hand, in the polymerization method of the procedure 2), the reaction can be controlled gently, and a polymer with a preferable degree of branching can be easily produced. Therefore, the polymerization method of procedure 2) is more preferable.

When a plurality of active hydrogen group-containing compounds (H) and/or polyisocyanates (N) are used, the reaction can be carried out in multiple stages. For example, in the reaction example shown in FIG. 3 , when a relatively high-branched polyol (PO1), a relatively low-branched polyol (PO2), and a relatively low-branched polyisocyanate (PI1) are reacted together, There is a high possibility of generating a prepolymer in an intermediate branched state between a relatively high branched prepolymer (PP1) and a relatively low branched prepolymer (PP2). A relatively high branched prepolymer is easily obtained by reacting a relatively high branched polyol (PO1) with a relatively low branched polyisocyanate (PI1) first and then reacting a relatively low branched polyol (PO2).

The reaction temperature at the time of using the catalyst is preferably less than 100°C, more preferably 50°C to 95°C, and particularly preferably 60°C to 85°C. When the reaction temperature is 100° C. or higher, it may be difficult to control the reaction rate, polymerization stability, and the like, and it may be difficult to generate a hydroxyl-terminated urethane prepolymer (UPH) having a desired molecular weight. The reaction temperature when a catalyst is not used is preferably 100°C or higher, more preferably 110°C or higher.

(Polyfunctional isocyanate compound (I)) As the polyfunctional isocyanate compound (I), a known one can be used, and compounds exemplified in the form of polyisocyanate (N) as a raw material of a hydroxyl-terminated urethane prepolymer (UPH) (specifically, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and trimethylolpropane adducts/biuret/ureaformate/trimer of these).

The compounding amount of the polyfunctional isocyanate compound (I) is not particularly limited. Preferably, the number of moles of isocyanate groups (NCO) contained in the polyisocyanate (I) is relative to the total number of moles of active hydrogen groups (H) contained in the hydroxyl-terminated urethane prepolymer (UPH). The ratio of the raw materials (NCO/H ratio) is determined in such a manner that the ratio (NCO/H ratio) is 0.20 to 4.00, preferably 0.40 to 3.00.

(Plasticizer (P)) The adhesive of the present invention may further contain one or more plasticizers (P) as needed from the viewpoint of reducing the adhesive force of the adhesive layer and improving the wettability. Although it does not specifically limit as a plasticizer (P), From a viewpoint of compatibility with other components, etc., an organic acid ester is preferable.

The content of the plasticizer (P) is preferably 10 parts by mass or more with respect to 100 parts by mass of the hydroxyl-terminated urethane prepolymer (UPH). The upper limit of the content of the plasticizer (P) is not particularly limited, but is preferably 300 parts by mass or less, more preferably 150 parts by mass or less. When the content of the plasticizer (P) is within the above range, the re-peelability becomes favorable.

Examples of esters of monobasic or polybasic acids and alcohols include isostearyl laurate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, and palmitic acid. Isostearyl, isocetyl stearate, octyldodecyl oleate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, phthalate Dibenzyl formate, Butyl benzyl phthalate, Diisodecyl adipate, Diisostearyl adipate, Dibutyl sebacate, Diisocetyl sebacate, Acetyl Tributyl citrate, Tributyl trimellitate, Trioctyl trimellitate, Trihexyl trimellitate, Trioleyl trimellitate, and Triisocetyl trimellitate esters, etc.

Examples of esters of other acids and alcohols include unsaturated fatty acids such as myristic acid, oleic acid, linoleic acid, hypolinolenic acid, isopalmitic acid, and isostearic acid, or chorismic acid and ethylene glycol, Esters of alcohols such as propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitan.

Examples of esters of monobasic acid or polybasic acid and polyalkylene glycol include polyethylene glycol dihexanoate, polyethylene glycol di-2-ethylhexanoate, polyethylene glycol dilaurate, and dioleic acid. polyethylene glycol, and adipic acid dipolyethylene glycol methyl ether, etc.

From the viewpoint of improving wettability, etc., the molecular weight (formula weight or Mn) of the organic acid ester is preferably 250 to 1,000, more preferably 400 to 900, and particularly preferably 500 to 850. When the molecular weight is 250 or more, the heat resistance of the adhesive layer becomes favorable, and when the molecular weight is 1,000 or less, the wettability of the adhesive becomes favorable.

(solvent) The adhesive of the present invention may contain one or more solvents as needed. As a solvent, a well-known thing can be used, and methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned. From the viewpoints of the solubility of the hydroxyl-terminated urethane prepolymer (UPH), the boiling point of the solvent, and the like, ethyl acetate, toluene, and the like are particularly preferred.

(Anti-deterioration agent) The adhesive of the present invention may contain one or more anti-deterioration agents as needed. Thereby, the fall of various characteristics by long-term use of an adhesive layer can be suppressed. As an anti-deterioration agent, a hydrolysis-resistant agent, an antioxidant, an ultraviolet absorber, a light stabilizer, etc. are mentioned.

＜Hydrolysis-resistant agent＞ When a carboxyl group is generated by a hydrolysis reaction of the adhesive layer in a (humid) heat environment, etc., a hydrolysis-resistant agent can be used in order to block the carboxyl group. As a hydrolysis-resistant agent, a carbodiimide type, an oxazoline type, an epoxy type, etc. are mentioned. Among them, from the viewpoint of the hydrolysis inhibitory effect, carbodiimide-based ones are preferred.

The carbodiimide-based hydrolysis-resistant agent is a compound having one or more carbodiimide groups in one molecule. Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, and diisobutylcarbodiimide. , dioctylcarbodiimide, diphenylcarbodiimide, and naphthylcarbodiimide, etc. The polycarbodiimide compound can be produced by subjecting a diisocyanate to a decarbonation condensation reaction in the presence of a carbodiimide catalyst. Here, as diisocyanate, 4,4'- diphenylmethane diisocyanate, 3,3'- dimethoxy- 4,4'- diphenylmethane diisocyanate, 3,3'- diphenylmethane diisocyanate, Dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2 , 4-toluene diisocyanate, 2,6-toluene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and Tetramethylxylylene diisocyanate, etc. Examples of the carbodiimide catalyst include 1-phenyl-2-phosphorol-1-oxide, 3-methyl-2-phosphorol-1-oxide, 1- -Ethyl-3-methyl-2-phosphole-1-oxide, 1-ethyl-2-phosphorol-1-oxide, and 3-phospholane of these Phosphalane oxides such as alkene isomers, etc.

Examples of oxazoline-based hydrolysis-resistant agents include 2,2'-o-phenylbis(2-oxazoline), 2,2'-m-phenylbis(2-oxazoline), 2,2'- p-phenylbis(2-oxazoline), 2,2'-p-phenylbis(4-methyl-2-oxazoline), 2,2'-m-phenylbis(4-methyl-2-oxazole) oxazoline), 2,2'-p-phenylbis(4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylbis(4,4'-dimethyl-2-oxazole) oxazoline), 2,2'-ethylidenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), 2,2'-hexamethylenebis(2 -oxazoline), 2,2'-octamethylenebis(2-oxazoline), 2,2'-ethylidenebis(4-methyl-2-oxazoline), and 2,2 '-diphenylene bis(2-oxazoline), etc.

Examples of epoxy-based hydrolysis-resistant agents include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycol; sorbitol, sorbitan, polypropylene Polyglycidyl ethers of aliphatic polyols such as triol, pentaerythritol, diglycerol, glycerol, and trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol; p-benzene Diglycidyl or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as dicarboxylic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, and sebacic acid; isophthalic acid Phenol, bis-(p-hydroxyphenyl)methane, 2,2-bis-(p-hydroxyphenyl)propane, tris-(p-hydroxyphenyl)methane, and 1,1,2,2-tetrakis(p-hydroxybenzene) diglycidyl ether or polyglycidyl ether of polyphenols such as ethane; N,N-diglycidylaniline, N,N-diglycidyltoluidine, and N,N,N',N'- N-glycidyl derivatives of amines such as tetraglycidyl-bis-(p-aminophenyl)methane; triglycidyl derivatives of aminophenol; triglycidyl tris(2-hydroxyethyl)iso Cyanurate, triglycidyl isocyanurate; o-cresol type epoxy resin and phenol novolac type epoxy resin and other epoxy resins.

The addition amount of the hydrolysis-resistant agent is not particularly limited, but is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4.5 parts by mass relative to 100 parts by mass of the hydroxyl-terminated urethane prepolymer (UPH). parts, particularly preferably 0.5 to 3 parts by mass.

＜Antioxidants＞ As an antioxidant, a radical scavenger, a peroxide decomposition agent, etc. are mentioned. As a radical scavenger, a phenol type compound, an amine type compound, etc. are mentioned. As a peroxide decomposer, a sulfur compound, a phosphorus compound, etc. are mentioned.

Examples of the phenolic compound include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, β -(3,5-Di-tert-butyl-4-hydroxyphenyl) stearyl propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2 ,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4' -Butylenebis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-[beta-(3-tert-butyl-4-hydroxy- 5-Methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, phenylpropionic acid, 3,5-bis(1,1- Dimethylethyl)-4-hydroxy-, C7-C9 side chain alkyl ester, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3', 5'-Di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid ] Ethylene glycol ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H , 5H) triketone, and tocopherol.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and 3,3'-thiodipropionate acid distearyl ester, etc.

Examples of phosphorus-based compounds include triphenyl phosphite, diphenyl isodecyl phosphite, 4,4'-butylene-bis(3-methyl-6-tert-butylphenyldi-decyl) Trialkyl) phosphite, cyclic neopentanetetraylbis(octadecyl phosphite), tris(nonylphenyl) phosphite, tris(mononylphenyl) phosphite, tris(mononylphenyl) phosphite (dinonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5 -Di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro -9-oxa-10-phosphaphenanthrene, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butyl) phenyl) phosphite, cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenyl)phosphite, and 2,2-methylenebis(4, 6-di-tert-butylphenyl) octyl phosphite, etc.

Thermal degradation of the hydroxyl-terminated urethane prepolymer (UPH) can be prevented by using an antioxidant. The amount of the antioxidant added is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the hydroxyl-terminated urethane prepolymer (UPH). , particularly preferably 0.2 to 2 parts by mass.

As the antioxidant, from the viewpoint of stability and antioxidant effect, it is preferable to use one or more phenolic compounds as a radical scavenger, and it is more preferable to use one or more phenolic compounds as a radical scavenger together with One or more phosphorus-based compounds as peroxide decomposers. Moreover, as antioxidant, it is especially preferable to use together the phenol type compound as a radical scavenger, and the phosphorus type compound as a peroxide decomposer, and to use these antioxidants together with the said hydrolysis-resistant agent.

＜Ultraviolet absorber＞ Examples of the ultraviolet absorber include benzophenone-based compounds, benzotriazole-based compounds, salicylic acid-based compounds, oxaniline-based compounds, cyanoacrylate-based compounds, and triazine-based compounds. The amount of UV absorber added is such that it does not inhibit the initiation and progress of polymerization of radically polymerizable monomers (MX) by irradiation with active energy rays, and is not easily affected by ambient light such as fluorescent lamps and sunlight. It is appropriately designed within the range where the reaction of the radical polymerizable monomer (MX) starts. When the radically polymerizable monomer (MX) is ultraviolet curable, the amount of the ultraviolet absorber added is designed according to the type of ultraviolet absorber, the wavelength region and the accumulated light intensity of the ultraviolet rays irradiated to the adhesive layer. The addition amount of the ultraviolet absorber is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2.5 parts by mass, and particularly preferably 0.2 to 2 parts by mass.

＜Light Stabilizer＞ Examples of the light stabilizer include hindered amine-based compounds, hindered piperidine-based compounds, and the like. The addition amount of the light stabilizer is not particularly limited, but is preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1.5 parts by mass relative to 100 parts by mass of the hydroxyl-terminated urethane prepolymer (UPH). parts, particularly preferably 0.2 to 1 part by mass.

(Antistatic Agent (AS)) The adhesive of the present invention may contain one or more antistatic agents (AS) as needed. As an antistatic agent (AS), an inorganic salt, an ionic liquid, an ionic solid, a surfactant, etc. are mentioned, Among them, an ionic liquid and an ionic solid are preferable. In addition, "ionic liquid" is also called normal temperature molten salt, and is a salt which has fluidity|liquidity at 25 degreeC.

Examples of inorganic salts include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, cupric chloride, ferrous chloride, ferric chloride, and ammonium sulfate. , potassium nitrate, sodium nitrate, sodium carbonate, and sodium thiocyanate, etc.

Examples of the ionic liquid containing imidazolium ions include 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium bis( Trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and the like.

Examples of the ionic liquid containing pyridinium ions include 1-methylpyridinium bis(trifluoromethylsulfonyl)imide, and 1-butylpyridinium bis(trifluoromethylsulfonyl)imide. Imide, 1-hexylpyridinium bis(trifluoromethylsulfonyl)imide, 1-octylpyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methyl pyridinium bis(trifluoromethylsulfonyl)imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis(trifluoromethylsulfonic acid) acyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methylpyridinium bis(perfluoroethylsulfonyl)imide, and 1-methylpyridinium bis(perfluorobutylsulfonyl)imide, etc.

Examples of the ionic liquid containing ammonium ions include 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, trimethylheptylammonium bis(trifluoromethanesulfonyl)imide base) imide, N,N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl- N-amylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, and Tri-n-butylmethylammonium bis-trifluoromethanesulfonimide, etc.

In addition, commercially available ionic liquids such as pyrrolidinium salts, phosphonium salts, and peronium salts can be suitably used.

The ionic solid is a salt of a cation and an anion like the ionic liquid, but shows a solid state at 25°C under normal pressure. As a cation, for example, an alkali metal ion, a phosphonium ion, a pyridinium ion, an ammonium ion, etc. are preferable.

Examples of ionic solids containing alkali metal ions include lithium bisfluorosulfonimide, lithium bistrifluoromethylsulfonimide, lithium bispentafluoroethylsulfonimide, Lithium bis-heptafluoropropyl sulfonimide, Lithium bis-nonane fluorobutyl sulfonimide, Sodium bis-fluorosulfonimide, Sodium bis-trifluoromethyl sulfonimide, Sodium Bispentafluoroethylsulfonimide, Sodium Bisheptafluoropropylsulfonimide, Sodium Bisnonane Fluorobutylsulfonimide, Potassium Bisfluorosulfonimide, Potassium Bistrifluoromethylsulfonimide, Potassium Bispentafluoroethylsulfonimide, Potassium Bisheptafluoropropylsulfonimide, and Potassium Bisnonanefluorobutylsulfonimide imide, etc.

Examples of ionic solids containing phosphonium ions include tetrabutylphosphonium bisfluorosulfoimide, tetrabutylphosphoniumbistrifluoromethylsulfoimide, and tetrabutylphosphoniumbispentafluoroethyl Sulfonyl imide, tetrabutylphosphonium bis-heptafluoropropyl sulfonyl imide, tetrabutylphosphonium bis-nonane fluorobutyl sulfonyl imide, tributylhexadecyl phosphonium bis Fluorosulfonimide, tributylhexadecylphosphonium bis-trifluoromethylsulfonimide, tributylhexadecylphosphonium bispentafluoroethylsulfonimide, tributyl Cetyl phosphonium bis-heptafluoropropyl sulfonyl imide, tributyl hexadecyl phosphonium bis-nonane fluorobutyl sulfonyl imide, tetraoctyl phosphonium bisfluorosulfonyl imide Amine, tetraoctylphosphonium bis-trifluoromethylsulfonimide, tetraoctylphosphonium bis-pentafluoroethylsulfonimide, tetraoctylphosphonium bis-heptafluoropropyl sulfonimide, And tetraoctylphosphonium dinonane fluorobutyl sulfonyl imide and so on.

Examples of ionic solids containing pyridinium ions include 1-hexadecyl-4-methylpyridinium bisfluorosulfonimide, 1-hexadecyl-4-methylpyridinium bis Trifluoromethylsulfonimide, 1-hexadecyl-4-methylpyridinium bis-pentafluoroethylsulfonimide, 1-hexadecyl-4-methylpyridinium bis Heptafluoropropylsulfonyl imide, and 1-hexadecyl-4-methylpyridinium bisnonane fluorobutylsulfonyl imide, etc.

Examples of ionic solids containing ammonium ions include lauryltrimethylammonium chloride, tributylmethylbistrifluoromethylsulfonimide, and tributylmethylbispentafluoroethylsulfonimide. Amine, tributylmethylbisheptafluoropropylsulfonimide, tributylmethylbisnonanefluorobutylsulfonimide, octyltributylbistrifluoromethylsulfonimide, Octyltributylbispentafluoroethylsulfonylimide,Octyltributylbisheptafluoropropylsulfonylimide,octyltributylbisnonanefluorobutylsulfonylimide Amine, Tetrabutylbisfluorosulfonimide, Tetrabutylbistrifluoromethylsulfonimide, Tetrabutylbispentafluoroethylsulfonimide, Tetrabutylbisheptafluoro Propyl sulfonimide, and tetrabutyl dinonane fluorobutyl sulfonimide, etc.

In addition, known ionic solids whose cations are pyrrolidinium ions, imidazolium ions, perionium ions, and the like can be suitably used.

Examples of the surfactant include nonionic surfactants and anionic surfactants, and either type is classified into low-molecular-weight surfactants and high-molecular-weight surfactants.

Examples of nonionic low molecular weight surfactants include glycerin fatty acid ester, polyoxyalkylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylene Ethylene alkylamine fatty acid ester, fatty acid diethanolamide, etc. Examples of the anionic low molecular weight surfactant include alkylsulfonates, alkylbenzenesulfonates, and alkyl phosphates. As an amphoteric low molecular surfactant, an alkylbetaine, an alkylimidazolium betaine, etc. are mentioned.

As a nonionic polymer surfactant, a polyether ester amide type, an ethylene oxide-epichlorohydrin type, a polyether ester type, etc. are mentioned. As anionic polymer surfactant, polystyrene sulfonic acid type etc. are mentioned. Examples of the amphoteric polymer surfactant include amino acid-type amphoteric surfactants such as higher alkyl aminopropionate, higher alkyl dimethyl betaine, and higher alkyl dihydroxyethyl betaine. Betaine-type amphoteric surfactants, etc.

The addition amount of the antistatic agent (AS) is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, relative to 100 parts by mass of the hydroxyl-terminated urethane prepolymer (UPH).

(leveler) The adhesive of the present invention may contain a leveling agent if necessary. By adding a leveling agent, the leveling property of the adhesive layer can be improved. As a leveling agent, an acrylic leveling agent, a fluorine-based leveling agent, a silicone-based leveling agent, etc. are mentioned. From the viewpoint of suppressing contamination by adherends after the adhesive sheet is peeled off again, an acrylic leveling agent or the like is preferred.

The amount of the leveling agent to be added is not particularly limited, but from the viewpoints of suppressing adherent contamination after re-peeling of the adhesive sheet and improving the leveling property of the adhesive layer, the amount of the leveling agent is higher than that of the hydroxyl-terminated urethane prepolymer (UPH). ) 100 parts by mass, preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, particularly preferably 0.1 to 1 part by mass.

(any other ingredients) The pressure-sensitive adhesive of the present invention may contain other arbitrary components as necessary within a range that does not impair the effects of the present invention. Examples of other optional components include catalysts, resins other than urethane resins, fillers (talc, calcium carbonate, titanium oxide, etc.), metal powders, colorants (pigments, etc.), foils , softener, conductive agent, silane coupling agent, lubricant, anti-corrosion agent, heat-resistant stabilizer, weather-resistant stabilizer, polymerization inhibitor, and defoamer, etc. When the adhesive of the present invention contains a catalyst, for the purpose of increasing the pot life of the adhesive, it is preferable to add a known catalyst action inhibitor such as acetone.

(mixing ratio) The adhesive of the present invention contains, as essential components, one or more hydroxyl-terminated urethane prepolymers (UPH) having a specific degree of branching α, and one or more polyfunctional isocyanate compounds (I), and further, optionally, one any of the above. The blending ratio of these is not particularly limited, and the preferred blending ratio is as follows. The amount of the one or more polyfunctional isocyanate compounds (I) is preferably 1 to 30 parts by mass, more preferably 5 parts by mass relative to 100 parts by mass of the one or more hydroxyl-terminated urethane prepolymers (UPH). to 25 parts by mass, particularly preferably 8 to 20 parts by mass. When the amount of the one or more polyfunctional isocyanate compounds (I) is 1 part by mass or more, the cohesive force of the adhesive layer becomes favorable, and when it is 30 parts by mass or less, the pot life becomes favorable.

(Manufacturing method of adhesive) The manufacturing method of the adhesive of this invention is not specifically limited. One or more kinds of polyfunctional isocyanate compounds (I), one or more kinds of polyfunctional isocyanate compounds (I), one or more kinds of polyfunctional isocyanate compounds (I), one or more kinds of polyfunctional isocyanate compounds (I), one or more kinds of polyfunctional isocyanate compounds (I), and optionally one or more other optional components, whereby the adhesive of the present invention can be produced.

[adhesive sheet] The adhesive sheet of the present invention includes a base material sheet and an adhesive layer containing a cured product of the adhesive of the present invention. The adhesive layer can be formed on one side or both sides of the substrate sheet. If necessary, the exposed surface of the adhesive layer may be covered with a release sheet. Furthermore, before attaching the adhesive sheet to the adherend, the release sheet can be peeled off.

FIG. 1 shows a schematic cross-sectional view of an adhesive sheet according to a first embodiment of the present invention. In FIG. 1 , reference numeral 10 is an adhesive sheet, reference numeral 11 is a base material sheet, reference numeral 12 is an adhesive layer, and reference numeral 13 is a release sheet. The adhesive sheet 10 is a single-sided adhesive sheet in which an adhesive layer is formed on one side of a base sheet. FIG. 2 shows a schematic cross-sectional view of an adhesive sheet according to a second embodiment of the present invention. In FIG. 2, reference numeral 20 is an adhesive sheet, reference numeral 21 is a base material sheet, reference numerals 22A and 22B are adhesive layers, and reference numerals 23A and 23B are release sheets. The adhesive sheet 20 is a double-sided adhesive sheet in which an adhesive layer is formed on both sides of the base sheet.

Although it does not specifically limit as a base material sheet, Resin sheet, paper, metal foil, etc. are mentioned. The base material sheet may be a laminate sheet in which any one or more layers are layered on at least one area of these base material sheets. The surface of the base sheet on the side where the adhesive layer is formed may be subjected to an easy-adhesion treatment such as corona discharge treatment and anchor coating agent application, if necessary.

The structural resin of the resin sheet is not particularly limited, and examples thereof include ester-based resins such as polyethylene terephthalate (PET); polyethylene (PE), polypropylene (PP), and the like Olefin-based resins; vinyl-based resins such as polyvinyl chloride; amide-based resins such as nylon 66; urethane-based resins (including foams); combinations of these, and the like. The thickness of the resin sheet other than the polyurethane sheet is not particularly limited, but is preferably 15 μm to 300 μm. The thickness of the polyurethane sheet (including the foam) is not particularly limited, but is preferably 20 μm to 50,000 μm.

Although it does not specifically limit as paper, Plain paper, coated paper, coated paper, etc. are mentioned. Although it does not specifically limit as a structural metal of a metal foil, Aluminum, copper, a combination of these, etc. are mentioned.

The release sheet is not particularly limited, and a known release sheet that has been subjected to a known release treatment such as coating of a release agent on the surface of a base material sheet such as a resin sheet or paper can be used.

[Manufacturing method of adhesive sheet] The adhesive sheet can be produced by a known method. First, the adhesive agent of this invention is apply|coated to the surface of a base material sheet, and the coating layer containing the adhesive agent of this invention is formed. A known method can be applied to the coating method, and examples thereof include a roll coater method, a notch coater method, a die coater method, a reverse coater method, a screen printing method, and a gravure coater method. Next, the coating layer is dried and cured to form an adhesive layer containing a cured product of the adhesive of the present invention. The heating and drying temperature is not particularly limited, but is preferably about 60°C to 150°C. The thickness of the adhesive layer (thickness after drying) varies depending on the application, but is preferably 0.1 μm to 200 μm. Next, if necessary, a release sheet is attached to the exposed surface of the adhesive layer by a known method. In this way, a single-sided adhesive sheet can be produced. By performing the above operation on both sides, a double-sided adhesive sheet can be produced.

Contrary to the above-described method, the adhesive of the present invention may be applied to the surface of the release sheet to form a coating layer containing the adhesive of the present invention, and then the coating layer may be dried and cured to form a coating layer containing the present invention. The adhesive layer of the hardened product of the adhesive is laminated, and the substrate sheet is laminated on the exposed surface of the adhesive layer.

The manufacturing method of the adhesive sheet preferably comprises: a coating step of applying an adhesive on the substrate sheet; a heating step of heating and drying the formed coating layer to form an adhesive layer of a cured product comprising the adhesive; In the winding step, the obtained adhesive sheet is wound on the core to form the form of the adhesive sheet roll; and the curing step is for curing the adhesive sheet roll.

As described above, according to the present invention, there can be provided an adhesive and an adhesive sheet using the adhesive, which have good initial curability and can be formed even when exposed to a heat environment, particularly a humid heat environment An adhesive layer that suppresses the increase in adhesive force and has good re-peelability. According to the first aspect of the present invention, there can be provided an adhesive and an adhesive sheet using the adhesive, the initial hardenability of the adhesive, and the re-peelability when exposed to a heat environment, particularly a humid heat environment (suppression of adhesion) can be provided. The effect of increasing the force) is good, and it is possible to form an adhesive layer with good substrate adhesion, scratch resistance, and curved surface adhesion. According to the second aspect of the present invention, there can be provided an adhesive and an adhesive sheet using the same, the initial hardenability of the adhesive and the re-peelability when exposed to a heat environment, especially a humid heat environment (suppression of adhesion) can be provided. The effect of increasing the force) is good, and it is possible to form an adhesive layer with good folding resistance, cutting properties, and heat resistance.

[use] The adhesive sheet of the present invention can be used in the form of a tape, a label, a sheet, and a double-sided tape. The adhesive sheet of the present invention can be preferably used as a surface protection sheet, a cosmetic sheet, a non-slip sheet, and the like. In addition, in this specification, unless otherwise specified, a "sheet" is assumed to include a "film" and a "tape". Flat panel displays such as liquid crystal displays (LCDs) and organic electroluminescence displays (OELDs), and touch panel displays combining the flat panel displays and touch panels are widely used in televisions (TVs), personal computers (PCs), In electronic equipment such as mobile phones and portable information terminals. The adhesive sheet of the present invention can be preferably used for flat panel displays and touch panel displays (these are collectively referred to as "displays"), and substrates (glass substrates, and Surface protection sheets such as ITO/glass substrates, etc.) and optical members, etc., with indium tin oxide (ITO) films formed on glass substrates. [Example]

Hereinafter, synthesis examples, examples of the present invention, and comparative examples will be described. In addition, in the following description, unless otherwise specified, "part" means mass part, "%" means mass %, and "RH" means relative humidity. Unless otherwise specified, the unit of the compounding amount in the table is "parts by mass". Unless otherwise specified, the compounding amount of the components other than the solvent is the non-volatile component conversion value.

[Evaluation items and evaluation methods for materials or hydroxyl-terminated urethane prepolymers] The evaluation items and evaluation methods of the material or the hydroxyl-terminated urethane prepolymer are as follows. (Mw, Mn) The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by gel permeation chromatography (GPC). The measurement conditions are as follows. In addition, Mw and Mn are polystyrene conversion values. Installation: SHIMADZU Prominence (manufactured by Shimadzu Corporation), String: Connect three SHODEX LF-804 (manufactured by Showa Denko Co., Ltd.) in series, Detector: Differential refractive index detector, Solvent: Tetrahydrofuran (THF), Flow rate: 1 mL/min, Solvent temperature: 40℃, Sample concentration: 0.2%, Sample injection volume: 200 μL.

(branch degree α) The branching degree α was measured using a device (GPC-MALS-VISCO) combining a multi-angle light scattering detector (MALS) with a viscosity detector (VISCO) and a gel permeation chromatography (GPC).

(Viscosity of hydroxyl-terminated urethane prepolymer solution) The viscosity of the hydroxyl-terminated urethane prepolymer solution at 25°C was measured by placing it in a glass bottle with a lid immediately after preparation, immersing it in a constant temperature water bath at 25°C, and then measuring the viscosity 1 hour later. . The viscosity was measured using a B-type viscometer (“TVB10 type viscometer” manufactured by Toki Sangyo Co., Ltd.).

(non-volatile components) The nonvolatile content of the hydroxyl-terminated urethane prepolymer solution was obtained by heating and drying about 1 g of a sample at 120° C. for 20 minutes, and then obtained from the change in mass after drying relative to before drying.

[Synthesis example of polyol] (Synthesis example Z-1) 100.0 parts of butyl ethyl propylene glycol (BEPD) and 4.0 parts of potassium hydroxide as the first components were put into an autoclave including a stirring device and a temperature control device, then heated to 100° C. and continuously charged under stirring as a second component. 150.0 parts of propylene oxide (PO) as an ingredient. To the obtained reaction product, 40.0 parts of water and 40.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and the mixture was stirred and mixed at 90° C. for 1 hour. After that, a filter covered with filter paper was used to remove the added alkali adsorbent. The reaction product that passed through the filter paper was subjected to dehydration treatment at 130 °C and a pressure of 2.7 kPa. As described above, a polyether polyol (HX-1) having a number average molecular weight (Mn) of 400, an average functional group order of 2, and a branching degree α of 0.45 was obtained. The composition of the raw materials, and the types and properties of the obtained polyols are shown in Table 1-1 and Table 1-2.

(Synthesis example Z-3, Synthesis example Z-11) A polyol was obtained in the same manner as in Synthesis Example Z-1, except that the types and amounts of the first component and the second component were changed. The composition of the raw materials, and the types and properties of the obtained polyols are shown in Table 1-1 and Table 1-2.

(Synthesis example Z-2) Into an autoclave including a stirring device and a temperature control device, 100 parts of terephthalic acid (TPA) as the first component, 27 parts of trimethylolpropane (TMP) as the second component, and 1,9-nonanediol (ND) 74 parts. It heated to 200 degreeC under the nitrogen atmosphere of normal pressure, and esterification reaction was performed while distilling the produced water out of the system. 0.01 part of tetraisopropyl titanate was added at the point of time when the distillation removal of the generated water was reduced, and the reaction was continued while reducing the pressure with a vacuum pump to obtain a number-average molecular weight (Mn) of 1,500 and an average functional group order of 3. , Polyester polyol (HX-2) with branching degree α of 0.35.

(Synthesis example Z-7, Synthesis example Z-10, Synthesis example Z-16) A polyol was obtained in the same manner as in Synthesis Example Z-2, except that the types and amounts of the first component, the second component, and the third component were changed. The composition of the raw materials, and the types and properties of the obtained polyols are shown in Table 1-1 and Table 1-2.

(Synthesis example Z-4) 100.0 parts of glycerol and 4.0 parts of potassium hydroxide as the first component were placed in an autoclave including a stirring device and a temperature control device, then heated to 100° C., and 1,2-ring as the second component was continuously charged under stirring. Oxybutane (1,2-BO) 334 parts. To the obtained reaction product, 40.0 parts of water and 40.0 parts of an alkali adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and the mixture was stirred and mixed at 90° C. for 1 hour. After that, the added alkali adsorbent was removed using a filter covered with filter paper. The reaction product that passed through the filter paper was subjected to dehydration treatment at 130 °C and a pressure of 2.7 kPa. The reaction product was charged into an autoclave including a stirring device and a temperature control device, and 0.10 part of zinc hexacyanocobaltate catalyst was further charged, and the temperature in the reactor was raised to 130° C., and added under stirring. 282 parts (10 mass % of total usage-amounts) of 1,2- butylene oxide (1,2-BO) as a 3rd component. After the reaction was performed for 2 hours and the catalyst was activated, 2538 parts (90% by mass of the total used amount) of 1,2-epoxybutane (1,2-BO) as the third component were continuously added at 100° C. The mixture was mixed and stirred at °C until the pressure became constant. The obtained mixture was vacuum stripped at 100° C. for 0.5 hours, and the unreacted third component was removed from the reactor. As described above, a polyether polyol (HX-S-2) having a number average molecular weight (Mn) of 3000, an average functional group order of 2, and a branching degree α of 0.05 was obtained. The raw material composition and the properties of the obtained polyol are shown in Table 1-1 and Table 1-2.

(Synthesis Example Z-5, Synthesis Example Z-6, Synthesis Example Z-9, Synthesis Example Z-12 to Synthesis Example Z-15) A polyol was obtained in the same manner as in Synthesis Example Z-4, except that the types and amounts of the first component, the second component, and the third component were changed. The composition of the raw materials, and the types and properties of the obtained polyols are shown in Table 1-1 and Table 1-2.

(Synthesis example Z-8) A round-bottomed flask including a stirrer, a thermometer, a nitrogen introduction tube, and a condenser was charged with polycarbonate diol (manufactured by Daicel Chemical Industry Co., Ltd.: trade name CD220, molecular weight 2011, hydroxyl value 55.8) 1854 g, 21 g of trimethylolpropane, 126 g of pentaerythritol, and 0.08 g of tetrabutyl titanate as a catalyst. Heating was performed while stirring under normal pressure. The reaction temperature was gradually increased, and after reaching 220° C., the temperature was maintained for 8 hours, and the reaction proceeded. Samples were taken at any time during the reaction, and the residual diol component (here, 1,6-hexanediol) and triol component (here, trimethylolpropane) were quantified by gas chromatography analysis, It was confirmed that the transesterification reaction reached an equilibrium state, and the reaction was terminated. As described above, a polycarbonate polyol (HX-S-6) having a number-average molecular weight (Mn) of 1,000, an average functional group order of three, and a branching degree α of 0.05 was obtained. The composition of the raw materials, and the types and properties of the obtained polyols are shown in Table 1-1 and Table 1-2.

Each abbreviation in Table 1-1 and Table 1-2 represents the following compounds. BEPD: Butyl Ethyl Propylene Glycol, TPA: terephthalic acid, AA: Adipic acid, PG: Propylene Glycol, IPA: isophthalic acid, PO: propylene oxide, TMP: Trimethylolpropane, 1,2-BO: 1,2-butylene oxide, EO: ethylene oxide, THF: Tetrahydrofuran, PD-9: 2,4-diethyl-1,5-pentanediol, ND: 1,9-nonanediol, MPD: 2-methylpentane-2,4-diol, CD220: polycarbonate diol (manufactured by Daicel Chemical Industry Co., Ltd.: trade name CD220, molecular weight 2011, hydroxyl value 55.8), PET: Pentaerythritol.

[Material] The materials used are as follows. Table 1-2 shows the active hydrogen group-containing compound (HX) used, the type of active hydrogen group-containing compound (HY), the number of functional groups, Mn, the average number of functional groups, and the degree of branching α. The kind of polyisocyanate (N) used, the number of functional groups, and Mn are shown in Table 1-2.

<Active hydrogen group-containing compound (HX)> (HX-1): Polyether polyol. (HX-2): polyester polyol. (HX-S-1): Polycaprolactone polyol. (HX-S-2): polyether polyol. (HX-S-3): polyether polyol. (HX-S-4): polyether polyol. (HX-S-5): polyester polyol. (HX-S-6): polycarbonate polyol. (HX-S-7): Polyether polyol, "DK polyol (DK polyol) G480" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. (HX-S-8): Polyether polyol, "Adeka polyether AM-302" manufactured by Adeka Corporation.

＜Active hydrogen group-containing compound (HY)＞ (HY-1): Polyether polyol. (HY-2): polyester polyol. (HY-L-1): Polyether polyol. (HY-L-2): polyether polyol. (HY-L-3): Polyether polyol. (HY-L-4): Polyether polyol. (HY-L-5): Polyether polyol. (HY-L-6): polyester polyol. (HY-L-7): Polyether polyol, "poly hardner D-100A" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd. (HY-L-8): polyester polyol, "Kuraray polyol P-1010" manufactured by Kuraray Corporation. (HY-L-9): Polyether polyol, "poly hardner D-40" manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.

＜Polyisocyanate (N)＞ (N-1): HDI, hexamethylene diisocyanate, manufactured by Sumika Covestro Urethane, Desmodur H. (N-2): IPDI, isophorone diisocyanate, manufactured by Sumika Covestro Urethane, Desmodur I. (N-3): TDI, toluene diisocyanate (mixture of 2,4-toluene diisocyanate (80% by mass) and 2,6-toluene diisocyanate (20% by mass)), manufactured by Tosoh Corporation, Cronite ( coronate) T-80. (N-4): HDI urate, Sumidur N-3300, manufactured by Sumika Bayer Urethane, hexamethylene diisocyanate (HDI)/isotrimer cyanate ester.

[Table 1-1] Synthesis example first ingredient second ingredient third ingredient type load type load type load type load type load Z-1 HX-1 BEPD 100 PO 150 Z-2 HX-2 TPA 100 TMP 27 ND 74 Z-3 HX-S-1 glycerin 100 ε-Caprolactone 660 Z-4 HX-S-2 glycerin 100 1,2-BO 334 1,2-BO 2820 Z-5 HX-S-3 Pentaerythritol 100 PO 39 EO 155 PO 820 EO 3290 Z-6 HX-S-4 3-Methylpentane-1,3,5-triol 100 EO 198 EO 450 Z-7 HX-S-5 AA 100 TMP 31 MPD 50 Z-8 HX-S-6 CD220 1854 TMP twenty one PET 126 Z-9 HY-1 BEPD 100 PO 150 PO 370 Z-10 HY-2 AA 100 1,2,6-Hexanetriol 82 Z-11 HY-L-1 PG 100 EO 426 Z-12 HY-L-2 PG 100 1,2-BO 426 1,2-BO 2100 Z-13 HY-L-3 PG 100 PO 85 EO 341 PO 1470 EO 5890 Z-14 HY-L-4 1,2,6-Hexanetriol 100 PO 198 PO 1190 Z-15 HY-L-5 PG 100 THF 426 THF 790 Z-16 HY-L-6 IPA 100 PD-9 113

[Table 1-2] type number of functional groups Mn Average number of functional groups branch degree α HX-1 Polyether polyol BEPD/PO 2 400 secondary 0.45 HX-2 polyester polyol ND/TPA/TMP 3 1500 Level 1 0.35 HX-S-1 Polycaprolactone polyol Glycerol/ε-Caprolactone 3 700 Level 1 0.05 HX-S-2 Polyether polyol Glycerol/1,2-BO 3 3000 secondary 0.05 HX-S-3 Polyether polyol Pentaerythritol/PO/EO 4 6000 Level 1 0.08 HX-S-4 Polyether polyol 3-Methylpentane-1,3,5-triol 3 1000 Level 1 0.28 HX-S-5 polyester polyol MPD/AA/TMP 3 3000 Level 1 0.05 HX-S-6 Polycarbonate Polyol CD220/TMP/PET 3 1000 Level 1 0.05 HX-S-7 Polyether polyol DK polyol (DK polyol) G480 3 350 secondary 0.05 HX-S-8 Polyether polyol Adeka polyether AM-302 3 3000 Level 1 0.10 HY-1 Polyether polyol BEPD/PO 2 1000 secondary 0.58 HY-2 polyester polyol 1,2,6-Hexanetriol/AA 3 1000 Level 1 0.55 HY-L-1 Polyether polyol PG/EO 2 300 Level 1 0.70 HY-L-2 Polyether polyol PG/1,2-BO 2 2000 secondary 0.85 HY-L-3 Polyether polyol PG/PO/EO 2 6000 Level 1 0.95 HY-L-4 Polyether polyol 1,2,6-Hexanetriol/PO 3 2000 secondary 0.65 HY-L-5 Polyether polyol PG/THF 2 1000 Level 1 0.95 HY-L-6 polyester polyol PD-9/IPA 2 2000 Level 1 0.95 HY-L-7 Polyether polyol poly hardner D-100A 2 1000 secondary 0.75 HY-L-8 polyester polyol Kuraray polyol P-1010 2 1000 Level 1 0.90 HY-L-9 Polyether polyol poly hardner D-40 2 400 secondary 0.90 N-1 Hexamethylene diisocyanate HDI 2 168.2 N-2 isophorone diisocyanate IPDI 2 222.2 N-3 Toluene Diisocyanate TDI 2 174.2 N-4 Hexamethylene diisocyanate urate HDI-Urate 3 504.6

<Polyfunctional isocyanate compound (I)> (I-1) HDI adduct, coronate HL, manufactured by Tosoh Corporation, hexamethylene diisocyanate (HDI)/trimethylolpropane (TMP) adduct. (I-2) HDI urethane, Sumidur N-3300, manufactured by Sumika Bayer Urethane, hexamethylene diisocyanate (HDI)/isocyanurate acid ester.

＜Antioxidant (O)＞ (O-1): IRGANOX 1010, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], phenolic antioxidants, BASF ( BASF) company.

＜Plasticizer (P)＞ (P-1): Adeka sizer RS700, polyetherester-based plasticizer, manufactured by Adeka Corporation. (P-2): Exceparl MOL, methyl oleate, manufactured by Kao Corporation.

＜Antistatic agent (AS)＞ (AS-1): ionic liquid, tri-n-butylmethylammonium bistrifluoromethanesulfonimide.

[Synthesis example of solution of hydroxyl-terminated urethane prepolymer (UPH)] (Synthesis Example 1) One-step dropwise addition method (Method 1) A four-necked flask including a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel was charged and mixed with 80.0 parts by mass of the active hydrogen group-containing compound (HX-S-1) and the active hydrogen group-containing compound (HY-L-5) 20.0 parts by mass, 42.8 parts of toluene, 0.020 parts by mass of dioctyltin dilaurate and 0.008 parts by mass of tin 2-ethylhexanoate as catalysts. After that, the temperature of the content liquid was gradually increased to 80°C. Into the dropping funnel, 25.0 parts by mass of polyisocyanate (N-1) and 24.5 parts by mass of toluene were charged and mixed, and the mixed solution was added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the reaction was carried out for 1 hour. The ratio (NCO/ H ratio) was 0.78. After the disappearance of the residual isocyanate group was confirmed by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to 40° C. to complete the reaction. Finally, 0.56 parts by mass of acetylacetone was added. As described above, a solution of a colorless and transparent hydroxyl-terminated urethane prepolymer (UPH-1) having a nonvolatile content of 65%, a viscosity of 3200 cps, and a colorless and transparent solution was obtained. The main formulation composition, NCO/H ratio, Mw and Mn of the obtained hydroxyl-terminated urethane prepolymer, and branching degree α are shown in Table 2-1. In each example of Table 2-1, Table 2-2, Table 3-1, Table 3-2, and Table 4, the conditions not described in the table were used as common conditions.

(Synthesis Example 2 to Synthesis Example 14, Synthesis Example 19 to Synthesis Example 33) One-step dropwise addition method (Method 1) In Synthesis Example 2 to Synthesis Example 14 and Synthesis Example 19 to Synthesis Example 33, the type of active hydrogen group-containing compound (H), the type of polyisocyanate (N), and the mixing ratio of these were changed, and the same Synthesis Example 1 Colorless and transparent hydroxyl-terminated urethane prepolymer (UPH-2) to hydroxyl-terminated urethane prepolymer (UPH-14) and hydroxyl-terminated urethane prepolymer were obtained in the same manner (UPH-19) ~ a solution of hydroxyl-terminated urethane prepolymer (UPH-33). In each synthesis example, the main preparation composition, NCO/H ratio, Mw and Mn and branching degree α of the obtained hydroxyl-terminated urethane prepolymer are shown in Table 2-1 and Table 2-2. , Table 3-1, Table 3-2.

(Synthesis Example 15) Bulk loading method (Method 2) 32.0 parts by mass of the active hydrogen group-containing compound (HX-S-7) and the active hydrogen group-containing compound were charged into a four-necked flask including a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel and mixed (HY-L-7) 68.0 parts by mass, polyisocyanate (N-1) 26.0 parts by mass, 67.8 parts by mass of toluene, and 0.020 part by mass of dioctyltin dilaurate as a catalyst. Then, the content liquid was heated up to 80 degreeC, and it was made to react for 3 hours. The ratio (NCO/ H ratio) was 0.75. After the disappearance of the residual isocyanate group was confirmed by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to 40° C. to complete the reaction. Finally, 0.56 parts by mass of acetylacetone was added. As described above, a solution of a colorless and transparent hydroxyl-terminated urethane prepolymer (UPH-15) having a non-volatile content of 65%, a viscosity of 1800 cps, and a colorless and transparent solution was obtained. The main formulation composition, NCO/H ratio, Mw and Mn of the obtained hydroxyl-terminated urethane prepolymer, and branching degree α are shown in Table 2-2.

(Synthesis Example 16, Synthesis Example 34) Bulk loading method (Method 2) In Synthesis Example 16 and Synthesis Example 34, the type of active hydrogen group-containing compound (H), the type of polyisocyanate (N), and the mixing ratio of these were changed, and a colorless and transparent compound was obtained in the same manner as in Synthesis Example 15. Hydroxy-terminated urethane prepolymer (UPH-16), solution of hydroxyl-terminated urethane prepolymer (UPH-34). In each synthesis example, the main preparation composition, NCO/H ratio, Mw, Mn and branching degree α of the obtained hydroxyl-terminated urethane prepolymer are shown in Table 2-2 and Table 3-2 middle.

(Synthesis Example 41, Synthesis Example 42) Bulk loading method (Method 2) In Synthesis Example 41 and Synthesis Example 42, the type of the active hydrogen group-containing compound (H), the type of polyisocyanate (N), and the compounding ratio of these were changed, and the same procedure as Synthesis Example 14 was used to obtain a comparison. Colorless and transparent solution of hydroxyl-terminated urethane prepolymer (UPC-41) and hydroxyl-terminated urethane prepolymer (UPC-42). In each synthesis example, the main compounding composition, NCO/H ratio, Mw and Mn of the obtained hydroxyl-terminated urethane prepolymer, and branching degree α are shown in Table 4.

(Synthesis Example 17) Two-stage reaction method (Method 3) Into a four-necked flask including a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel, 80.0 parts by mass of the active hydrogen group-containing compound (HX-S-2) and 50.5 parts by mass of toluene were charged and mixed as 0.020 mass part of dioctyltin dilaurate and 0.008 mass part of tin 2-ethylhexanoate of catalyst. After that, the temperature of the content liquid was gradually increased to 80°C. Into the dropping funnel, 4.0 parts by mass of polyisocyanate (N-1) and 4.0 parts by mass of toluene were charged and mixed, and the mixed solution was added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the reaction was carried out for 1 hour. After confirming that the residual isocyanate group disappeared by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to 60° C. or lower. After adding and mixing 20.0 parts by mass of the active hydrogen group-containing compound (HY-L-6) to the content liquid, the content liquid was gradually heated up to 80°C. Into the dropping funnel, 1.5 parts by mass of polyisocyanate (N-1) and 3.0 parts by mass of toluene were charged and mixed, and the mixed solution was added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the reaction was carried out for 1 hour. The ratio (NCO/ H ratio) was 0.65. After the disappearance of the residual isocyanate group was confirmed by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to 40° C. to complete the reaction. Finally, 0.46 parts by mass of acetylacetone was added. As described above, a solution of a colorless and transparent hydroxyl-terminated urethane prepolymer (UPH-17) having a non-volatile content of 65% and a viscosity of 7000 cps was obtained. The main formulation composition, NCO/H ratio, Mw and Mn of the obtained hydroxyl-terminated urethane prepolymer, and branching degree α are shown in Table 2-2.

(Synthesis Example 35) Two-stage reaction method (Method 3) In Synthesis Example 35, a colorless and transparent hydroxyl-terminated amino group was obtained in the same manner as in Synthesis Example 17, except that the type of active hydrogen group-containing compound (H), the type of polyisocyanate (N), and the mixing ratio of these were changed. A solution of formate prepolymer (UPH-35). The main formulation composition, NCO/H ratio, Mw, Mn, and branching degree α of the obtained hydroxyl-terminated urethane prepolymer are shown in Table 3-2.

(Synthesis Example 18) Two-stage reaction method (Method 4) Into a four-necked flask including a stirrer, a reflux cooling tube, a nitrogen introduction tube, a thermometer, and a dropping funnel, 20.0 parts by mass of the active hydrogen group-containing compound (HY-L-6) and 50.5 parts by mass of toluene were charged and mixed as 0.020 mass part of dioctyltin dilaurate and 0.008 mass part of tin 2-ethylhexanoate of catalyst. After that, the temperature of the content liquid was gradually increased to 80°C. Into the dropping funnel, 1.5 parts by mass of polyisocyanate (N-1) and 3.0 parts by mass of toluene were charged and mixed, and the mixed solution was added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the reaction was carried out for 1 hour. After confirming that the residual isocyanate group disappeared by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to 60° C. or lower. To this content liquid, 80.0 parts by mass of the active hydrogen group-containing compound (HX-S-2) was added and mixed, and the content liquid was gradually heated up to 80°C. Into the dropping funnel, 4.0 parts by mass of polyisocyanate (N-1) and 4.0 parts by mass of toluene were charged and mixed, and the mixed solution was added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the reaction was carried out for 1 hour. The ratio (NCO/ H ratio) was 0.65. After the disappearance of the residual isocyanate group was confirmed by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to 40° C. to complete the reaction. Finally, 0.46 parts by mass of acetylacetone was added. As described above, a solution of a colorless and transparent hydroxyl-terminated urethane prepolymer (UPH-18) having a nonvolatile content of 65%, a viscosity of 2800 cps, and a colorless and transparent solution was obtained. The main formulation composition, NCO/H ratio, Mw and Mn of the obtained hydroxyl-terminated urethane prepolymer, and branching degree α are shown in Table 2-2.

(Synthesis Example 36) Two-stage reaction method (Method 4) In Synthesis Example 36, a colorless and transparent hydroxyl-terminated amino group was obtained in the same manner as in Synthesis Example 18, except that the type of active hydrogen group-containing compound (H), the type of polyisocyanate (N), and the mixing ratio of these were changed. A solution of formate prepolymer (UPH-36). The main formulation composition, NCO/H ratio, Mw, Mn, and branching degree α of the obtained hydroxyl-terminated urethane prepolymer are shown in Table 3-2.

[table 2-1] raw material Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Synthesis Example 11 One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) type branch degree α UPH-1 UPH-2 UPH-3 UPH-4 UPH-5 UPH-6 UPH-7 UPH-8 UPH-9 UPH-10 UPH-11 HX-1 0.45 80.0 HX-2 0.35 80.0 HX-S-1 0.05 80.0 HX-S-2 0.05 80.0 60.0 HX-S-3 0.08 80.0 100.0 60.0 HX-S-4 0.28 80.0 HX-S-5 0.05 80.0 40.0 HX-S-6 0.05 80.0 HX-S-7 0.05 HX-S-8 0.10 HY-1 0.58 HY-2 0.55 20.0 HY-L-1 0.70 HY-L-2 0.85 HY-L-3 0.95 HY-L-4 0.65 HY-L-5 0.95 20.0 20.0 20.0 20.0 40.0 HY-L-6 0.95 20.0 20.0 20.0 HY-L-7 0.75 HY-L-8 0.90 HY-L-9 0.90 N-1 25.0 5.5 5.0 32.0 8.0 5.5 4.5 N-2 6.0 23.0 23.0 8.5 N-3 N-4 NCO/H 0.78 0.65 0.58 0.74 0.59 0.74 0.83 0.53 0.65 0.80 0.64 Mn (×1000) 20 25 twenty two 18 25 19 13 20 28 27 20 Mw (×1000) 58 130 90 80 140 82 45 80 150 110 80 branch degree α 0.31 0.45 0.42 0.55 0.40 0.40 0.58 0.52 0.40 0.30 0.50

[Table 2-2] raw material Synthesis Example 12 Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 16 Synthesis Example 17 Synthesis Example 18 One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) All-in-one method (method 2) All-in-one method (method 2) Two-stage reaction method (method 3) Two-stage reaction method (method 4) type Divergence α UPH-12 UPH-13 UPH-14 UPH-15 UPH-16 UPH-17 UPH-18 HX-1 0.45 HX-2 0.35 HX-S-1 0.05 HX-S-2 0.05 80.0 80.0 80.0 80.0 HX-S-3 0.08 HX-S-4 0.28 HX-S-5 0.05 HX-S-6 0.05 HX-S-7 0.05 32.0 HX-S-8 0.10 75.0 HY-1 0.58 HY-2 0.55 HY-L-1 0.70 HY-L-2 0.85 20.0 HY-L-3 0.95 HY-L-4 0.65 HY-L-5 0.95 HY-L-6 0.95 20.0 100.0 20.0 20.0 HY-L-7 0.75 68.0 HY-L-8 0.90 25.0 HY-L-9 0.90 N-1 5.0 26.0 4.5 5.5 5.5 N-2 N-3 N-4 5.0 6.0 NCO/H 0.59 0.30 0.36 0.75 0.43 0.65 0.65 Mn (×1000) 25 25 20 15 6 35 20 Mw (×1000) 110 85 35 41 twenty two 140 85 branch degree α 0.45 0.23 0.50 0.26 0.28 0.33 0.72

[Table 3-1] raw material Synthesis Example 19 Synthesis Example 20 Synthesis Example 21 Synthesis Example 22 Synthesis Example 23 Synthesis Example 24 Synthesis Example 25 Synthesis Example 26 Synthesis Example 27 Synthesis Example 28 One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) type branch degree α UPH-19 UPH-20 UPH-21 UPH-22 UPH-23 UPH-24 UPH-25 UPH-26 UPH-27 UPH-28 HX-1 0.45 HX-2 0.35 15.0 HX-S-1 0.05 HX-S-2 0.05 15.0 HX-S-3 0.08 15.0 15.0 10.0 HX-S-4 0.28 15.0 HX-S-5 0.05 15.0 15.0 15.0 HX-S-6 0.05 HX-S-7 0.05 HX-S-8 0.10 HY-1 0.58 85.0 HY-2 0.55 85.0 HY-L-1 0.70 85.0 HY-L-2 0.85 85.0 HY-L-3 0.95 85.0 100.0 HY-L-4 0.65 85.0 HY-L-5 0.95 85.0 70.0 HY-L-6 0.95 85.0 20.0 HY-L-7 0.75 HY-L-8 0.90 HY-L-9 0.90 N-1 30.0 7.0 2.5 9.5 14.0 15.0 2.2 N-2 15.0 9.0 14.0 N-3 N-4 NCO/H 0.62 0.83 0.69 0.79 0.75 0.81 0.77 0.63 0.76 0.78 Mn (×1000) 10 17 28 33 twenty three twenty one 18 20 twenty three 33 Mw (×1000) 25 35 50 55 45 45 35 40 41 50 branch degree α 0.79 0.75 0.66 0.66 0.71 0.63 0.61 0.64 0.72 0.75

[Table 3-2] raw material Synthesis Example 29 Synthesis Example 30 Synthesis Example 31 Synthesis Example 32 Synthesis Example 33 Synthesis Example 34 Synthesis Example 35 Synthesis Example 36 One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) One-stage dropwise addition (method 1) All-in-one method (method 2) Two-stage reaction method (method 3) Two-stage reaction method (method 4) type branch degree α UPH-29 UPH-30 UPH-31 UPH-32 UPH-33 UPH-34 UPH-35 UPH-36 HX-1 0.45 HX-2 0.35 HX-S-1 0.05 HX-S-2 0.05 5.0 35.0 HX-S-3 0.08 70.0 15.0 15.0 15.0 HX-S-4 0.28 HX-S-5 0.05 40.0 15.0 HX-S-6 0.05 HX-S-7 0.05 HX-S-8 0.10 HY-1 0.58 HY-2 0.55 HY-L-1 0.70 HY-L-2 0.85 HY-L-3 0.95 60.0 85.0 85.0 HY-L-4 0.65 HY-L-5 0.95 30.0 85.0 85.0 HY-L-6 0.95 95.0 HY-L-7 0.75 HY-L-8 0.90 65.0 HY-L-9 0.90 N-1 2.5 9.0 N-2 7.0 3.0 15.0 15.0 N-3 2.3 N-4 2.4 NCO/H 0.50 0.59 0.61 0.37 0.27 0.65 0.75 0.75 Mn (×1000) 25 28 25 30 7 16 twenty two 20 Mw (×1000) 70 85 58 95 twenty one 35 55 40 branch degree α 0.61 0.38 0.63 0.43 0.78 0.41 0.48 0.78

[Table 4] raw material Synthesis Example 41 Synthesis Example 42 All-in-one method (method 2) All-in-one method (method 2) type branch degree α UPC-41 UPC-42 HX-1 0.45 HX-2 0.35 HX-S-1 0.05 100.0 HX-S-2 0.05 HX-S-3 0.08 HX-S-4 0.28 HX-S-5 0.05 HX-S-6 0.05 HX-S-7 0.10 HY-1 0.58 HY-2 0.55 HY-L-1 0.70 HY-L-2 0.85 HY-L-3 0.95 HY-L-4 0.65 HY-L-5 0.95 HY-L-6 0.95 HY-L-7 0.75 HY-L-8 0.90 HY-L-9 0.90 100.0 N-1 4.5 21.6 N-2 N-3 N-4 NCO/H 0.13 0.51 Mn (×1000) 6 1 Mw (×1000) 12 1.5 branch degree α 0.15 0.92

[Manufacture of adhesives and adhesive sheets] (Example 1) 100 parts by mass of the solution of the hydroxyl-terminated urethane prepolymer (UPH-1) obtained in Synthesis Example 1, 15 parts by mass of the polyfunctional isocyanate compound (I-1), and 1 part by mass of the antioxidant ( O-1), 15 parts by mass of plasticizer (P-1), and 100 parts by mass of ethyl acetate as a solvent were stirred with a disperser to obtain a urethane-based adhesive. In addition, the usage-amount of each material other than a solvent shows the non-volatile content conversion value (The same is true for other Examples and Comparative Examples). The main formulation compositions are shown in Table 5.

A 50 μm-thick polyethylene terephthalate film (PET film, Lumirror T-60: manufactured by Toray Corporation) was prepared as a substrate sheet. The obtained adhesive was applied to one side of the base sheet so that the thickness of the adhesive layer after drying was 12 μm, and dried at 100° C. for two minutes to form an adhesive layer. A release sheet (Super Stik SP-PET38: manufactured by Lintec) having a thickness of 38 μm was attached to the adhesive layer to obtain an adhesive sheet. After curing at 23°C-50% RH for one week, various evaluations were performed.

(Example 2 to Example 57, Comparative Example 1, Comparative Example 2) In each of Examples 2 to 57, Comparative Example 1, and Comparative Example 2, except that the preparation composition of the adhesive was changed as shown in Table 5 and Table 7, urethane was produced in the same manner as in Example 1. Ester-based adhesives and adhesive sheets using the same. In each example of Table 5 and Table 7, the conditions not described in the table were set as common conditions.

[Evaluation Items and Evaluation Methods of Adhesive Sheets] The evaluation items and evaluation methods of the adhesive sheet are as follows.

(Substrate Adhesion) For the adhesive layer of the obtained adhesive sheet, half-cuts were performed 11 times at intervals of 1 mm in two mutually orthogonal linear directions to form 100 squares of 1 mm. After rubbing the entire 100 grids back and forth 20 times with fingers, the number of grids remaining on the substrate sheet was visually counted. The evaluation criteria are as follows. ⊚: The number of remaining cells is 71 to 100, which is excellent. ○: The number of remaining cells is 51 to 70, which is good. △: The number of remaining cells is 21 to 50, which is practical. ×: The number of remaining cells is 0 to 20, and it is not practical.

(initial hardening) The release sheet was peeled off from the obtained adhesive sheet. Rub the surface of the exposed adhesive layer with a fingertip, and visually observe whether the components of the adhesive layer adhere to the fingertip and the surface of the adhesive layer for rubbing marks. The evaluation criteria are as follows. ⊚: The components of the adhesive layer did not adhere to the fingertips, and no traces after friction remained on the surface of the adhesive layer, which was excellent. (circle) : The component of an adhesive layer does not adhere to a fingertip, but the trace after rubbing remains slightly on the surface of an adhesive layer, and it is good. △: The components of a few adhesive layers are attached to the fingertips, which is sticky, and the surface of the adhesive layer is slightly rubbed, which is practical. ×: The components of the adhesive layer were clearly adhered to the fingertips, and there was a sticky feeling, and scratches after rubbing remained on the surface of the adhesive layer, and it was not practical.

(scratch resistance) The release sheet was peeled off from the obtained adhesive sheet. The front end (pen tip) of a POM pen (tip diameter 0.8 mm) inclined at an angle of 45° with respect to the surface of the exposed adhesive layer was brought into contact with the surface of the adhesive layer. Keeping this state, move the pen tip horizontally by about 10 cm so as to draw a straight line. The position was changed, and the same operation was performed on a total of 10 locations. The presence or absence of damage was visually observed at each site, and the number of damaged sites was determined. Visual inspection was performed under fluorescent light. The evaluation criteria are as follows. ⊚: No damage and excellent. ○: There is damage in one to two parts, which is good. △: There are damages in three to five parts, but it is practical. ×: There are damages in six or more places, and it is not practical.

(surface adhesion) A test piece having a width of 25 mm and a length of 40 mm was cut out from the obtained adhesive sheet. Next, the release sheet was peeled off from the test piece in an environment of 23°C-50%RH, and the exposed adhesive layer was stuck along the peripheral surface of a polypropylene cylinder (diameter 30 mmϕ, height 300 mm). At this time, the width direction of the test piece was merged with the height direction of the cylinder. After the sample was placed in an environment of 23° C.-50% RH for three days, the degree of adhesion of the test piece to the cylinder was visually observed. The evaluation criteria are as follows. (circle) : The edge part of a test piece does not float, and it is good. △: The edge of the test piece is lifted, and the width of the peeled part is 1 mm or more and less than 3 mm, which is practical. ×: The edge of the test piece was lifted, and the width of the peeled portion was 3 mm or more, which was not practical.

(Repeelability (60℃-90%RH, 24 hours)) A test piece having a width of 25 mm and a length of 100 mm was cut out from the obtained adhesive sheet. Next, the peeling sheet was peeled off from the test piece in an environment of 23° C.-50% RH, the exposed adhesive layer was attached to the caustic soda glass plate, and a 2 kg roller was pressed back and forth from the test piece once. Then, it was left to stand in the environment of 60°C-90%RH for 24 hours, and air-cooled for 30 minutes in the environment of 23°C-50%RH. Next, according to JIS Z 0237, using a tensile tester (tensilon: manufactured by Orientec), the adhesive force was measured under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180°. Easy to peel again when the adhesion is low. The evaluation criteria are as follows. ◎: Less than 50 mN/25 mm, excellent. ○: 50 mN/25 mm or more and less than 100 mN/25 mm, good. △: 100 mN/25 mm or more and less than 300 mN/25 mm, practical. ×: It exceeds 300 mN/25 mm and cannot be used practically.

(folding resistance) A test piece having a width of 25 mm and a length of 40 mm was cut out from the obtained adhesive sheet. Next, the peeling sheet was peeled off from the test piece in an environment of 60° C., about half of the exposed adhesive layer in the longitudinal direction was attached to a caustic soda glass plate with a thickness of 10 mm, and the rest was folded back in the 180° direction and attached. Place at 60°C for three days. After that, the degree of adhesion with the caustic soda glass plate was visually observed at the bent portion and the end portion of the portion to which the test piece was attached. The evaluation criteria are as follows. ⊚: There is no floating at the bent portion and the end portion, which is excellent. (circle) : The bending part and/or the edge part floated, and the width|variety of the peeled part was less than 1 mm, and it was good. △: The bent portion and/or the end portion is raised, and the width of the peeled portion is 1 mm or more and less than 3 mm, which is practical. ×: The bent portion and/or the edge portion was lifted, and the width of the peeled portion was 3 mm or more, which was not practical.

(cutting) A 100 mm square test piece was cut out from the obtained adhesive sheet. As a punching machine, SA1008 small punching machine III type (manufactured by TESTER SANGYO) was prepared. The punching process was continuously performed 50 times using a circular Thomson blade with a diameter of 10 mm, and the cuttability was evaluated. The evaluation criteria are as follows. ⊚: No adhesive component adhered to the blade, and the circular-shaped adhesive sheet punched out by the peeling sheet was cleanly peeled off with a light force, which was excellent. ○: The adhesive component was slightly adhered to the blade, but the circular-shaped adhesive sheet punched out by the peeling sheet could be peeled off cleanly with a light force, which was good. △: The adhesive component is slightly adhered to the blade, or there is a slight resistance when the peeling sheet is peeled off from the punched circular-shaped adhesive sheet, which is practical. ×: The component of the adhesive was significantly adhered to the blade, or the resistance when the peeling sheet was peeled off from the punched circular-shaped adhesive sheet was large, and it was not practical.

(Heat resistance (150°C, 1 hour)) A test piece having a width of 25 mm and a length of 100 mm was cut out from the obtained adhesive sheet. Next, the peeling sheet was peeled off from the test piece in an environment of 23° C.-50% RH, the exposed adhesive layer was attached to the caustic soda glass plate, and a 2 kg roller was pressed back and forth from the test piece once. Next, it was left to stand in an environment of 150° C. for 1 hour, and air-cooled for 30 minutes in an environment of 23° C.-50% RH. Next, according to JIS Z 0237, using a tensile tester (tensilon: manufactured by Orientec), the adhesive force was measured under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180°. Easy to peel again when the adhesion is low. The evaluation criteria are as follows. ◎: Less than 500 mN/25 mm, excellent. ○: 500 mN/25 mm or more and less than 1000 mN/25 mm, good. △: 1000 mN/25 mm or more and less than 3000 mN/25 mm, practical. ×: It exceeds 3000 mN/25 mm and cannot be used practically.

[Evaluation results] The evaluation results are shown in Tables 6 and 8. In Synthesis Example 1 to Synthesis Example 36, one or more compounds containing an active hydrogen group-containing compound (HX) having a branching degree α of 0.5 or less and/or an active hydrogen group-containing compound (HY) having a branching degree α exceeding 0.5 were used. Active hydrogen group-containing compound (H) and polyisocyanate (N) to obtain hydroxyl-terminated urethane prepolymer (UPH-1) - hydroxyl-terminated urethane prepolymer with branching degree α of 0.2 to 0.8 material (UPH-36). In Example 1 to Example 57 using a hydroxyl-terminated urethane prepolymer (UPH-1) to a hydroxyl-terminated urethane prepolymer (UPH-36) with a branching degree α of 0.2 to 0.8 , and the evaluation results of the initial hardening property and re-peelability (60°C-90%RH) of the obtained adhesive sheet were good. Regarding other evaluation items, the evaluation results were also favorable.

In Synthesis Example 1 to Synthesis Example 13, Synthesis Example 16, and Synthesis Example 17, one or more active hydrogen group-containing compounds (H) contain 50% by mass or more of active hydrogen group-containing compounds (H) having a branching degree α of 0.5 or less ( HX), the branching degree α of the hydroxyl-terminated urethane prepolymer (UPH) is 0.2-0.6. Initial curability and exposure of the adhesive sheets obtained in Examples 1 to 22, Example 25, and Example 26 using the hydroxyl-terminated urethane prepolymer (UPH) obtained in these synthesis examples The re-peelability (the effect of suppressing the increase in the adhesive force) in a hot environment, especially in a humid and hot environment, is good, and furthermore, the substrate adhesion, scratch resistance, and curved surface adhesion are good.

In Synthesis Example 19 to Synthesis Example 29, Synthesis Example 31, Synthesis Example 33, and Synthesis Example 36, one or more active hydrogen group-containing compounds (H) contain 50% by mass or more of active hydrogen group-containing groups with a branching degree α exceeding 0.5 The compound (HY), the branching degree α of the hydroxyl-terminated urethane prepolymer (UPH) exceeds 0.6 and is 0.8 or less. The initial stage of the adhesive sheet obtained in Example 28 to Example 46, Example 48, Example 50, and Example 53 using the hydroxyl-terminated urethane prepolymer (UPH) obtained in these synthesis examples Curability and releasability (the effect of suppressing the increase in adhesive force) when exposed to a thermal environment, particularly a humid-heat environment, are good, and furthermore, the folding resistance, cutting properties, and heat resistance are good.

In Synthesis Example 41, an active hydrogen group-containing compound (HX) having a branching degree α of 0.5 or less and a polyisocyanate (N) were used to obtain a hydroxyl-terminated urethane prepolymer for comparison with a branching degree α of less than 0.2. material (UPC-1). In Synthesis Example 42, a hydroxyl-terminated urethane prepolymer (UPC-2) having a branching degree α exceeding 0.8 was obtained by using the active hydrogen group-containing compound (HY) and polyisocyanate (N) exceeding 0.5. ). In Comparative Example 1 and Comparative Example 2 using the comparative hydroxyl-terminated urethane prepolymer (UPC-1) or the comparative hydroxyl-terminated urethane prepolymer (UPC-2), the The obtained adhesive sheet had poor evaluation results of initial curability and re-peelability (60°C-90%RH). Regarding many other evaluation items, the evaluation results were also poor.

[table 5] adhesive Urethane Prepolymer (UPH) or (UPC) Polyfunctional isocyanate compound (I) Antioxidants AS agent Plasticizer type Allocated amount I-1 I-2 O-1 AS-1 P-1 P-2 Example 1 UPH-1 100 15 1 15 Example 2 UPH-2 100 15 1 15 Example 3 UPH-3 100 15 1 15 Example 4 100 1 1 15 Example 5 100 5 1 15 Example 6 100 25 1 15 Example 7 100 40 1 15 Example 8 100 15 1 15 Example 9 100 15 1 0.5 15 Example 10 100 15 15 Example 11 100 15 1 15 Example 12 100 15 1 50 Example 13 100 15 1 150 Example 14 100 15 1 Example 15 UPH-4 100 15 1 15 Example 16 UPH-5 100 15 1 15 Example 17 UPH-6 100 15 1 15 Example 18 UPH-7 100 15 1 15 Example 19 UPH-8 100 15 1 15 Example 20 UPH-9 100 15 1 15 Example 21 UPH-10 100 15 1 15 Example 22 UPH-11 100 15 1 15 Example 23 UPH-12 100 15 1 15 Example 24 UPH-13 100 15 1 15 Example 25 UPH-14 100 15 1 15 Example 26 UPH-15 100 15 1 15 Example 27 UPH-16 100 15 1 15 Example 28 UPH-17 100 15 1 15 Example 29 UPH-18 100 15 1 15 Comparative Example 1 UPC-41 100 15 Comparative Example 2 UPC-42 100 15

[Table 6] adhesive layer Substrate Adhesion initial hardening scratch resistance Surface Adhesion Repeelability (60℃-90%RH, 24 hours) Example 1 〇 ◎ ◎ △ 〇 Example 2 ◎ ◎ ◎ 〇 ◎ Example 3 ◎ ◎ ◎ 〇 ◎ Example 4 ◎ 〇 〇 △ 〇 Example 5 ◎ 〇 ◎ 〇 〇 Example 6 ◎ ◎ ◎ 〇 ◎ Example 7 ◎ ◎ ◎ △ ◎ Example 8 ◎ ◎ ◎ 〇 ◎ Example 9 ◎ ◎ ◎ 〇 ◎ Example 10 ◎ ◎ ◎ 〇 〇 Example 11 ◎ ◎ ◎ 〇 ◎ Example 12 ◎ ○ ○ 〇 ◎ Example 13 ◎ △ △ 〇 ◎ Example 14 ◎ ◎ ◎ 〇 〇 Example 15 ◎ ◎ 〇 〇 ◎ Example 16 ◎ ◎ ◎ 〇 ◎ Example 17 ◎ ◎ ◎ △ ◎ Example 18 ◎ 〇 △ 〇 〇 Example 19 ◎ ◎ △ 〇 ◎ Example 20 ◎ ◎ ◎ △ ◎ Example 21 〇 ◎ ◎ △ ◎ Example 22 〇 ◎ 〇 〇 ◎ Example 23 ◎ △ ◎ 〇 ◎ Example 24 △ ◎ ◎ 〇 ◎ Example 25 ◎ △ △ 〇 △ Example 26 △ ◎ △ 〇 〇 Example 27 △ △ ◎ 〇 △ Example 28 〇 ◎ ◎ 〇 ◎ Example 29 ◎ △ ◎ 〇 △ Comparative Example 1 × × 〇 × × Comparative Example 2 × × × △ ×

[Table 7] adhesive Urethane Prepolymer (UPH) or (UPC) Polyfunctional isocyanate compound (I) Antioxidants AS agent Plasticizer type Allocated amount I-1 I-2 O-1 AS-1 P-1 P-2 Example 30 UPH-19 100 15 1 15 Example 31 UPH-20 100 10 1 15 Example 32 UPH-21 100 10 1 15 Example 33 UPH-22 100 10 1 15 Example 34 UPH-23 100 1 1 15 Example 35 100 7 1 15 Example 36 100 15 1 15 Example 37 100 30 1 15 Example 38 100 15 1 15 Example 39 100 15 1 0.5 15 Example 40 100 15 15 Example 41 100 15 1 15 Example 42 100 15 1 50 Example 43 100 15 1 150 Example 44 100 15 1 Example 45 UPH-24 100 15 1 15 Example 46 UPH-25 100 15 1 15 Example 47 UPH-26 100 15 1 15 Example 48 UPH-27 100 15 1 15 Example 49 UPH-28 100 15 1 15 Example 50 UPH-29 100 15 1 15 Example 51 UPH-30 100 15 1 15 Example 52 UPH-31 100 15 1 15 Example 53 UPH-32 100 15 1 15 Example 54 UPH-33 100 15 1 15 Example 55 UPH-34 100 15 1 15 Example 56 UPH-35 100 15 1 15 Example 57 UPH-36 100 15 1 15 Comparative Example 1 UPC-41 100 15 Comparative Example 2 UPC-42 100 15

[Table 8] adhesive layer Folding resistance initial hardening tailoring Heat resistance (150℃, 1 hour) Repeelability (60℃-90%RH, 24 hours) Example 30 ◎ 〇 〇 〇 〇 Example 31 ◎ ◎ ◎ ◎ ◎ Example 32 〇 ◎ ◎ ◎ ◎ Example 33 〇 △ 〇 ◎ ◎ Example 34 ◎ 〇 ◎ 〇 〇 Example 35 ◎ ◎ ◎ ◎ 〇 Example 36 ◎ ◎ ◎ ◎ ◎ Example 37 ◎ ◎ ◎ ◎ ◎ Example 38 ◎ ◎ ◎ ◎ ◎ Example 39 ◎ ◎ ◎ ◎ ◎ Example 40 ◎ ◎ ◎ 〇 〇 Example 41 ◎ ◎ ◎ ◎ ◎ Example 42 ◎ 〇 〇 ◎ ◎ Example 43 ◎ △ △ ◎ ◎ Example 44 ◎ ◎ ◎ 〇 〇 Example 45 〇 ◎ ◎ ◎ ◎ Example 46 〇 ◎ △ ◎ ◎ Example 47 ◎ ◎ △ ◎ ◎ Example 48 ◎ ◎ ◎ ◎ ◎ Example 49 ◎ ◎ ◎ △ ◎ Example 50 〇 ◎ 〇 ◎ ◎ Example 51 △ ◎ △ ◎ ◎ Example 52 〇 ◎ ◎ ◎ ◎ Example 53 △ ◎ △ ◎ ◎ Example 54 ◎ 〇 ◎ 〇 〇 Example 55 △ ◎ △ ◎ ◎ Example 56 △ ◎ △ ◎ ◎ Example 57 ◎ ◎ ◎ ◎ ◎ Comparative Example 1 × × × × × Comparative Example 2 ◎ × ◎ × ×

The present invention is not limited to the above-described embodiments and examples, and can be appropriately changed in design as long as they do not depart from the gist of the present invention.

10, 20: Adhesive sheet 11, 21: substrate sheet 12, 22A, 22B: Adhesive layer 13, 23A, 23B: peel off sheet

FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to a first embodiment of the present invention. 2 is a schematic cross-sectional view of an adhesive sheet according to a second embodiment of the present invention. FIG. 3 is an image diagram of a production example of a prepolymer.

10: Adhesive sheet

11: substrate sheet

12: Adhesive layer

13: peel off sheet

Claims (11)

An adhesive comprising: Hydroxy-terminated urethane prepolymer (UPH), the hydroxyl-terminated urethane prepolymer (UPH) is one or more active hydrogen group-containing compounds having a plurality of active hydrogen groups in one molecule ( H), reaction products with more than one polyisocyanate (N); and Polyfunctional isocyanate compound (I), in the adhesive, The branching degree in the hydroxyl-terminated urethane prepolymer (UPH) measured by gel permeation chromatography-multi-angle laser light scattering was 0.2-0.8. The adhesive according to claim 1, wherein the one or more active hydrogen group-containing compounds (H) contain 50% by mass or more of a branching degree measured by gel permeation chromatography-multi-angle laser light scattering method of 0.5 or less Compounds containing active hydrogen groups (HX), The branching degree in the hydroxyl-terminated urethane prepolymer (UPH) measured by gel permeation chromatography-multi-angle laser light scattering was 0.2-0.6. The adhesive according to claim 2, wherein at least one active hydrogen group-containing compound (H) contains 50% by mass or more of a branching degree measured by gel permeation chromatography-multi-angle laser light scattering method of 0.3 or less Compounds containing active hydrogen groups (HX-S). The adhesive according to claim 2, wherein the one or more active hydrogen group-containing compounds (H) contain 50 mass % or more and less than 100 mass % of the amount of the Active hydrogen group-containing compounds (HX) with a branching degree of 0.5 or less, containing more than 0 mass % and less than 50 mass % of active hydrogen group-containing compounds with a branching degree measured by gel permeation chromatography-multi-angle laser light scattering method exceeding 0.5 Hydrogen-based compounds (HY). The adhesive according to claim 1, wherein the one or more active hydrogen group-containing compounds (H) contain 50% by mass or more of compounds having a branching degree of more than 0.5 as measured by gel permeation chromatography-multi-angle laser light scattering Active hydrogen based compounds (HY), In the hydroxyl-terminated urethane prepolymer (UPH), the degree of branching measured by gel permeation chromatography-multi-angle laser light scattering exceeds 0.6 and is 0.8 or less. The adhesive according to claim 5, wherein the one or more active hydrogen group-containing compounds (H) contain 50% by mass or more of a branching degree measured by a gel permeation chromatography-multi-angle laser light scattering method of more than 0.6 containing Active hydrogen-based compounds (HY-L). The adhesive according to claim 5, wherein the one or more active hydrogen group-containing compounds (H) contain 50 mass % or more and less than 100 mass % of the amount of the Active hydrogen group-containing compounds (HY) having a branching degree of more than 0.5, including more than 0 mass % and less than 50 mass % of active hydrogen group-containing compounds having a branching degree measured by gel permeation chromatography-multi-angle laser light scattering method of 0.5 or less Hydrogen-based compounds (HX). The adhesive according to claim 1 or claim 2, further comprising a plasticizer. The adhesive according to claim 1 or claim 2, further comprising an antistatic agent. The adhesive according to claim 1 or claim 2, further comprising one or more anti-deterioration agents selected from the group consisting of antioxidants, hydrolysis-resistant agents, ultraviolet absorbers, and light stabilizers. An adhesive sheet comprising a base material sheet and an adhesive layer of a hardened product comprising the adhesive according to any one of Claims 1 to 10.

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