Moisture-curable resin composition, adhesive for electronic component, cured body, and electronic component

Abstract

A moisture-curable resin composition comprising a moisture-curable urethane resin (A) as a polyol, wherein the moisture-curable urethane resin (A) is a prepolymer obtained from at least a polyol A and a polyol B with a polyisocyanate, wherein the polyol A is a linear polyol, and the polyol B is a polyol having a branched chain.

Description

Moisture-curable resin composition, adhesive for electronic components, cured product, electronic component

[0001] The present invention relates to a moisture-curable resin composition, an adhesive for electronic components containing the composition, a cured product of the composition, and an electronic component containing the cured product.

[0002] Conventionally, adhesive tapes have often been used to bond components of portable electronic devices such as smartphones, but in recent years, moisture-curable resin compositions, which allow for automated production, have come to be used as adhesives.

[0003] Various types of adhesives have been proposed. For example, Patent Document 1 discloses an invention relating to a moisture-curable hot-melt pressure-sensitive adhesive containing a urethane polymer having an isocyanate group, which is obtained by reacting a polyol compound (A) with a polyisocyanate (B), and having a storage modulus of a certain level or less. Patent Document 2 discloses an invention relating to an adhesive composition characterized by having a base agent containing a urethane prepolymer and an isocyanate silane compound, and a curing agent containing a multifunctional polyol compound obtained by modifying the terminals of a specific type of isocyanate with rosin diol.

[0004] JP 2023-016218 A JP 2014-122301 A

[0005]

[0003] Adhesives used in the context of promoting automation of production processes for electronic devices and the like are required to have improved initial adhesive strength and long-term reliability. To improve initial adhesive strength, it is necessary to increase the molecular weight of the base agent, such as a urethane prepolymer. However, increasing the molecular weight results in a deterioration of adhesive strength in high-temperature environments, which is problematic from the perspective of long-term reliability. Therefore, with conventional adhesives, there is a trade-off between initial adhesive strength and high-temperature adhesive strength, making it difficult to achieve the above performance.

[0006] Therefore, an object of the present invention is to provide a moisture-curable resin composition that can easily increase initial adhesive strength and easily maintain adhesive strength even in a high-temperature environment.

[0007] As a result of extensive investigation, the present inventors have found that the above-mentioned problems can be solved by blending two types of polyols, a linear polyol and a branched polyol, into a moisture-curable resin composition. That is, the present invention provides the following [1] to

[13] .

[0008] [1] A moisture-curable resin composition comprising a moisture-curable urethane resin (A) obtained by prepolymerizing at least polyol A and polyol B with a polyisocyanate as polyols, wherein the polyol A is a linear polyol containing structural units derived from a polycarbonate polyol, and the polyol B is a polyol having a branched chain containing 6 or more carbon atoms. [2] The moisture-curable resin composition according to [1], wherein the polyol B is a rosin polyol. [3] The moisture-curable resin composition according to [1] or [2], wherein the content of the moisture-curable urethane resin (A) per 100 parts by mass of the moisture-curable resin composition is 35 parts by mass or more and 100 parts by mass or less. [4] The moisture-curable resin composition according to any one of [1] to [3], wherein the polycarbonate polyol contains structural units derived from a polyether polycarbonate polyol. [5] The moisture-curable resin composition according to any one of [1] to [4], wherein the moisture-curable resin composition is liquid at 25°C. [6] The moisture-curable resin composition according to any one of [1] to [5], wherein the hydroxyl value of the polyol B is 5 to 200 mgKOH / g. [7] The moisture-curable resin composition according to any one of [1] to [6], further comprising a radically polymerizable compound and a photopolymerization initiator. [8] The moisture-curable resin composition according to [7], wherein the radically polymerizable compound comprises a monofunctional radically polymerizable compound. [9] The moisture-curable resin composition according to [8], wherein the content of the monofunctional radically polymerizable compound is 80 parts by mass or more per 100 parts by mass of the radically polymerizable compound.

[10] The moisture-curable resin composition according to [8] or [9], wherein the monofunctional radically polymerizable compound comprises a polyoxyethylene (meth)acrylate.

[11] An adhesive for electronic components, comprising the moisture-curable resin composition according to any one of [1] to

[10] .

[12] A cured product of the moisture-curable resin composition according to any one of [1] to

[10] .

[13] An electronic component comprising the cured product according to

[12] .

[0009] According to the present invention, it is possible to provide a moisture-curable resin composition that can easily increase initial adhesive strength and easily maintain adhesive strength even in a high-temperature environment.

[0010] 1 is a schematic diagram for explaining a method for measuring shear adhesive strength. FIG. 2 is a schematic diagram for explaining a method for performing a hanging test.

[0011] [Moisture-curable resin composition] The moisture-curable resin composition of the present invention contains, as a moisture-curable resin, a moisture-curable urethane resin (A) obtained by prepolymerizing at least polyol A and polyol B with polyisocyanate as polyols. Hereinafter, each component constituting the moisture-curable resin composition will be described in detail.

[0012] (Moisture-curing urethane resin (A)) As described above, the moisture-curing urethane resin (A) is obtained by prepolymerizing at least polyol A and polyol B with a polyisocyanate. For example, when prepolymerizing polyol A and polyol B to obtain a moisture-curing urethane resin (A), polyol A and polyol B may be prepolymerized with a polyisocyanate, respectively, and then mixed to obtain the prepolymerized product. Alternatively, polyol A and polyol B may be mixed and the mixed polyol may be prepolymerized with a polyisocyanate. The moisture-curing urethane resin (A) may be a mixture of at least one of those obtained by prepolymerizing polyol A with a polyisocyanate and those obtained by prepolymerizing polyol B with a polyisocyanate, and a mixture of polyol A and polyol B obtained by prepolymerizing a mixture of polyol A and polyol B with a polyisocyanate.

[0013] The above description has been given of a case in which the moisture-curing urethane resin (A) is obtained by prepolymerizing only polyol A and polyol B as polyols. However, the moisture-curing urethane resin (A) is not limited to the above. It may also be obtained by prepolymerizing polyols other than polyol A and polyol B (hereinafter also referred to as "other polyols") with a polyisocyanate. In this case, the moisture-curing urethane resin (A) can be obtained, for example, by any of the following methods (1) to (3). (1) A method in which polyol A, polyol B, and the other polyol are each prepolymerized with a polyisocyanate and mixed together. (2) A method in which polyol A, polyol B, and the other polyol are mixed, and the mixed polyol is prepolymerized with a polyisocyanate. (3) A method in which at least two of polyol A, polyol B, and the other polyol are mixed, and the mixed polyol is prepolymerized with a polyisocyanate and the remaining polyol is prepolymerized with a polyisocyanate are mixed together.

[0014] In the present invention, it is preferable to obtain a moisture-curable urethane resin (A) by mixing at least polyol A and polyol B and prepolymerizing the mixed polyol with polyisocyanate. As a result, both polyol A and polyol B are introduced into one molecule of the moisture-curable urethane (A) resin, improving the cohesive strength of the moisture-curable resin composition and making it easier to improve adhesion. Although the reason for this is unclear, it is presumed that the incorporation of polyol A and polyol B into the main chain of the polyurethane resin lengthens the main chain portion of the polyurethane resin, thereby improving the cohesive strength, and that the distance between the hydroxyl groups of polyol B is short, increasing the urethane bond density.

[0015] The urethane resin constituting the moisture-curing urethane resin (A) can be obtained by reacting a polyol with a polyisocyanate having two or more isocyanate groups per molecule. The reaction is preferably carried out in a molar ratio of [NCO] / [OH] between the hydroxyl groups (OH) in the polyol and the isocyanate groups (NCO) in the polyisocyanate, in the range of 1.1 to 2.5, preferably 1.15 to 2.0, and more preferably 1.2 to 1.8. By keeping [NCO] / [OH] within the above range, it becomes easier to incorporate multiple isocyanate groups into one molecule without increasing the molecular weight of the moisture-curing urethane resin (A) more than necessary. In this case, the urethane resin constituting the moisture-curing urethane resin (A) may be obtained by reacting a mixture of at least two of polyol A, polyol B, and other polyols used as needed with a polyisocyanate, as described above, or by reacting one of polyol A, polyol B, or other polyols used as needed with a polyisocyanate.

[0016] <Polyol A> Polyol A is a linear polyol containing structural units derived from a polycarbonate polyol. In this specification, the term "linear polyol" refers to a polyol whose molecular structure is a linear structure consisting of a main chain and has no branched chains, or if it has a branched chain, the number of carbon atoms therein is less than 6. The number of carbon atoms in the branched chain is not particularly limited, but is preferably 4 or less, more preferably 2 or less, and even more preferably 1 or less. Here, the longest of the linear carbon-containing skeletons connecting two hydroxyl groups is the main chain of polyol A. Note that the linear carbon-containing skeleton connecting two hydroxyl groups may have at least one of a branched chain having a carbon number of less than 6 and a hydroxyl group, but typically, no hydroxyl group is bonded to a carbon atom located other than at both ends of the skeleton. For example, in the case of polyol A having a structure represented by the following formula (1), the carbon atom (X) to which one hydroxyl group is bonded to the carbon atom (Y) to which the other hydroxyl group is bonded constitutes the main chain of polyol A. Therefore, polyol A has a structure in which a hydroxyl group is bonded to each of the carbon atoms at both ends of the main chain. Note that polyol A is not limited to the structure represented by formula (1) below, and may have other structures. In formula (1), R represents an organic group having a carbon number of less than 6 and which may have at least one of a branched chain and a hydroxyl group, and R １ and R ２ each independently represents a hydrogen atom or an organic group having less than 6 carbon atoms. The organic group represented by R has, for example, 1 to 500 carbon atoms.

[0017] The polyol A may contain structural units derived from polyols other than polycarbonate polyols, such as polyester polyols, polyether polyols, and polyalkylene diols. Among these, structural units derived from polyester polyols are preferred. The polyol A may be a diol having two hydroxyl groups or a polyol having three or more hydroxyl groups, but a diol having two hydroxyl groups is preferred. That is, the polyol A preferably contains structural units derived from polycarbonate diols, and may also contain structural units derived from polycarbonate diols and diols other than polycarbonate diols. The polyol A may contain structural units derived from only one type of polyol (i.e., polycarbonate polyol), or may contain structural units derived from two or more types of polyols, but preferably contains structural units derived from only one type of polyol. For example, a polycarbonate polyol such as the polyether polycarbonate polyol described below may be used as the polyol A.

[0018] <<Polycarbonate polyol>> Polycarbonate polyol has a structure in which structural units derived from a polyhydroxy compound are linked by carbonate bonds. The method for producing the polycarbonate polyol is not particularly limited, and it may be produced using a polyhydroxy compound as a raw material by a known method such as a phosgene method or a transesterification method.

[0019] The polyhydroxy compound is generally a dihydroxy compound. The polyhydroxy compound may be any of an aliphatic polyol, an alicyclic polyol having an alicyclic structure, an aromatic polyhydroxy compound, etc., but the polyhydroxy compound is preferably an aliphatic polyol or an alicyclic polyol, more preferably an aliphatic polyol. The aliphatic polyol is a divalent linear aliphatic polyol or an aliphatic polyol having a branched chain with less than 6 carbon atoms.

[0020] The aliphatic polyol may not have, for example, an ether bond. In such a case, examples of the aliphatic polyol include alkanediols having 2 to 16, and preferably about 4 to 12, carbon atoms. Specific examples include linear aliphatic polyols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, and 1,16-hexadecanediol; and branched aliphatic polyols such as neopentyl glycol and 3-methyl-1,5-pentanediol. Among these, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and 3-methyl-1,5-pentanediol are preferred, and 1,6-hexanediol and 3-methyl-1,5-pentanediol are more preferred. These aliphatic diols may be used alone or in combination of two or more.

[0021] The polycarbonate polyol is preferably a polycarbonate diol. Specific examples of the polycarbonate diol include compounds represented by the following formula (2):

[0022] In formula (2), R is a divalent hydrocarbon group having 4 to 16 carbon atoms, and n is an integer of 2 to 120.

[0023] In formula (2), R is preferably an aliphatic saturated hydrocarbon group. When R is an aliphatic saturated hydrocarbon group, heat resistance and flexibility tend to be improved. R consisting of an aliphatic saturated hydrocarbon group may have a chain structure or a cyclic structure, but a chain structure is preferred. Furthermore, R having a chain structure may be either linear or branched. n is preferably 2 to 25, more preferably 2 to 20, even more preferably 5 to 20, and most preferably 5 to 15. The number of carbon atoms in R is preferably 4 to 12, more preferably 6 to 10. Furthermore, the R contained in the polycarbonate diol may be used alone or in combination of two or more types. When two or more types of R are used in combination, for example, a linear aliphatic saturated hydrocarbon group and a branched aliphatic saturated hydrocarbon group may be used in combination.

[0024] <<Polyether Polycarbonate Polyol>> The polycarbonate polyol preferably contains a constituent component derived from a polyether polycarbonate polyol having a polyether skeleton. The polyether polycarbonate polyol has an ether bond in a constituent unit derived from a polyhydroxy compound, and a polyether polyol may be used as the polyhydroxy compound. The polyether polycarbonate polyol has a polyether skeleton and a carbonate bond. Furthermore, the polyether polycarbonate polyol preferably has two or more carbonate bonds in the molecule. The polyether polycarbonate polyol has an ether bond in a constituent unit derived from a polyhydroxy compound, and a polyether polyol may be used as the polyhydroxy compound.

[0025] In polyether polycarbonate polyols, the polyether skeleton typically has a structure in which divalent hydrocarbon groups are linked by ether bonds. The divalent hydrocarbon group is not particularly limited, but may have, for example, 2 to 12 carbon atoms, preferably 3 to 8 carbon atoms. The divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring, with an aliphatic hydrocarbon group being preferred. The aliphatic hydrocarbon group may be linear, branched, or may have an alicyclic structure, with a linear structure being preferred.

[0026] The polyether polycarbonate polyol is preferably a polyether polycarbonate diol. The polyether polycarbonate diol preferably has a structure in which multiple polyether skeletons are bonded via carbonate bonds. The polyether polycarbonate diol preferably has hydroxyl groups at both ends of the molecule. Specifically, the polyether polycarbonate diol is more preferably a compound represented by the following formula (3):

[0027] In the above formula (3), R represents a divalent hydrocarbon group having 2 to 12 carbon atoms, n is an integer of 2 to 90, and m is an integer of 1 to 35. In addition, in formula (3), multiple R may be the same or different.

[0028] In the above formula (3), R preferably has 2 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, even more preferably 3 to 5 carbon atoms, and most preferably 4 carbon atoms. R may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring; however, an aliphatic hydrocarbon group is preferred, an aliphatic saturated hydrocarbon group is more preferred, and a linear alkylene group having 3 to 8 carbon atoms is even more preferred. Therefore, specific preferred R groups include trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene; among these, trimethylene, tetramethylene, and pentamethylene are more preferred, and tetramethylene is most preferred. These alkylene groups may be used alone or in combination. In the above formula (3), n is 2 to 90, preferably 2 to 45, more preferably 2 to 15, even more preferably 2 to 10, and most preferably 2 to 5. Furthermore, m is 1 to 35, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 6, and most preferably 2 to 6.

[0029] The polyether polycarbonate diol is preferably produced by a known method such as a phosgene method or an ester exchange method using polyoxyalkylene glycol as a raw material. Therefore, the above-mentioned polyether skeleton is preferably derived from polyoxyalkylene glycol. Preferred examples of polyoxyalkylene glycol include polypropylene glycol, polytetramethylene ether glycol, and copolymerized polyether glycol of propylene oxide and tetrahydrofuran, among which polytetramethylene ether glycol (PTMG) is more preferred. Note that only one type of polyoxyalkylene glycol may be used, or two or more types may be used in combination.

[0030] <<Polyester Polyol>> Examples of polyester polyols include polyester polyols obtained by reacting polycarboxylic acid with polyol, and poly-ε-caprolactone polyols obtained by ring-opening polymerization of ε-caprolactone. Among these, polyester polyols obtained by reacting polycarboxylic acid with polyol are preferred. Furthermore, the polyester polyol is preferably a crystalline polyol. The polyester polyols may be used alone or in combination of two or more. Furthermore, polyester diols are preferred as polyester polyols.

[0031] Examples of polycarboxylic acids that can be used as raw materials for polyester polyols include divalent aromatic carboxylic acids such as terephthalic acid, isophthalic acid, 1,5-naphthalic acid, and 2,6-naphthalic acid, divalent aliphatic carboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, and dodecamethylene dicarboxylic acid, trivalent or higher aromatic carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid, and naphthalene tricarboxylic acid, and trivalent or higher aliphatic carboxylic acids such as cyclohexane tricarboxylic acid and hexane tricarboxylic acid. These polycarboxylic acids may be used alone or in combination of two or more.

[0032] Examples of polyols that can be used as raw materials for polyester polyols include linear aliphatic polyols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and diethylene glycol, aliphatic polyols having a branched structure such as neopentyl glycol, and aliphatic polyols having a cyclic skeleton such as cyclohexanediol. These polyols may be used alone or in combination of two or more.

[0033] <<Polyether Polyols>> Examples of polyether polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, ring-opening polymers of tetrahydrofuran, and ring-opening polymers of 3-methyltetrahydrofuran, as well as random or block copolymers of these or their derivatives, and bisphenol-type polyoxyalkylene modified products. Here, the bisphenol-type polyoxyalkylene modified product is a polyether polyol obtained by addition reaction of an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) with the active hydrogen moiety of a bisphenol-type molecular skeleton. The polyether polyol may be a random copolymer or a block copolymer. The bisphenol-type polyoxyalkylene modified product preferably has one or more alkylene oxides attached to both ends of the bisphenol-type molecular skeleton. The bisphenol-type polyoxyalkylene modified product is not particularly limited, and examples include A-type, F-type, and S-type, with bisphenol A-type being preferred. One type of polyether polyol may be used alone, or two or more types may be used in combination. The polyether polyol is preferably a polyether diol.

[0034] The hydroxyl value of polyol A is preferably 10 to 900 mgKOH / g, more preferably 20 to 450 mgKOH / g, and even more preferably 30 to 200 mgKOH / g. When the hydroxyl value of polyol A is within the above range, the molecular weight of polyol A becomes appropriately high, making it easier to increase the initial adhesive strength and the adhesive strength under high temperature environments. The hydroxyl value may be measured according to JIS K 1557-1. The hydroxyl values ​​of polyol B and other polyols described below are also measured in the same manner.

[0035] When polyol A is used, a chain extender may be used. The chain extender is used in addition to the above-mentioned polyol as part of polyol A or as a component other than polyol A. In this specification, chain extenders are not considered to be included in other polyols. The chain extender may be prepolymerized, for example, together with polyol A, or polyol A, polyol B, and other polyols used as needed, to form a moisture-curable urethane resin. In this case, the moisture-curable urethane resin may be obtained, for example, by prepolymerizing a mixture of polyol A and a chain extender, or a mixture of polyol A, polyol B, other polyols used as needed, and a chain extender with polyisocyanate, or by further chain-extending polyol A, or polyol A, polyol B, and other polyols used as needed prepolymerized with polyisocyanate using a chain extender. The use of a chain extender can further improve the cohesive strength of the moisture-curable resin composition, making it easier to control the balance between rotation speed and adhesive strength. As the chain extender, for example, in the case of producing a urethane prepolymer having an isocyanate group, a low-molecular-weight compound having at least two active hydrogens that react with the isocyanate group is preferred, and at least one selected from polyols and polyamines is more preferred.

[0036] Examples of polyols that can be used as chain extenders include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol, as well as 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and 2-methyl-1,8-octanediol. diols having an ether group such as diethylene glycol and propylene glycol; diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 1,4-dihydroxyethylcyclohexane; diols having an aromatic group such as xylylene glycol, 1,4-dihydroxyethylbenzene and 4,4'-methylenebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane and pentaerythritol; and polyols having a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid.

[0037] Examples of amines that can be used as chain extenders include hydroxyamines such as N-methylethanolamine and N-ethylethanolamine, and polyamines such as ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine. These chain extenders may be used alone or in combination of two or more.

[0038] The chain extender may be used in an amount of, for example, 0.01 parts by mass or more and 50 parts by mass or less, preferably 0.05 parts by mass or more and 30 parts by mass or less, and more preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total polyol to be prepolymerized.

[0039] The amount of polyol A used is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 25 parts by mass or more, and preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less, relative to 100 parts by mass of the total polyols. When the amount of polyol A used is a certain amount or more, the cohesive strength is increased and adhesiveness is easily improved. Furthermore, when the amount of polyol A used is a certain amount or less, it is easy to use the amount of polyol B used in a certain amount or more. Polyol A may be used alone or in combination of two or more types.

[0040] <Polyol B> Polyol B is a polyol having a branched chain. The branched chain constituting polyol B is a branched chain having 6 or more carbon atoms and is other than the main chain. Like polyol A, polyol B also has the longest linear carbon-containing skeleton connecting two hydroxyl groups as the main chain. The number of carbon atoms in the carbon-containing skeleton that forms the main chain is preferably about 2 to 50, and more preferably about 2 to 20. Polyol B is preferably at least one selected from polyether-based polyols such as α-[2,2-bis(hydroxymethyl)butyl]-ω-methoxypoly(oxyethylene), rosin polyols, and poly(meth)acrylic polyols. Furthermore, at least one selected from rosin polyols and poly(meth)acrylic diols is more preferred, with rosin polyols being even more preferred. Polyol B may be a diol having two hydroxyl groups or a polyol having three or more hydroxyl groups, but a diol having two hydroxyl groups is preferred. Furthermore, polyol B may contain structural units derived from only one type of polyol, or may contain structural units derived from two or more types of polyols.

[0041] <<Rosin Polyol>> The rosin polyol is not particularly limited as long as it is a compound having a rosin skeleton and two or more hydroxyl groups in the molecule. The number of rosin skeletons is preferably two or more, and more preferably two. In rosin polyols, the rosin skeleton forms a branched chain. Rosin polyols include those in which the skeleton excluding the rosin skeleton is a polyether type such as polypropylene glycol (PPG) or a polyester type such as condensation polyester polyol, lactone polyester polyol, or polycarbonate diol.

[0042] Specific examples of rosin polyols include rosin esters obtained by reacting a rosin component with a polyhydric alcohol, epoxy-modified rosin esters obtained by reacting a rosin component with an epoxy compound, and modified rosins having hydroxyl groups, such as polyethers having a rosin skeleton. These rosin polyols can be produced by conventionally known methods. The epoxy-modified rosin ester is not particularly limited as long as it is a reaction product of reaction components including rosins and epoxy resins, and various known rosins can be used. The rosins may be used alone or in combination of two or more, and the epoxy resins may be used alone or in combination of two or more.

[0043] <<Rosins>> The rosins are not particularly limited, and various known rosins can be used. Examples of the rosins include natural rosin, purified rosin (hereinafter, natural rosin and purified rosin are collectively referred to as unmodified rosin), hydrogenated rosin, and disproportionated rosin.

[0044] Examples of natural rosins include natural rosins (gum rosin, tall oil rosin, wood rosin) derived from Pinus massoniana, Slash pine (Pinus elliottii), Merkusii pine (Pinus merkusii), Caribbean pine (Pinus caribaea), Pinus kesiya, Loblolly pine (Pinus taeda), and Great King pine (Pinus palustris).

[0045] The purified rosin can be obtained by various known means. Specifically, it can be obtained by various known purification means such as distillation, extraction, recrystallization, adsorption, etc. Furthermore, the purified rosin obtained may be further subjected to the disproportionation and hydrogenation procedures described below, either alone or in combination of two or more thereof.

[0046] Hydrogenated rosin can be obtained by various known means. Specifically, for example, the unmodified rosin can be heated under hydrogen pressure in the presence of a hydrogenation catalyst to cause a reaction (hydrogenation). Disproportionated rosin can be obtained by various known means. Specifically, for example, the unmodified rosin can be heated in the presence of a disproportionation catalyst to cause a reaction (disproportionation). Furthermore, for the purpose of improving color tone, the purified rosin, hydrogenated rosin, and disproportionated rosin can be further subjected to a dehydrogenation treatment.

[0047] The poly(meth)acrylic polyol is preferably a poly(meth)acrylic diol. The poly(meth)acrylic polyol is preferably a polymer polymerized via a chain transfer agent. The poly(meth)acrylic polyol polymerized via a chain transfer agent can be obtained, for example, by polymerizing a (meth)acrylic monomer using a chain transfer agent having two hydroxyl groups. In this case, the poly(meth)acrylic polyol has a structural unit derived from the chain transfer agent having two hydroxyl groups and a structural unit derived from the (meth)acrylic monomer. The structural unit derived from the (meth)acrylic monomer becomes a polymer portion formed by polymerizing the (meth)acrylic monomer. The structural unit derived from the chain transfer agent forms the main chain skeleton, and the structural unit (polymer portion) derived from the (meth)acrylic monomer forms a branched chain.

[0048] Examples of chain transfer agents having two hydroxyl groups include thiodiols such as 1-thioglycerol.

[0049] The (meth)acrylic monomer is not particularly limited, but examples thereof include polymethyl(meth)acrylate, polyethyl(meth)acrylate, polyn-propyl(meth)acrylate, polyi-propyl(meth)acrylate, polyn-butyl(meth)acrylate, polyi-butyl(meth)acrylate, polyt-butyl(meth)acrylate, poly2-ethylhexyl(meth)acrylate, poly2-hydroxyethyl(meth)acrylate, poly4-hydroxybutyl(meth)acrylate, polyglycidyl(meth)acrylate, polyoctyl(meth)acrylate, polypropyl(meth)acrylate, poly2-ethyloctyl(meth)acrylate, polynonyl(meth)acrylate, polyisononyl(meth)acrylate, polydecyl(meth)acrylate, polyisodecyl(meth)acrylate, polylauryl(meth)acrylate, polyisotetradecyl(meth)acrylate, polycyclohexyl(meth)acrylate, and polybenzyl(meth)acrylate. Examples of (meth)acrylic acid and (meth)acrylic acid esters having a polar group include (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycidyl (meth)acrylate. A chain transfer agent having two hydroxyl groups may be used to form a copolymer of an alkyl (meth)acrylate and a monomer other than an acrylic (meth)acrylic monomer.In this case, examples of the monomer other than alkyl (meth)acrylate include aromatic vinyls such as styrene, vinyl toluene, and α-methylstyrene; vinyl cyanides such as (meth)acrylonitrile; vinyl monomers containing a carboxyl group such as (meth)acrylic acid, fumaric acid, maleic acid, and itaconic acid; or alkyl esters thereof; alkane polyol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and oligoethylene glycol di(meth)acrylate; (meth)acrylates having an aromatic ring such as benzyl (meth)acrylate; (meth)acrylamide compounds such as N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide; and ether compounds. Examples of the ether compound include those having an ether bond, such as polyalkylene glycol monoacrylic ether (meth)acrylates, such as polyethylene glycol monomethyl ether (meth)acrylate and polypropylene glycol monomethyl ether (meth)acrylate.

[0050] Examples of poly(meth)acrylic polyols include copolymers obtained by copolymerizing a hydroxyl group-containing (meth)acrylate with a monomer copolymerizable with the hydroxyl group-containing (meth)acrylate. Examples of the monomer copolymerizable with the hydroxyl group-containing (meth)acrylate include the alkyl(meth)acrylates and monomers other than the alkyl(meth)acrylates described above, and it is preferable to use at least an alkyl(meth)acrylate.

[0051] Furthermore, the poly(meth)acrylic polyol may be one polymerized via a chain transfer agent, even when a hydroxyl group-containing (meth)acrylate is used. Specifically, the poly(meth)acrylic polyol may be obtained by polymerizing a (meth)acrylic monomer containing a hydroxyl group-containing (meth)acrylate using a chain transfer agent having one or more hydroxyl groups. As a result, the hydroxyl group is contained in the structural unit derived from the hydroxyl group-containing (meth)acrylate and the structural unit derived from the chain transfer agent. In this case, the chain transfer agent may have two hydroxyl groups as described above, but may also have one hydroxyl group and one thiol. By using one hydroxyl group and one thiol, the hydroxyl group contained in the structural unit derived from the chain transfer agent to the hydroxyl group contained in the structural unit derived from the hydroxyl group-containing (meth)acrylate can form the main chain.

[0052] The hydroxyl value of polyol B is preferably 2 to 500 mgKOH / g, more preferably 5 to 200 mgKOH / g, and even more preferably 10 to 150 mgKOH / g. When the hydroxyl value of polyol B is within the above range, the molecular weight of polyol B becomes appropriately high, which makes it easier to increase the initial adhesive strength and the adhesive strength under high temperature environments.

[0053] In the above description, it is assumed that polyol B is a polyol having a branched chain. However, in another aspect, polyol B may be a poly(meth)acrylic polyol polymerized via a chain transfer agent. By using a poly(meth)acrylic polyol polymerized via a chain transfer agent as polyol B, a polyol B with low linearity can be easily obtained. Therefore, in addition to the above-mentioned polyol A, by using a poly(meth)acrylic polyol polymerized via a chain transfer agent as polyol B, the cohesive strength of the moisture-curable resin composition can be improved, and the adhesion can be improved. Details of the poly(meth)acrylic polyol polymerized via a chain transfer agent are as described above.

[0054] As described above, the moisture-curing urethane resin (A) is a prepolymer of at least polyol A and polyol B as polyols. The amount of polyol B used relative to 100 parts by mass of the total polyols used as raw materials for the moisture-curing urethane resin (A) is, for example, 15 parts by mass or more, preferably 20 parts by mass or more, and more preferably 25 parts by mass or more. In this way, using a certain amount of polyol B makes it easier to improve adhesion. The reason for this is unclear, but it is presumed that the introduction of branched chains into the moisture-curing urethane resin (A) increases the density of urethane bonds within the molecules of the moisture-curing urethane resin (A). In addition, the amount of polyol B used is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 75 parts by mass or less relative to 100 parts by mass of the total polyols, from the viewpoint of properly curing the moisture-curing resin composition and making it easy to apply, and from the viewpoint of making it easier to use a certain amount of polyol A. Polyol B may be used alone or in combination of two or more types.

[0055] <Other Polyols> As described above, the moisture-curable urethane resin (A) may be obtained by prepolymerizing other polyols in addition to polyol A and polyol B. The other polyols are not particularly limited as long as they are polyols other than at least polyol A and polyol B, and examples thereof include polyester polyols and polyether polyols. The polyester polyols and polyether polyols are as explained in the section on polyol A, and therefore detailed explanations thereof will be omitted. The other polyols preferably include polyether polyols, and more preferably include polypropylene glycol.

[0056] The hydroxyl value of the other polyol is preferably 5 to 200 mgKOH / g, more preferably 10 to 100 mgKOH / g, and even more preferably 15 to 50 mgKOH / g. When the hydroxyl value of the other polyol is within the above range, the molecular weight of the other polyol becomes appropriately high, which makes it easier to increase the initial adhesive strength and the adhesive strength under high temperature environments.

[0057] The amount of the other polyol used is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less, relative to 100 parts by mass of the total polyols. When the amount of the other polyol used is a certain amount or less, it becomes easier to use the amounts of polyol A and polyol B at least at certain amounts. The amount of the other polyol used may be 0 parts by mass or more, relative to 100 parts by mass of the total polyols. The other polyols may be used alone or in combination of two or more.

[0058] The content of the moisture-curable urethane resin (A) in the moisture-curable resin composition of the present invention is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less, and even more preferably 35 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the moisture-curable resin composition. When the content of the moisture-curable urethane resin (A) is within the above range, it is easy to increase the initial adhesive strength and to maintain the adhesive strength even in a high-temperature environment.

[0059] When the moisture-curable resin composition of the present invention is a hot-melt type described later, the content of the moisture-curable urethane resin (A) is preferably 70 parts by mass or more and 100 parts by mass or less, more preferably 80 parts by mass or more and 100 parts by mass or less, and even more preferably 90 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the moisture-curable resin composition.

[0060] Furthermore, when the moisture-curable resin composition of the present invention contains a radically polymerizable compound described below and is a photo-moisture-curable resin composition, the content of the moisture-curable urethane resin (A) is preferably 20 parts by mass or more and 80 parts by mass or less, more preferably 30 parts by mass or more and 70 parts by mass or less, and even more preferably 35 parts by mass or more and 65 parts by mass or less, relative to 100 parts by mass of the moisture-curable resin composition.

[0061] <Polyisocyanate> As the polyisocyanate used as a raw material for the moisture-curable urethane resin (A), aromatic polyisocyanates and aliphatic polyisocyanates are preferably used. Examples of aromatic polyisocyanates include compounds in which an isocyanate group is bonded to an aromatic ring, such as diphenylmethane diisocyanate, liquid modified diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, and naphthalene-1,5-diisocyanate. Examples of aliphatic polyisocyanates include compounds in which an isocyanate group is bonded to a carbon atom constituting an aliphatic hydrocarbon, such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, and dicyclohexylmethane diisocyanate. Among these, diphenylmethane diisocyanate and modified products thereof are preferred as polyisocyanates, from the viewpoint of enhancing adhesive strength after full curing. Polyisocyanates may be used alone or in combination of two or more.

[0062] The number average molecular weight of the moisture-curable urethane resin (A) is not particularly limited, but is preferably 1500 to 50,000, more preferably 2000 to 40,000, and even more preferably 3300 to 30,000. When the number average molecular weight is equal to or greater than the lower limit, for example, after application or photocuring, the composition has a certain level of hardness and is more likely to have excellent shape retention. Furthermore, when the number average molecular weight is equal to or less than the upper limit, the moisture-curable resin composition tends to have appropriate fluidity, for example, even at room temperature (e.g., 25 ° C.), before curing, and is more likely to have good applicability. Furthermore, when the number average molecular weight is within the above range, adhesive strength and the like are more likely to be improved.

[0063] In this specification, the number average molecular weight refers to the number average molecular weight calculated using a standard sample measured by gel permeation chromatography (GPC). Examples of the standard sample include polystyrene, polymethyl methacrylate, and polyethylene glycol. For example, to measure the number average molecular weight calculated using polystyrene, a polystyrene standard sample with a known molecular weight is measured using GPC.

[0064] When polystyrene standard samples are used as the standard samples, nine samples with the following weight-average molecular weights are used as the polystyrene standard samples ("Shodex Standard SM-105" manufactured by Resonac Corporation). Standard sample numbers for each sample (weight-average molecular weight): S-1.3 (1270), S-3.2 (3180), S-6.9 (6,940), S-22 (21,800), S-53 (52,500), S-333 (333,000), S-609 (609,000), S-1345 (1,350,000), and S-2704 (2,700,000).

[0065] The molecular weight is plotted against the elution time indicated by the peak top of each standard sample peak, and the resulting approximate straight line is used as a calibration curve. The thermoplastic (meth)acrylic polymer may be dissolved in tetrahydrofuran (THF) to prepare a 0.2% by mass solution, and the solution may be analyzed using a GPC apparatus with tetrahydrofuran (THF) as the eluent to measure the number average molecular weight. The cured product may be dissolved in tetrahydrofuran (THF) to prepare a 0.2% by mass solution, and the solution may be analyzed using a GPC apparatus with tetrahydrofuran (THF) as the eluent to measure the number average molecular weight. The first layer of the interlayer film (the first layer obtained by peeling off the first layer, if the interlayer film is a multilayer interlayer film) may be dissolved in tetrahydrofuran (THF) to prepare a 0.2% by mass solution, and the solution may be analyzed using a GPC apparatus with tetrahydrofuran (THF) as the eluent to measure the number average molecular weight. When the thermoplastic (meth)acrylic polymer, the cured product, or the first layer contains a compound having an amide group, the compound may be dissolved in dimethylformamide or N-methylpyrrolidone instead of tetrahydrofuran (THF) to prepare a 0.2% by mass solution. In this case, lithium bromide-containing dimethylformamide or lithium bromide-containing N-methylpyrrolidone may be used as the eluent. When the interlayer film is used, it is preferable to leave the interlayer film in a constant temperature and humidity chamber (humidity 30% (±3%), temperature 23°C) for one month before preparing the solution. The number average molecular weight can be analyzed using the following GPC device.

[0066] GPC apparatus (manufactured by Waters, RI: 2414, autosampler Alliance: e2695, guard column: KF-G, column: two Shodex KF806L columns in series).

[0067] (Radical Polymerizable Compound) In addition to the moisture-curable urethane resin (A) described above, the moisture-curable resin composition of the present invention preferably contains a compound having a radically polymerizable group (hereinafter simply referred to as a "radical polymerizable compound"). By containing a radically polymerizable compound, the moisture-curable resin composition can be made photocurable, and a certain level of adhesive strength can be imparted simply by irradiating light, making it easier to ensure appropriate initial adhesive strength. Furthermore, a certain level of hardness can be achieved simply by irradiating light, making it easier to ensure ease of handling. Furthermore, by using it in combination with a photopolymerization initiator, as described below, it is possible to increase the initial adhesive strength even immediately after photocuring. The radically polymerizable compound may have a radically polymerizable group in its molecule. Compounds having an unsaturated double bond are preferred as the radically polymerizable group, and compounds having a (meth)acryloyl group or a vinyl group are particularly preferred in terms of reactivity. The radically polymerizable compound is not particularly limited, but may be appropriately selected depending on the application, usage environment, required performance, etc., so that the glass transition temperature after polymerization is within a certain range and the compound has a certain level of viscoelasticity after photocuring or moisture curing.

[0068] Specific examples of compounds having a (meth)acryloyl group (hereinafter also referred to as "(meth)acrylic compounds") include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, urethane (meth)acrylates, etc. In addition, in this specification, "(meth)acryloyl group" means an acryloyl group or a (meth)acryloyl group, "(meth)acrylate" means an acrylate or a methacrylate, and the same applies to other similar terms.

[0069] The (meth)acrylic acid ester compound may be monofunctional, bifunctional, trifunctional or higher. Examples of monofunctional (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and lauryl (meth)acrylate. alkyl (meth)acrylates such as acrylate, isomyristyl (meth)acrylate, and stearyl (meth)acrylate; (meth)acrylates having an alicyclic structure such as cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentenyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as propyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and 2-butoxyethyl (meth)acrylate; alkoxyethylene glycol (meth)acrylates such as methoxyethylene glycol (meth)acrylate and ethoxyethylene glycol (meth)acrylate; polyoxyethylene (meth)acrylates such as methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate.

[0070] The (meth)acrylic acid ester compound may also have an aromatic ring, and examples thereof include phenylalkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate, and phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate. Furthermore, the (meth)acrylate may also be a (meth)acrylate having multiple benzene rings, such as a fluorene skeleton or a biphenyl skeleton, and specific examples include fluorene-type (meth)acrylate and ethoxylated o-phenylphenol acrylate. Further examples include phenoxypolyoxyethylene (meth)acrylates such as phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxydiethylene glycol (meth)acrylate, and nonylphenoxypolyethylene glycol (meth)acrylate.

[0071] Further, examples of the monofunctional (meth)acrylic acid ester compound include (meth)acrylates having a heterocyclic structure such as tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, various imide (meth)acrylates, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoroethyl (meth)acrylate. Other examples include trifluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexahydrophthalate, N-acryloyloxyethyl hexahydrophthalimide, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl (meth)acrylate, and 2-(meth)acryloyloxyethyl phosphate.

[0072] Examples of bifunctional (meth)acrylic acid ester compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(

[0043] Examples of suitable di(meth)acrylates include ethylene oxide-added bisphenol A di(meth)acrylate, propylene oxide-added bisphenol A di(meth)acrylate, ethylene oxide-added bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, polycaprolactone diol di(meth)acrylate, and polybutadiene diol di(meth)acrylate.

[0073] Furthermore, examples of the (meth)acrylic acid ester compounds having three or more functional groups include trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. The (meth)acrylic acid ester compound is preferably a monofunctional (meth)acrylic acid ester compound.

[0074] The epoxy (meth)acrylate may be, for example, a product of reacting an epoxy compound with (meth)acrylic acid. The reaction between the epoxy compound and (meth)acrylic acid may be carried out in the presence of a basic catalyst according to a conventional method. The epoxy (meth)acrylate may be monofunctional or multifunctional, such as bifunctional, but multifunctional is preferred, and bifunctional is more preferred. Examples of epoxy compounds that can be used as raw materials for synthesizing the above-mentioned epoxy (meth)acrylates include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, 2,2'-diallyl bisphenol A type epoxy resins, hydrogenated bisphenol type epoxy resins, propylene oxide-added bisphenol A type epoxy resins, resorcinol type epoxy resins, biphenyl type epoxy resins, sulfide type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, phenol novolac type epoxy resins, o-cresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, naphthalene phenol novolac type epoxy resins, glycidylamine type epoxy resins, alkyl polyol type epoxy resins, rubber-modified type epoxy resins, glycidyl ester compounds, and bisphenol A type episulfide resins.

[0075] Among the above epoxy (meth)acrylates, commercially available ones include, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, and EBECRYL Examples of suitable acrylates include RDX63182 (all manufactured by Daicel Allnex Corporation), EA-1010, EA-1020, EA-5323, EA-5520, EACHD, and EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, and Epoxy Ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, and Denacol Acrylate DA-911 (all manufactured by Nagase ChemteX Corporation).

[0076] The urethane (meth)acrylate can be, for example, a product obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group. A catalytic amount of a tin-based compound or the like can be used as a catalyst for the reaction between the isocyanate compound and the (meth)acrylic acid derivative. The urethane (meth)acrylate may be monofunctional or multifunctional, such as bifunctional. The urethane (meth)acrylate may have an isocyanate group.

[0077] Examples of the isocyanate compound used to obtain the urethane (meth)acrylate include polyisocyanate compounds such as isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

[0078] Alternatively, the isocyanate compound may be a chain-extended polyisocyanate compound obtained by reacting a polyol with an excess of an isocyanate compound. Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

[0079] Examples of the (meth)acrylic acid derivative having a hydroxyl group include mono(meth)acrylates of dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol, mono(meth)acrylates or di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin, and epoxy(meth)acrylates such as bisphenol A-type epoxy(meth)acrylate. The (meth)acrylic acid derivatives for obtaining the urethane(meth)acrylate may be used alone or in combination of two or more.

[0080] The polyfunctional urethane (meth)acrylate may be one obtained by reacting a polyisocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group. The monofunctional urethane (meth)acrylate may be one obtained by reacting a monoisocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group, but examples include urethane (meth)acrylates obtained by reacting a monoisocyanate compound with a mono(meth)acrylate of a dihydric alcohol. Other examples include one obtained by reacting a trihydric or higher alcohol with a compound having an isocyanate group and a (meth)acryloyl group, and a polyisocyanate compound.

[0081] Among the above urethane (meth)acrylates, commercially available ones include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, EBECRYL8411, EBECRYL8412, EBECRYL8413, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9270, and EBECRYL2 10, EBECRYL4827, EBECRYL4396, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel Allnex Co., Ltd.), CN8888 (manufactured by Sartomer Co., Ltd.), Art Resin UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (both manufactured by Negami Kogyo), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U- 108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA -7200, UA-W2A (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.), CN-902, CN-973, CN-9021, CN-9782, CN-9833 (all manufactured by Arkema), Viscoat #216 (manufactured by Osaka Organic Chemical Industry Ltd.), GENOMER 1122 (manufactured by Rahn), and the like. The above-mentioned (meth)acrylic compounds may be used alone or in combination of two or more.

[0082] As the radical polymerizable compound, other radical polymerizable compounds besides those mentioned above can also be used as appropriate. Examples of other radical polymerizable compounds include (meth)acrylamide compounds such as N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-dimethylaminopropyl(meth)acrylamide, and vinyl compounds such as styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0083] The radical polymerizable compound may be a monofunctional compound or a polyfunctional compound, but preferably contains at least a monofunctional compound, and more preferably contains a polyoxyethylene (meth)acrylate. The content of the monofunctional compound is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, and preferably 100 parts by mass or less, more preferably 99 parts by mass or less, even more preferably 98 parts by mass or less, relative to 100 parts by mass of the radical polymerizable compound. Furthermore, when a monofunctional compound is contained, it is preferable to contain a monofunctional (meth)acrylic compound, but a monofunctional (meth)acrylic compound may be used in combination with a compound other than a monofunctional (meth)acrylic compound, such as a vinyl compound.

[0084] The content of the radical polymerizable compound in the moisture-curable resin composition is preferably 75 parts by mass or less, more preferably 65 parts by mass or less, and even more preferably 60 parts by mass or less, relative to 100 parts by mass of the moisture-curable resin composition. Further, the radical polymerizable compound does not have to be contained in the moisture-curable resin composition. Therefore, the content of the radical polymerizable compound may be 0 parts by mass or more. However, from the viewpoint of appropriately imparting photocurability, it is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. When the moisture-curable resin composition is a hot-melt moisture-curable resin composition described later, the content of the radical polymerizable compound is typically 0 parts by mass, but may contain a certain amount, for example, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less, relative to 100 parts by mass of the moisture-curable resin composition.

[0085] (Photopolymerization Initiator) When the moisture-curable resin composition of the present invention contains a radically polymerizable compound, it preferably further contains a photopolymerization initiator. By containing a photopolymerization initiator, it is possible to appropriately impart photocurability to the moisture-curable resin composition. The photopolymerization initiator is not particularly limited, but examples thereof include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Specific examples include benzophenone-based compounds, acetophenone-based compounds such as α-hydroxyalkylphenones, acylphosphine oxide-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and alkylphenone-based compounds such as 2,2-dimethoxy-1,2-diphenylethan-1-one. Among these, at least one selected from acetophenone-based compounds and alkylphenone-based compounds is preferred. Among the above photopolymerization initiators, commercially available ones include, for example, Omnirad 184, Omnirad 369, Omnirad 379, Omnirad 651, Omnirad 784, Omnirad 819, Omnirad 907, Omnirad 2959, Omnirad TPO (all manufactured by IGM Resins), Irgacure OXE01 (manufactured by BASF), benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0086] The content of the photopolymerization initiator in the moisture-curable resin composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the radical polymerizable compound. When the content of the photopolymerization initiator is within these ranges, the resulting moisture-curable resin composition has excellent photocurability and storage stability. Furthermore, by setting the content within the above range, the photoradical polymerizable compound is appropriately cured, making it easier to improve adhesive strength.

[0087] (Filler) The moisture-curable resin composition of the present invention may contain a filler. By containing a filler, the moisture-curable resin composition of the present invention has suitable thixotropy and mechanical strength, and can sufficiently retain its shape after application. As the filler, a particulate filler may be used. As the filler, inorganic fillers are preferred, such as silica, talc, titanium oxide, zinc oxide, calcium carbonate, etc. are examples. Among them, silica is preferred because the resulting curable resin composition has excellent ultraviolet transmittance. In addition, the filler may be subjected to a hydrophobic surface treatment such as a silylation treatment, an alkylation treatment, or an epoxidation treatment. One type of filler may be used alone, or two or more types may be used in combination. The content of the filler is preferably 0.3 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 7 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the moisture-curable prepolymer. By setting the content of the filler within the above range, it is easier to improve the flexibility after curing.

[0088] (Other Additives) The moisture-curable resin composition of the present invention may contain other additives such as a silane coupling agent, a moisture-cure accelerating catalyst, wax particles, an ionic liquid, a dehydrating agent, a colorant, foamed particles, expanded particles, and a reactive diluent, and among these, it is preferable to contain a dehydrating agent. The moisture-curable resin composition may have a reduced storage stability due to the inclusion of moisture in the air, but by containing a dehydrating agent, it is possible to maintain good storage stability.

[0089] Examples of dehydrating agents include organic silane compounds. From the viewpoint of stably maintaining the storage stability of the moisture-curable resin composition over a long period of time, it is preferable to use a formate-based compound as the dehydrating agent. For example, at least one selected from triethyl orthoformate and ethyl orthoformate can be used as the formate-based compound. The dehydrating agent may further contain a monoisocyanate-based compound in addition to the formate-based compound. The inclusion of a monoisocyanate-based compound further improves the storage stability of the moisture-curable resin composition. For example, at least one selected from p-toluenesulfonyl isocyanate and 2-acryloyloxyethyl isocyanate can be used as the monoisocyanate-based compound. When a formic acid-based compound and a monoisocyanate-based compound are used together, the ratio of their use (formic acid-based compound / monoisocyanate-based compound) is not particularly limited, but may be, for example, a mass ratio of 1 / 1 to 2 / 1, preferably 1 / 1 to 1.7 / 1.

[0090] The content of the dehydrating agent is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the moisture-curable resin composition. When the content of the dehydrating agent is within the above range, the storage stability of the moisture-curable resin composition can be improved without deteriorating the various physical properties.

[0091] The moisture-curable resin composition of the present invention may be diluted with a solvent as needed. When the moisture-curable resin composition is diluted with a solvent, the parts by mass of the moisture-curable resin composition are based on the solid content, i.e., the parts by mass excluding the solvent.

[0092] In addition, the moisture-curing resin composition of the present invention may contain a moisture-curing resin other than the moisture-curing urethane resin (A) described above (hereinafter also referred to as "other moisture-curing resins"). Examples of other moisture-curing resins include hydrolyzable silyl group-containing resins. The hydrolyzable silyl group-containing resin cures when the hydrolyzable silyl group in the molecule reacts with moisture in the air or the adherend. The hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in one molecule, or may have two or more hydrolyzable silyl groups. Among these, it is preferable to have hydrolyzable silyl groups at both ends of the main chain of the molecule.

[0093] The moisture-curable resin composition of the present invention can be produced by mixing the components constituting the moisture-curable resin composition using a mixer. For example, a method of mixing a urethane prepolymer and, if necessary, a radical polymerizable compound, a photopolymerization initiator, a filler, and other additives can be used. Examples of mixers include a homodisper, a homomixer, a universal mixer, a planetary mixer (planetary stirring device), a kneader, and a three-roll mill.

[0094] (Method of Use of Moisture-Curable Resin Composition) As described above, the moisture-curable resin composition of the present invention contains a moisture-curable urethane resin (A) and a radically polymerizable compound, and can be used as a photo-moisture-curable resin composition. The photo-moisture-curable resin composition may be solid at room temperature (25°C), but is preferably liquid at room temperature from the viewpoint of workability and application. The moisture-curable resin composition of the present invention can also be used as a hot-melt type. When used as a hot-melt type, it is solid at room temperature (25°C) but liquefied by heating. The hot-melt type moisture-curable resin composition is applied to an adherend in a heated state and then cooled to solidify and exhibit a certain initial adhesive strength.

[0095] The moisture-curable resin composition of the present invention is cured and used as a cured product. When the moisture-curable resin composition of the present invention has photocurability, it is preferable to first photocure it by irradiating it with light to, for example, bring it to a B-stage state (semi-cured state), and then further cure it by moisture to fully cure it.

[0096] Here, when the photo-curable resin composition is placed between adherends and the adherends are bonded together, it is applied to one of the adherends and then photo-cured by light irradiation, for example, to a B-stage state. The other adherend is then placed on top of the moisture-curable resin composition that has cured to the B-stage state, and the adherends are temporarily bonded with an appropriate adhesive strength (initial adhesive strength). The moisture-curable resin composition in the B-stage state is then fully cured by moisture curing, and the overlapping adherends are bonded together with sufficient adhesive strength via the moisture-curable resin composition. The light irradiated during photo-curing is not particularly limited as long as it is light that cures the radical polymerizable compound, but ultraviolet light is preferred. Furthermore, when the moisture-curable resin composition is cured by moisture, it can be left in the atmosphere for a predetermined time.

[0097] When the moisture-curable resin composition is a hot melt type, it is preferably applied to an adherend in a heated, molten state, and then solidified to have an appropriate adhesive strength (initial adhesive strength). Alternatively, for example, it may be applied to one adherend, solidified, and then the other adherend is superimposed on the other adherend to temporarily bond the adherends with an appropriate adhesive strength (initial adhesive strength). It is then fully cured by moisture curing, and the superimposed adherends are bonded with sufficient adhesive strength via the moisture-curable resin composition. When the moisture-curable resin composition is a hot melt type, it may be photocurable, or it may be applied to one adherend, photocured before superimposing the other adherend, and then fully cured by moisture curing.

[0098] Furthermore, application of the moisture-curable resin composition to the adherend is preferably performed using a dispenser. Examples of dispensers include air dispensers, jet dispensers, mono-pump dispensers, screw dispensers, and handgun dispensers. In the present invention, by setting the viscosity within the predetermined range as described above, the moisture-curable resin composition can be applied with good applicability using a dispenser, for example, in the form of a thin line of 1 mm or less, preferably about 0.1 to 0.7 mm. Furthermore, with a dispenser, the moisture-curable resin composition may be heated to about 70 to 100°C and applied.

[0099] The moisture-curable resin composition of the present invention is preferably used as an adhesive for electronic components. Therefore, the present invention can also provide electronic components containing a cured product of the moisture-curable resin composition. In this case, the adherend of the cured product is not particularly limited, but is preferably various components constituting electronic devices. Preferred electronic devices are portable electronic devices such as smartphones, mobile phones, tablet devices, portable game consoles, and notebook computers. Examples of various components constituting electronic devices include electronic components or substrates on which electronic components are attached. More specifically, examples include various electronic components provided in display elements, substrates on which electronic components are attached, and semiconductor chips. Among these, use for display elements is more preferred. The material of the adherend may be metal, glass, plastic, or the like. The shape of the adherend is not particularly limited, and examples include films, sheets, plates, panels, trays, rods, boxes, and housings.

[0100] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0101] In the present examples, various physical properties were measured as follows.

[0102] (Initial adhesive strength) As shown in Figure 1, a moisture-curable resin composition 20 was applied to an aluminum substrate 21 (AL6063 substrate) having a width of 25 mm, a length of 100 mm, and a thickness of 1 mm using a dispenser along the width direction of the substrate 21 so as to have a length of 25 mm and a width of 2 mm. When the moisture-curable resin composition was a photo-moisture-curable resin composition, the photo-moisture-curable resin composition was applied at room temperature, and when it was a hot melt type, it was heated to 80°C and applied. Next, in the case of a photo-moisture-curable resin composition, ultraviolet light of 1000 mW / cm was applied using a UV-LED (wavelength 365 nm) within 1 minute after completion of application. ２ Illuminance of 4500 mJ / cm ２ The composition was photocured by irradiating with an irradiation dose of 1000 μm. In the case of a hot melt type, after application, the composition was left for 20 minutes in an environment of 25°C and 50% RH without irradiating with ultraviolet light. Then, a glass plate 22 having a width of 25 mm, a length of 100 mm, and a thickness of 1.7 mm was bonded to an aluminum substrate 21 via a moisture-curing resin composition 20, and a 100 g weight was placed and pressed for 20 seconds. After removing the weight, the composition was left to moisture-cure at 25°C and 50% RH for 24 hours to obtain a sample 23 for measuring initial adhesive strength. The sample 23 obtained by the above procedure was set in an adhesive strength measurement device (Shimadzu Corporation, "TCE-N300"). After 1 minute from setting, a shear test was performed at a shear rate of 12.7 mm / min to measure the initial adhesive strength.

[0103] (High-temperature adhesive strength) As shown in Figure 1, a moisture-curable resin composition 20 was applied to an aluminum substrate 21 (AL6063 substrate) having a width of 25 mm, a length of 100 mm, and a thickness of 1 mm using a dispenser along the width direction of the substrate 21 so as to have a length of 25 mm and a width of 2 mm. When the moisture-curable resin composition was a photo-moisture-curable resin composition, the photo-moisture-curable resin composition was applied at room temperature, and when it was a hot-melt type, it was heated to 80°C and applied. Next, in the case of a photo-moisture-curable resin composition, ultraviolet light of 1000 mW / cm was applied using a UV-LED (wavelength 365 nm) within 1 minute after completion of application. ２ Illuminance of 4500 mJ / cm ２The composition was photocured by irradiating the composition with an irradiation dose of 1000 μm at 2000 μm. Furthermore, in the case of a hot melt type, after completion of application, the composition was left for 20 minutes in an environment of 25°C and 50% RH without UV irradiation. Thereafter, a glass plate 22 having a width of 25 mm, a length of 100 mm, and a thickness of 1.7 mm was bonded to an aluminum substrate 21 via the composition, and a 100 g weight was placed and pressed for 20 seconds. After removing the weight, the composition was left to cure at 25°C and 50% RH for 24 hours to obtain a sample 23 for measuring high-temperature adhesive strength. The sample 23 obtained by the above procedure was left to stand for 10 minutes in a universal testing machine equipped with an 80°C chamber, and then the sample 23 was set in an adhesive strength measuring device (Shimadzu Corporation, "TCE-N300"). One minute after setting, a shear test was performed at a shear rate of 12.7 mm / min to measure the shear stress, and the measured value was taken as the high-temperature adhesive strength.

[0104] (Hanging test) As shown in FIG. 2(A), a moisture-curable resin composition 11 was applied to an aluminum substrate 10 (AL6063 substrate) having a width of 25 mm, a length of 100 mm, and a thickness of 1 mm using a dispenser along the width direction of the substrate 10 so as to have a length of 25 mm and a width of 2 mm. When the moisture-curable resin composition 11 was a photo-moisture-curable resin composition, the photo-moisture-curable resin composition was applied at room temperature, and when it was a hot-melt type, it was heated to 80°C and applied. Next, in the case of a photo-moisture-curable resin composition, ultraviolet light of 1000 mW / cm was applied using a UV-LED (wavelength 365 nm) within 1 minute after completion of application. ２ Illuminance of 4500 mJ / cm ２The composition was photocured by irradiating the composition with an irradiation dose of 1000 μm at 25°C and then left for 5 minutes in an environment of 25°C and 50% RH. In the case of a hot melt type, after application, the composition was left for 20 minutes in an environment of 25°C and 50% RH without irradiating with ultraviolet light. Next, as shown in FIG. 2(B), a glass plate 12 having a width of 25 mm, a length of 100 mm, and a thickness of 1.7 mm was placed on top of the photocured moisture-curing resin composition 11, and a 100 g weight 13 was placed on the aluminum substrate 10 for 20 seconds to bond the glass plate 12 to the aluminum substrate 10 via the moisture-curing resin composition 11. After removing the weight 13, the composition was left for 24 hours in an atmosphere of 25°C and 50% RH to moisture-cure the moisture-curing resin composition 11, thereby obtaining a test specimen 15. The glass plate 12 and the aluminum substrate 10 were overlapped by 20 mm in the longitudinal direction, and the moisture-curing resin composition 11 was positioned in the center of the overlapping portion of the substrate 10 and the glass plate 12. Six test specimens 15 were prepared using the above method, and the glass plate 12 was fixed so that the length direction was aligned vertically as shown in Figure 2(C). Weights 17 of 600 g, 700 g, and 800 g were hung from these test specimens 15, resulting in two test specimens 15 each with a 600 g weight 17 hung from them, a 700 g weight 17 hung from them, and an 800 g weight 17 hung from them. In each test specimen 15, a circular hole 16 with a diameter of 8 mm was formed in the center below the aluminum substrate 10 as shown in Figure 2(C), and a weight 17 was hung through the hole 16 as shown in Figure 2(D). Each test specimen 15 with the weight 17 suspended as described above was left for 10 days, and a hanging test was performed to check for the presence or absence of the aluminum substrate 10. The largest weight at which the aluminum substrate 10 was judged to have fallen off was recorded. In this case, if the weight at which neither of the two test specimens fell off was judged to have fallen off, that weight was judged to have fallen off. On the other hand, if one test specimen fell off but the other did not, a retest was performed. In the retest, a new test specimen 15 was prepared, and a weight 17 of that weight was suspended from the newly prepared test specimen 15. The newly prepared test specimen 15 was left in this state for 10 days, and a hanging test was performed to check for the presence or absence of the aluminum substrate 10. In this case, if the aluminum substrate 10 did not fall off in the retest, that weight was judged to have fallen off.If the weight fell off in the retest, the heaviest weight that was lighter than the weight and was judged to be "not fallen off" was recorded as the measurement result. Note that if the 600 g weight 17 was not judged to be "not fallen off", it was recorded as "not recorded". The weight was hung by placing the test specimen 35 in an environment of 60°C and 95% RH. Based on the above test results, the hanging test was evaluated. The evaluation criteria are as follows: A: The record was 800 g. B: The record was 700 g. C: The record was 600 g. D: No record.

[0105] The components used in the examples and comparative examples are as follows. (Urethane Prepolymer) Urethane prepolymer 1 was produced according to the following Synthesis Example 1. [Synthesis Example 1] 40.48 parts by mass of a linear polycarbonate diol having a branched chain with one carbon atom ("C-2050" manufactured by Kuraray Co., Ltd., hydroxyl value 54.6 mgKOH / g) as polyol A and 40.48 parts by mass of rosin diol ("D-6011" manufactured by Arakawa Chemical Industries, Ltd.) as polyol B were placed in a 500 mL separable flask and mixed by stirring under vacuum (20 mmHg or less) at 100°C for 30 minutes. The pressure was then returned to normal, and 19.05 parts by mass of diphenylmethane diisocyanate ("Pure MDI" manufactured by Nisso Shoji Co., Ltd.) was added as a polyisocyanate. The mixture was stirred at 80°C for 3 hours to carry out the reaction. After the temperature had subsided, the temperature was raised to 100°C to carry out the reaction, thereby obtaining urethane prepolymer 1 (number average molecular weight 7000).

[0106] Urethane prepolymer 2 was produced according to the following Synthesis Example 2. [Synthesis Example 2] Urethane prepolymer 2 (number average molecular weight 7000) was obtained in the same manner as in Synthesis Example 1, except that the types and compositions of polyol A, polyol B, and polyisocyanate were changed as shown in Tables 1 and 2.

[0107] Urethane prepolymer 3 was produced according to the following Synthesis Example 3. [Synthesis Example 3] Urethane prepolymer 3 (number average molecular weight 10,000) was obtained in the same manner as in Synthesis Example 1, except that the types and blending ratios of polyol A, polyol B, and polyisocyanate were changed as shown in Tables 1 and 2.

[0108] Urethane prepolymer 4 was produced according to the following Synthesis Example 4. [Synthesis Example 4] Urethane prepolymer 4 (number average molecular weight 3700) was obtained in the same manner as in Synthesis Example 1, except that the types and blending ratios of polyol A, polyol B, and polyisocyanate were changed as shown in Tables 1 and 2.

[0109] Urethane prepolymer 5 was produced according to the following Synthesis Example 5. [Synthesis Example 5] Urethane prepolymer 5 (number average molecular weight 4,200) was obtained in the same manner as in Synthesis Example 1, except that the types and blending ratios of polyol A, polyol B, and polyisocyanate were changed as shown in Tables 1 and 2.

[0110] Urethane prepolymer 6 was produced according to the following Synthesis Example 6. [Synthesis Example 6] Urethane prepolymer 6 (number average molecular weight 3650) was obtained in the same manner as in Synthesis Example 1, except that the types and compositions of polyol A, polyol B, and polyisocyanate were changed as shown in Tables 1 and 2.

[0111] Urethane prepolymer 7 was produced according to the following Synthesis Example 7. [Synthesis Example 7] Urethane prepolymer 7 (number average molecular weight 3,350) was obtained in the same manner as in Synthesis Example 1, except that the types and compositions of polyol A, polyol B, and polyisocyanate were changed as shown in Tables 1 and 2.

[0112] Urethane prepolymer 8 was produced according to the following Synthesis Example 8. [Synthesis Example 8] Urethane prepolymer 8 (number average molecular weight 3100) was obtained in the same manner as in Synthesis Example 1, except that the types and compositions of polyol A, polyol B, and polyisocyanate were changed as shown in Tables 1 and 2.

[0113]

[0114] * In Synthesis Examples 2, 3, 5, and 7, polyether polycarbonate diol ("NT-2006" manufactured by Mitsubishi Chemical Corporation) was used as Polyol A, and in Synthesis Examples 2 and 5, polyacrylic diol ("Actflow UT-1001" manufactured by Soken Chemical & Engineering Co., Ltd.) was used as Polyol B. * "Molecular weight" in Tables 1 and 2 respectively represents the number average molecular weight.

[0115] The acrylic copolymer resin used in Synthesis Examples 3 and 8 above was prepared according to Synthesis Example 9 below. [Synthesis Example 9] 50 parts by weight of IDAA: isodecyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 45 parts by weight of benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 11 parts by weight of 1-thioglycerol (manufactured by Asahi Chemical Industry Co., Ltd.) were added to a 2-L separable flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser. Next, nitrogen gas was blown in for 30 minutes to replace the atmosphere inside the reaction vessel with nitrogen, and the reaction vessel was heated to 60°C while stirring. After 30 minutes, 0.063 parts by weight of azobisisobutyronitrile as a polymerization initiator was diluted with 5 parts by weight of benzyl acrylate and added to the reaction vessel. The mixture was then reacted at 60°C for 30 minutes, followed by a reaction at 80°C for 2 hours. The reaction solution was then cooled to obtain an acrylic copolymer resin solution.

[0116] The components other than the urethane prepolymer used in the examples and comparative examples were as follows: (Radical polymerizable compounds) Methoxypolyethylene glycol acrylate: "MPE-400A" manufactured by Osaka Organic Chemicals, monofunctional (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate: "MEDOL-10" manufactured by Osaka Organic Chemicals, monofunctional N-vinyl-ε-caprolactam: "V-cap" manufactured by Ashland, monofunctional urethane acrylate (1): "CN8888" manufactured by Sartomer, multifunctional urethane acrylate (2): "EBECRYL4396" manufactured by Daicel Allnex, monofunctional

[0117] The radically polymerizable compounds were mixed according to the formulations shown in Table 3 to prepare acrylic formulations A to D.

[0118] *The units of values ​​in Table 3 are parts by mass.

[0119] (Photopolymerization initiator) 2,2-dimethoxy-1,2-diphenylethan-1-one: "Omnirad 651" manufactured by BASF Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide: "Omnirad 819" manufactured by BASF (Filler) Silica: "AEROSIL RY-200S" manufactured by Nippon Aerosil Co., Ltd.

[0120] [Examples 1 to 9, Comparative Examples 1 to 5] According to the formulations shown in Table 4, each material was stirred at a temperature of 50°C using a planetary stirring device (Thinky Corporation, "Awatori Rentaro"), and then uniformly mixed at a temperature of 50°C using a ceramic three-roll mill to obtain moisture-curable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5. Examples 1 to 3 and Comparative Example 1 were hot-melt types that became solid at 25°C, while the other Examples and Comparative Examples were liquid at 25°C.

[0121]

[0122] The moisture-curing resin compositions of the above examples contain a moisture-curing urethane resin (A) in which polyol A, a linear polyol containing structural units derived from polycarbonate polyol, and polyol B, a polyol having a branched chain with 6 or more carbon atoms, are prepolymerized with polyisocyanate. Therefore, both the initial adhesive strength and high-temperature adhesive strength were good, and even when a hanging test was performed, excellent adhesive properties were exhibited. In contrast, the resin composition prepared in the comparative example did not contain a moisture-curing urethane resin (A) in which polyol A and polyol B were prepolymerized with polyisocyanate, and at least one of the initial adhesive strength and high-temperature adhesive strength was not good. Furthermore, as a result of performing the hanging test, it can be seen that the adhesion was generally insufficient.

[0123] 10, 21 Aluminum substrate 11, 20 Moisture-curable resin composition 12, 22 Glass plate 13 Weight 15 Test piece 16 Hole 17 Weight 23 Sample

Claims

1. A moisture-curable resin composition comprising a moisture-curable urethane resin (A) obtained by prepolymerizing at least polyol A and polyol B with polyisocyanate as polyols, wherein the polyol A is a linear polyol containing structural units derived from polycarbonate polyol, and the polyol B is a polyol having a branched chain with 6 or more carbon atoms.

2. The moisture-curable resin composition according to claim 1, wherein said polyol B is a rosin polyol.

3. A moisture-curing resin composition according to claim 1 or 2, wherein the content of the moisture-curing urethane resin (A) per 100 parts by mass of the moisture-curing resin composition is 35 parts by mass or more and 100 parts by mass or less.

4. The moisture-curable resin composition according to claim 1 or 2, wherein the polycarbonate polyol contains structural units derived from a polyether polycarbonate polyol.

5. The moisture-curable resin composition according to claim 1 or 2, which is liquid at 25°C.

6. The moisture-curable resin composition according to claim 1 or 2, wherein the hydroxyl value of the polyol B is 5 to 200 mgKOH / g.

7. The moisture-curable resin composition according to claim 1 or 2, further comprising a radical polymerizable compound and a photopolymerization initiator.

8. The moisture-curable resin composition according to claim 7, wherein the radically polymerizable compound comprises a monofunctional radically polymerizable compound.

9. The moisture-curable resin composition according to claim 8, wherein the content of the monofunctional radically polymerizable compound is 80 parts by mass or more per 100 parts by mass of the radically polymerizable compound.

10. The moisture-curable resin composition according to claim 8, wherein the monofunctional radically polymerizable compound comprises a polyoxyethylene (meth)acrylate.

11. An adhesive for electronic components, comprising the moisture-curable resin composition according to claim 1 or 2.

12. A cured product of the moisture-curable resin composition according to claim 1 or 2.

13. An electronic component comprising the cured product according to claim 12.

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