Easily dismantled thermosetting resin composition and dismantling method

Abstract

An easily detachable thermosetting resin composition according to the present invention contains a thermosetting component; and a cured product which is obtained by thermally curing this thermosetting resin composition has a structure represented by formula (1).

Description

[Technical Field]

[0001] The present invention relates to an easily dismantled thermosetting resin composition and a dismantling method, more particularly to an easily dismantled thermosetting resin composition, a structure including a cured product of the easily dismantled thermosetting resin composition, a semiconductor device including a cured product of the easily dismantled thermosetting resin composition, a method for dismantling the cured product of the easily dismantled thermosetting resin composition, and a method for recycling materials constituting the structure. [Background technology]

[0002] In recent years, there has been a trend toward using lightweight metals such as aluminum and resins instead of steel in automobile and other structures in order to reduce weight, and composites of these metals with cured thermosetting resins are becoming more common. Meanwhile, to promote the effective use of metals and other resources, active research and development efforts are being conducted to separate, recover, and reuse metals from scrap composite materials used in automobiles and other vehicles. Therefore, it is important to recover the metals by removing the cured thermosetting resins from the composite materials while minimizing damage to the metals.

[0003] For example, Patent Document 1 discloses a treatment liquid capable of efficiently decomposing and dissolving a cured product of a thermosetting resin composition at low temperature, in order to recover carbon fibers from carbon fiber reinforced plastics that use carbon fibers as a reinforcing material, or to recover semiconductor elements and the like from semiconductor packages obtained by sealing semiconductor elements with a cured epoxy resin (encapsulating resin). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2020-50689 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the method for decomposing a cured product of a thermosetting resin composition as disclosed in Patent Document 1 focuses on a treatment liquid for decomposition, and does not disclose a technical idea regarding the decomposability and dismantling property of the thermosetting resin composition itself. The present inventors have newly focused on the dismantling property of the thermosetting resin composition itself and, as a result of extensive research, have found that it is effective for the cured product of the thermosetting resin composition to have a predetermined structure. That is, when the cured product of the thermosetting resin composition is subjected to a solution treatment, the predetermined structural portion is released. It was thought that this would make the network in the hardened material more susceptible to breakdown, making the hardened material more susceptible to disintegration. [Means for solving the problem]

[0006] The present invention provides the following easily dismantlable thermosetting resin composition, a structure comprising a cured product of the easily dismantlable thermosetting resin composition, a semiconductor device comprising a cured product of the easily dismantlable thermosetting resin composition, a method for dismantling a cured product of the easily dismantlable thermosetting resin composition, and a method for recycling materials constituting the structure.

[0007] [1] An easily dismantlable thermosetting resin composition containing a thermosetting component, The easily dismantlable thermosetting resin composition has a structure represented by the following formula (1), wherein the cured product obtained after thermally curing the easily dismantlable thermosetting resin composition has a structure represented by the following formula (1): [ka] (In formula (1), R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms.) [2] The easily dismantlable thermosetting resin composition according to [1], The easily dismantlable thermosetting resin composition, wherein the thermosetting component has an -Si-O- structure. [3] The easily dismantlable thermosetting resin composition according to [1] or [2], The easily dismantlable thermosetting resin composition, wherein the thermosetting component comprises a thermosetting resin and a curing agent, and the thermosetting component and the curing agent both have an -Si-O- structure. [4] The easily dismantlable thermosetting resin composition according to [1] or [2], The easily dismantlable thermosetting resin composition, wherein the thermosetting component comprises a thermosetting resin and a curing agent, and the curing agent has an -Si-O- structure. [5] The easily dismantlable thermosetting resin composition according to [1] or [2], The easily dismantlable thermosetting resin composition, wherein the thermosetting component comprises a thermosetting resin and a curing agent, and the thermosetting resin has an -Si-O- structure. [6] The easily dismantlable thermosetting resin composition according to any one of [3] to [5], The easily dismantlable thermosetting resin composition, wherein the curing agent comprises a phenol-based curing agent. [7] The easily dismantlable thermosetting resin composition according to any one of [3] to [6], The easily dismantlable thermosetting resin composition includes one or more thermosetting resins selected from the group consisting of epoxy resins, phenoxy resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, silicone resins, cyanate resins, bismaleimide resins, and acrylic resins. [8] The easily dismantlable thermosetting resin composition according to [7], The easily dismantlable thermosetting resin composition, wherein the thermosetting resin comprises an epoxy resin. [9] The easily dismantlable thermosetting resin composition according to any one of [1] to [8], The easily dismantlable thermosetting resin composition further comprises an inorganic filler, the content of which is 10 to 98 mass % relative to the total amount of the easily dismantlable thermosetting resin composition.

[10] The easily dismantlable thermosetting resin composition according to any one of [1] to [9], An easily dismantlable thermosetting resin composition comprising a silyl ether-modified novolac resin.

[11] The easily dismantlable thermosetting resin composition according to any one of [1] to

[10] , An easily dismantlable thermosetting resin composition containing a phenolic resin having a weight average molecular weight (Mw) of 500 to 10,000.

[12] A structure comprising a cured product of the easily dismantlable thermosetting resin composition according to any one of [1] to

[11] .

[13] A semiconductor element; a sealing material that seals the semiconductor element; Equipped with The semiconductor device, wherein the encapsulant is made of a cured product of the easily dismantlable thermosetting resin composition according to any one of [1] to

[11] .

[14] A method for dismantling a cured product of the easily dismantlable thermosetting resin composition according to any one of [1] to

[11] , A dismantling method comprising the step of immersing the cured product of the easily dismantlable thermosetting resin composition in a solvent to dismantle it.

[15] The disassembly method according to

[14] , The disassembly method, wherein the solvent is a solvent containing fluoride ions.

[16] The disassembly method according to

[14] or

[15] , The disassembly method, wherein the immersion is carried out at -20 to 200°C.

[17] The disassembly method according to any one of

[14] to

[16] , The disassembly method, wherein the immersion is carried out at 5 to 30°C.

[18] A method for recycling materials constituting the structure according to

[12] , immersing the structure in a solvent to dismantle the cured product of the easily dismantlable thermosetting resin composition; and recovering said material from said structure. [Effects of the Invention]

[0008] According to the present invention, the cured product of the thermosetting resin composition can be easily dismantled, thereby improving the recyclability of resources. DETAILED DESCRIPTION OF THE INVENTION

[0009] In this specification, the notation "a to b" in the description of a range of values ​​means a to b, unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass to 5% by mass." Furthermore, the lower and upper limits of a range of values ​​can be arbitrarily combined with the lower and upper limits of other ranges of values.

[0010] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more.

[0011] In the description of groups (atomic groups) in this specification, when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both groups having no substituents and groups having a substituent. For example, the term "alkyl group" encompasses not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups). In addition, in the description of groups (atomic groups) in this specification, when there is no indication as to whether they are straight-chain, branched, or cyclic, they may be any of straight-chain, branched, or cyclic.

[0012] Unless otherwise specified, the term "organic group" as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, a "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound.

[0013] Hereinafter, embodiments of the present invention will be described in detail.

[0014] 1.Easily dismantled thermosetting resin composition The easily dismantlable thermosetting resin composition of this embodiment (hereinafter also simply referred to as "resin composition") contains a thermosetting component, and the cured product obtained after thermal curing of the resin composition has a structure represented by the following formula (1): Furthermore, the thermal curing conditions are preferably 175°C for 2 minutes.

[0015] [ka] (In formula (1), R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms.)

[0016] As a result, when the cured product of the resin composition of this embodiment is subjected to a solution treatment, the structure of formula (1) is released, the crosslinked structure in the cured product is destroyed, and easy dismantling is achieved. The structure of formula (1) may be formed by the thermosetting reaction of a thermosetting component.

[0017] In this embodiment, "easily dismantlable" means that when the cured product is treated with a solution, the cured product is decomposed into a gel and solubilized. The presence or absence of the structure represented by formula (1) in the cured product can be confirmed by common analytical means such as gas chromatography, high-performance liquid chromatography, thin-layer chromatography, NMR, and IR. The analysis target for confirmation may be the state of the cured product, or a decomposition solution obtained after decomposing the cured product. Gas chromatography mass spectrometry (GC-MS) is preferred because it allows confirmation from the state of the cured product. Furthermore, the analysis target may be a decomposition treatment solution of the cured product, because it makes it easier to distinguish from structures due to coupling agents, etc., as described below.

[0018] Furthermore, the cured product of this embodiment preferably has the structure of formula (1) as a repeating unit. The number of repeats is not particularly limited, but the average number of repeats may be 5 to 1,500.

[0019] In formula (1), R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. The hydrocarbon group having 1 to 30 carbon atoms may be linear, branched, or cyclic, and may or may not have a substituent. The hydrocarbon group having 1 to 30 carbon atoms is preferably a linear alkyl, alkenyl or alkynyl group having 1 to 20 carbon atoms, and more preferably a linear alkyl, alkenyl or alkynyl group having 1 to 10 carbon atoms. The branched hydrocarbon group having 3 to 20 carbon atoms is preferably a branched alkyl, alkenyl, or alkynyl group having 3 to 20 carbon atoms, more preferably a branched alkyl, alkenyl, or alkynyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl, alkenyl, or alkynyl group having 3 to 6 carbon atoms. The cyclic hydrocarbon group having 3 to 20 carbon atoms is preferably a cycloalkyl, cycloalkenyl, or cycloalkynyl group having 3 to 20 carbon atoms, and more preferably a cycloalkenyl or cycloalkynyl group having 5 to 10 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The aromatic group may have a substituent, and examples of the substituent include a hydrocarbon group, a hydroxyl group, a halogen atom, and an amino group. The alkoxyl group having 1 to 30 carbon atoms is preferably an alkoxyl group having 1 to 10 carbon atoms, and more preferably an alkoxyl group having 1 to 6 carbon atoms. Specific examples include a methoxy group, an ethoxy group, and an isopropyloxy group.

[0020] The resin composition of this embodiment contains a thermosetting component. The thermosetting component may be any component that contains a group that polymerizes / crosslinks when acted upon by an active chemical species such as a radical, and specifically may be either a thermosetting resin or a curing agent. The resin composition of this embodiment may contain only one type of thermosetting component, or may contain two or more types of thermosetting components.

[0021] The resin composition of this embodiment preferably contains a thermosetting resin and a curing agent. In this case, it is preferable that at least one of the thermosetting resin and the curing agent has an -Si-O- structure. This allows the cured product of the resin composition of this embodiment to have the structure represented by formula (1), and the cured product is soluble in a solvent, resulting in easy dismantling.

[0022] The resin composition of the present embodiment can be made by combining various components so that the cured product has a structure represented by formula (1), and specific examples include resin compositions in the following forms.

[0023] <1> A resin composition containing a phenolic resin (P) having an -Si-O- structure. <2> A resin composition comprising a thermosetting resin and a phenolic resin (P) having an -Si-O- structure as a curing agent. <3> A resin composition containing an epoxy resin (A) having an -Si-O- structure. <4> A resin composition comprising: a silicone resin (organopolysiloxane) (C1) as a thermosetting resin having two or more alkenyl groups bonded to silicon atoms in one molecule; and an organohydrogenpolysiloxane (C2) as a curing agent having two or more hydrogen atoms bonded to silicon atoms in one molecule. <5> A resin composition comprising an acrylic / vinyl resin obtained by reacting unsaturated bonds having an -Si-O- structure in the main chain.

[0024] Each embodiment will be described in detail below.

[0025] First Embodiment In the first embodiment, a resin composition containing a phenolic resin (P) having an -Si-O- structure will be described. In this case, the curing agent may not have an -Si-O- structure, and a known curing agent may be used. Known curing agents will be described later.

[0026] The phenolic resin (P) having an -Si-O- structure may be a phenolic resin modified with a silyl ether having a phenolic hydroxyl group. Specific examples include silyl ether-modified novolak resins represented by the following formula (P1):

[0027] [ka]

[0028] In formula (P1), x and y are both integers, and x+y is 2-200. In addition, in formula (P1), in order to obtain good dismantling properties and moldability, x:y=1:99 to 99:1 is preferable, x:y=2:98 to 75:25 is more preferable, and x:y=5:95 to 50:50 is even more preferable. In addition, in formula (P1), D has a structure represented by the following formula (P1-1).

[0029] [ka]

[0030] In formula (P1-1), R9 represents a divalent hydrocarbon group having 2 to 10 carbon atoms. 10 each independently represents a hydrogen atom, a monovalent hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. z is an integer of 0 to 10. Among these, R9 is preferably a divalent hydrocarbon group having 2 to 5 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and even more preferably a propenyl group. 10 are each independently preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkyl group, even more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group.

[0031] The weight-average molecular weight (Mw) of the phenolic resin (P1) is not particularly limited, but is preferably 500 to 10,000, more preferably 1,000 to 8,000, and even more preferably 1,500 to 5,000. The number-average molecular weight (Mn) of the phenolic resin (P1) is not particularly limited, but is preferably 100 to 5,000, more preferably 300 to 3,000, and even more preferably 600 to 1,000. In this embodiment, Mw and Mn can be calculated by gel permeation chromatography (GPC).

[0032] The phenolic resin (P) can be synthesized by reacting a silyl ether, a phenol, and an aldehyde in the presence of an acid catalyst.

[0033] The silyl ethers are preferably those having a phenolic hydroxyl group, and examples thereof include those represented by the following formula (P1-2).

[0034] [ka]

[0035] In formula (P1-2), R9 represents a divalent hydrocarbon group having 2 to 10 carbon atoms. 10 each independently represents a hydrogen atom, a monovalent hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. z is an integer of 0 to 10. Among these, R9 is preferably a divalent hydrocarbon group having 2 to 5 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and even more preferably a propenyl group. 10 are each independently preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and are also preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.

[0036] Examples of phenols include, but are not limited to, phenol; cresols such as orthocresol, meta-cresol, and para-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, and 3,5-xylenol; 2,3,5-trimethylphenol, 2-ethylphenol, 4-ethylphenol, 2-isopropylphenol, 4-isopropylphenol, n-butylphenol, isobutylphenol, tert-butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, benzylphenol, cumylphenol, allylphenol, and kaolin. Examples of suitable phenols include alkylphenols such as rudanol, urushiol, thitsiol, and laccol; naphthols such as 1-naphthol and 2-naphthol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol; substituted monohydric phenols such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, and trinitrophenol; and polyhydric phenols such as resorcinol, alkylresorcinol, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, and naphthalene. These may be used alone or in combination of two or more. Among these, the phenols may include one or more selected from the group consisting of phenol, cresol, xylenol, and alkylphenols. From the viewpoint of cost, phenol is preferably used. can.

[0037] The aldehydes are not particularly limited, and examples thereof include formaldehydes such as formalin and paraformaldehyde; trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butylaldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. These aldehydes may be used alone or in combination of two or more. Among these, the aldehydes may include formaldehyde or acetaldehyde, and from the viewpoints of productivity and cost, formalin or paraformaldehyde can be used.

[0038] The catalyst used in synthesizing the phenolic resin (P) may be catalyst-free, or an acidic catalyst may be used from the viewpoint of producing a novolac phenolic resin. The acidic catalyst is not particularly limited, but examples thereof include acids such as oxalic acid, hydrochloric acid, sulfuric acid, diethyl sulfate, and paratoluenesulfonic acid, and metal salts such as zinc acetate, which may be used alone or in combination of two or more.

[0039] The reaction solvent used in synthesizing the phenolic resin (P) may be water, or an organic solvent. A non-aqueous system using a non-polar solvent can be used as the organic solvent. Examples of the organic solvent include alcohols, ketones, and aromatics. Examples of the alcohols include methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, and glycerin. Examples of the ketones include acetone and methyl ethyl ketone. Examples of the aromatics include toluene and xylene. These may be used alone or in combination of two or more.

[0040] The molar ratio of phenols (P) to aldehydes (F) (F / P molar ratio) may be, for example, 0.2 to 1.0 mol, preferably 0.3 to 0.9 mol, of aldehydes per 1 mol of phenols. By setting the aldehydes within the above range, the amount of unreacted phenols can be reduced, and the yield can be increased.

[0041] The reaction temperature may be, for example, 40° C. to 120° C., and preferably 60° C. to 110° C. The reaction time is not particularly limited and may be appropriately determined depending on the types of starting materials, the molar ratio of the starting materials, the amount and type of catalyst used, and the reaction conditions.

[0042] In this way, the phenol resin (P) can be obtained.

[0043] Second Embodiment In the second embodiment, a case where a phenolic resin (P) having an -Si-O- structure is used as a curing agent will be described. In this case, the thermosetting resin may or may not have an -Si-O- structure, but the second embodiment will describe a case where the thermosetting resin does not have an -Si-O- structure. The thermosetting resin is not particularly limited, but known epoxy resins can be used. Known epoxy resins will be described later.

[0044] The phenolic resin (P) and epoxy resin as curing agents are adjusted so that the equivalent ratio (EP) / (OH) of the number of epoxy groups (EP) in the total thermosetting resin to the number of phenolic hydroxyl groups (OH) in the total phenolic resin is preferably 0.8 to 1.6, more preferably 0.9 to 1.3, and even more preferably 1.0 to 1.2. When the equivalent ratio is within the above range, the curing properties of the resulting resin composition of this embodiment can be improved.

[0045] Other components contained in the resin composition of the second embodiment will be described later.

[0046] <Third embodiment> In the third embodiment, a resin composition containing an epoxy resin (A) having an -Si-O- structure will be described. In this case, the curing agent may or may not have an -Si-O- structure, but the third embodiment will be described with respect to a case where the curing agent does not have an Si-O- structure. The curing agent is not particularly limited, but a known curing agent may be used. Known curing agents will be described later.

[0047] Specific examples of the epoxy resin (A) having an -Si-O- structure include an epoxy resin (A1) having an -Si-O- structure obtained by epoxidizing the phenolic resin (P1) having an -Si-O- structure described in the first embodiment, a bifunctional or higher functional epoxy compound (A2) having a structure represented by the following formula (A2), and an organosiloxane epoxy compound (A3) having a structure represented by the following formula (A3).

[0048] [Epoxy resin (A1)] Examples of the epoxy resin (A1) having an —Si—O— structure obtained by epoxidizing the phenolic resin (P1) having an —Si—O— structure include those represented by the following formula (A1).

[0049] [ka]

[0050] In formula (A1), x and y are both integers, and x+y is 2-200. In addition, in terms of obtaining good dismantling properties and moldability, in formula (A1), x:y=1:99 to 99:1 is preferable, x:y=2:98 to 75:25 is more preferable, and x:y=5:95 to 50:50 is even more preferable. In addition, in formula (A1), D has a structure represented by the following formula (A1-1).

[0051] [ka]

[0052] In formula (A1-1), R9 represents a divalent hydrocarbon group having 2 to 10 carbon atoms. 10 each independently represents a hydrogen atom, a monovalent hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. z is an integer of 0 to 10. Among these, R9 is preferably a divalent hydrocarbon group having 2 to 5 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and even more preferably a propenyl group. 10 are each independently preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and are also preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methyl group.

[0053] The epoxy resin (A1) can be produced by epoxidizing the above phenolic resin (P1) by a known method.

[0054] [Epoxy compound (A2)] The epoxy compound (A2) is a di- or higher functional epoxy compound having a structure represented by the following formula (A2).

[0055] [ka]

[0056] In formula (A2), m and n are integers, and m+n=4. R3 is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic, heterocycloalkyl, cycloalkenyl, heteroaryl, alkoxyaryl, alkoxyalkyl. B independently represents an arylene, an arylene ether, an alkylene-arylene, an alkylene-arylene alkylene, an alkenylene-arylene, an alkenylene-arylenealkenylene, an alkylene-arylene-alkenylene, an alkynylenearylene, an alkynylene-arylene-alkynylene, a heteroarylene, an alkylene-heteroarylene, an alkylene-heteroarylene-alkylene, an alkenylene-heteroarylene, an alkenylene-heteroarylene-alkenylene, an alkylene-heteroarylene-alkenylene, an alkynylene Heteroarylene, alkynylene-heteroarylene-alkynylene, alkylene, alkylene-hetero-alkylene, alkenylene, alkenylene-hetero-alkenylene, alkylene-hetero-alkenylene, alkynylene, cycloalkylene, alkylene-cycloalkylene, alkylene-cycloalkylenealkylene, alkenylene-cycloalkylene, alkenylenecycloalkylene-alkenylene, alkylene-cycloalkylenealkenylene, alkynylene-cycloalkylene, alkynylenecycloalkylene-alkynylene, hetero Cycloalkylene, alkyleneheterocycloalkylene, alkylene-heterocycloalkylenealkylene, alkenylene-heterocycloalkylene, alkenyleneheterocycloalkylene-alkenylene, alkyleneheterocycloalkylene-alkenylene, alkynyleneheterocycloalkylene, alkynylene-heterocycloalkylenealkynylene, cycloalkenylene, alkylene-cycloalkenylene, alkylene-cycloalkenylene-alkylene, alkenylene-cycloalkenylene, alkenylene-cycloalkenylene-alkenylene alkylenecycloalkenylene-alkenylene, alkynylene-cycloalkenylene, alkynylene-cycloalkenylene-alkynylene, heterocycloalkenylene, alkylene-heterocycloalkenylene, alkylene-heterocycloalkenylene-alkylene, alkenylene-heterocycloalkenylene, alkenylene-heterocycloalkenylene-alkenylene, alkylene-heterocycloalkenylene-alkenylene, alkynyleneheterocycloalkenylene, alkynylene-heterocycloalkenylene, or alkynylene.

[0057] Specific examples of the di- or higher functional epoxy compound (A2) include those represented by the following formulae (A2-1) to (A2-19).

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] The epoxy compound (A2) can be obtained, for example, as follows. The method includes a step of partially epoxidizing a polyhydric alcohol having one or more hydroxy groups with epihalohydrin in the presence of a base to obtain a partially epoxidized alcohol, and a step of reacting the partially epoxidized alcohol with a compound having a structure represented by any one of the following formulas (4-1) to (4-3) in the presence of an acidic catalyst, thereby obtaining a mixture containing an epoxy compound (A2) having an —Si—O— structure.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] (wherein R5 to R8 are each independently hydrogen, alkyl, alkenyl, alkynyl, methylene, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclic, heterocycloalkyl, cycloalkenyl, heteroaryl, alkoxy, alkoxyaryl, alkoxyalkyl, or aryloxy; R 11 is hydrogen, alkyl, aryl, aralkyl, alkenyl, or alkynyl)

[0067] [Epoxy compound (A3)] The epoxy compound (A3) has a structure represented by the following formula (A3).

[0068] [ka]

[0069] In formula (A3), R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. R 12 are each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. w is an integer of 1 to 50.

[0070] As the epoxy compound (A3), commercially available products can be used, and examples thereof include the double-end epoxy-modified silicones "X-22-163," "X-22-163A," "X-22-163B," "X-22-163C," and "KF-105" (all manufactured by Shin-Etsu Silicones Co., Ltd.).

[0071] Specific examples of the epoxy compound (A3) include those represented by the following formula (A3-1).

[0072] [ka]

[0073] In formula (A3-1), R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. Among these, R1 and R2 are preferably alkyl groups having 1 to 30 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and even more preferably methyl groups.

[0074] The epoxy compound represented by the formula (A3-1) may be a commercially available product, for example, alicyclic epoxy group-containing linear siloxane bifunctional oligomer "X-40-2669" (manufactured by Shin-Etsu Silicones Co., Ltd.).

[0075] The physical properties of the epoxy resin (A) having an —Si—O— structure of this embodiment will be described below.

[0076] The weight average molecular weight (Mw) of the epoxy resin (A) having an —Si—O— structure of the present embodiment is not particularly limited, but is preferably 500 to 10,000, more preferably 1,000 to 7,000, and even more preferably 2,000 to 6,000. The number average molecular weight (Mn) of the epoxy resin (A) having an —Si—O— structure of the present embodiment is not particularly limited, but is preferably 100 to 5,000, more preferably 300 to 3,000, and even more preferably 600 to 1,000.

[0077] The viscosity of the epoxy resin (A) having an —Si—O— structure of this embodiment is preferably in the range of 1 to 40,000 mPa·s.

[0078] The epoxy resin (A) having an -Si-O- structure of this embodiment preferably has an epoxy equivalent weight (EEW) in the range of 100 to 600 g / mEq, where EEW means the mass (grams) of a resin containing 1 epoxy equivalent.

[0079] In the third embodiment, the resin composition preferably uses a known phenol-based curing agent.

[0080] The phenolic curing agent as the curing agent and the epoxy resin (A) having an -Si-O- structure are adjusted so that the equivalent ratio (EP) / (OH) of the number of epoxy groups (EP) in all thermosetting resins to the number of phenolic hydroxyl groups (OH) in all phenolic resins is preferably 0.8 to 1.6, more preferably 0.9 to 1.3, and even more preferably 1.0 to 1.2. When the equivalent ratio is within the above range, the curing properties of the resulting resin composition of this embodiment can be improved.

[0081] Other components contained in the resin composition of the third embodiment will be described later.

[0082] <Fourth embodiment> In the fourth embodiment, a resin composition will be described which contains, as a thermosetting resin, an organopolysiloxane (silicone resin) (C1) having two or more alkenyl groups bonded to silicon atoms in one molecule, and, as a curing agent (crosslinking agent), an organohydrogenpolysiloxane (C2) having two or more hydrogen atoms bonded to silicon atoms in one molecule.

[0083] (Organopolysiloxane (C1)) The organopolysiloxane (C1) having two or more silicon-bonded alkenyl groups per molecule is preferably a linear organopolysiloxane, preferably a linear organopolysiloxane having 2 to 8 silicon-bonded alkenyl groups per molecule. Specific examples include those having a structure represented by the following formula (C1-1):

[0084] [ka]

[0085] In formula (C1-1), R 13are the same or different, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 12 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms. R 13 Specific examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and cyclohexyl groups; fluorine-substituted alkyl groups in which some or all of the hydrogen atoms bonded to carbon atoms of these alkyl groups have been substituted with halogen atoms such as chlorine atoms, fluorine atoms, and bromine atoms, for example, trifluoromethyl and 3,3,3-trifluoropropyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, and cyclohexenyl groups; and aryl groups such as phenyl group. Among these, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 8 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms are preferred. s is an integer of 5 to 50,000, and preferably an integer of 10 to 20,000.

[0086] The alkenyl groups in the organopolysiloxane (C1) may be present either at the molecular chain terminals or on the side chains, but it is preferred that the alkenyl groups are present only at the terminals.

[0087] Among the organopolysiloxanes (C1), specific examples of the vinyl group-containing linear organopolysiloxane (C1-2) include those represented by the following formula (C1-2).

[0088] [ka]

[0089] In formula (C1-2), R 1 and R 2 are each independently a methyl group or a vinyl group, and at least one of them is a vinyl group.

[0090] The vinyl group-containing linear organopolysiloxane (C1-2) may contain a first vinyl group-containing linear organopolysiloxane (C1-2') having two or more vinyl groups in the molecule and having a vinyl group content of 0.4 mol% or less. The vinyl group content of the first vinyl group-containing linear organopolysiloxane (C1-2') may be 0.1 mol% or less.

[0091] The vinyl group-containing linear organopolysiloxane (C1-2) may also contain a first vinyl group-containing linear organopolysiloxane (C1-2') and a second vinyl group-containing linear organopolysiloxane (C1-2'') having a vinyl group content of 0.5 to 15 mol %.

[0092] By combining a first vinyl group-containing linear organopolysiloxane (C1-2') with a second vinyl group-containing linear organopolysiloxane (C1-2'') with a high vinyl group content as the raw rubber used to make the silicone rubber, it is possible to unevenly distribute the vinyl groups and more effectively create a variation in crosslink density within the crosslinked network of the silicone rubber. As a result, the tear strength of the release film is more effectively increased, and dimensional stability and transferability are easier to control.

[0093] Specifically, the vinyl group-containing linear organopolysiloxane (C1-2) may be, for example, a vinyl group-containing linear organopolysiloxane represented by the formula (C1-2) above, wherein R 1 is a vinyl group and / or R 2 a first vinyl group-containing linear organopolysiloxane (C1-2') having two or more units in the molecule in which R is a vinyl group and containing 0.4 mol % or less of the unit; 1 is a vinyl group and / or R 2 It is preferable to use a second vinyl group-containing linear organopolysiloxane (C1-2'') containing 0.5 to 15 mol % of units in which each of the units is a vinyl group.

[0094] The first vinyl group-containing linear organopolysiloxane (C1-2') preferably has a vinyl group content of 0.01 to 0.2 mol %. The second vinyl group-containing linear organopolysiloxane (C1-2'') preferably has a vinyl group content of 0.8 to 12 mol %.

[0095] Furthermore, when the first vinyl group-containing linear organopolysiloxane (C1-2') and the second vinyl group-containing linear organopolysiloxane (C1-2'') are combined and blended, the ratio of (C1-2') to (C1-2'') is not particularly limited, but for example, the weight ratio of (C1-2'):(C1-2'') is preferably 50:50 to 95:5, and more preferably 80:20 to 90:10.

[0096] The first and second vinyl group-containing linear organopolysiloxanes (C1-2') and (C1-2'') may each be used alone or in combination of two or more.

[0097] The organopolysiloxane (C1) may also contain a vinyl group-containing branched organopolysiloxane having a branched structure.

[0098] (Organohydrogenpolysiloxane (C2)) The organohydrogenpolysiloxane (C2) having two or more hydrogen atoms bonded to silicon atoms in one molecule includes those having a structure represented by the following formula (C2).

[0099] [ka]

[0100] In formula (C2), R 14are each independently an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group or tolyl group; or a group in which some or all of the hydrogen atoms bonded to carbon atoms of these groups have been substituted with a hydroxyl group, a cyano group, a halogen atom, or the like. A monovalent hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group or an aryl group, is preferred. t is an integer of 2 or greater, preferably 2 to 50, and more preferably 3 to 30.

[0101] The amount of organohydrogenpolysiloxane (C2) blended is appropriately set depending on the number of moles of alkenyl groups in organopolysiloxane (C1) having two or more alkenyl groups per molecule, but it is preferably investigated so that the number of moles of SiH groups in organohydrogenpolysiloxane (C2) is in the range of 0.5 to 20, more preferably 0.8 to 5, of the alkenyl groups in silicone resin (C1).

[0102] The organohydrogenpolysiloxane (C2) is classified into a linear organohydrogenpolysiloxane (C2-1) having a linear structure and a branched organohydrogenpolysiloxane (C2-2) having a branched structure, and may contain either one or both of these.

[0103] The linear organohydrogenpolysiloxane (C2-1) has a linear structure and a structure in which hydrogen is directly bonded to Si (≡Si-H), and is a polymer that undergoes a hydrosilylation reaction with the vinyl groups of the vinyl group-containing organopolysiloxane (C1-2) and with vinyl groups of components contained in the raw materials of the release layer 1, thereby crosslinking these components.

[0104] The molecular weight of the linear organohydrogenpolysiloxane (C2-1) is not particularly limited, but for example, the weight average molecular weight is preferably 20,000 or less, and more preferably 1,000 or more and 10,000 or less.

[0105] The weight average molecular weight of the linear organohydrogenpolysiloxane (C2-1) can be measured, for example, by polystyrene conversion using GPC (gel permeation chromatography) using chloroform as a developing solvent.

[0106] Furthermore, it is generally preferred that the linear organohydrogenpolysiloxane (C2-1) does not contain a vinyl group, which effectively prevents the crosslinking reaction from proceeding within the linear organohydrogenpolysiloxane (C2-1) molecule.

[0107] As the linear organohydrogenpolysiloxane (C2-1) described above, for example, one having a structure represented by the following formula (C2-1) is preferably used.

[0108] [ka]

[0109] In formula (C2-1), R 4 is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, a hydrocarbon group combining these, or a hydride group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, and a propyl group, with a methyl group being preferred. Examples of the alkenyl group having 1 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

[0110] Also, R 5 is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, a hydrocarbon group combining these, or a hydride group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, and a propyl group, with a methyl group being preferred. Examples of the alkenyl group having 1 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

[0111] In addition, in formula (C2-1), multiple R 4 are independent of each other and may be different or the same. 5 The same applies to multiple R 4 and R 5 At least two of these are hydride groups.

[0112] Also, R 6 is a substituted or unsubstituted alkyl group or aryl group having 1 to 8 carbon atoms, or a hydrocarbon group combining these. Examples of alkyl groups having 1 to 8 carbon atoms include methyl groups, ethyl groups, and propyl groups, with methyl groups being preferred. Examples of aryl groups having 1 to 8 carbon atoms include phenyl groups. 6 are independent of each other and may be different from each other or may be the same.

[0113] In addition, R in formula (C2-1) 4 ,R 5 ,R 6 Examples of the substituent include a methyl group and a vinyl group, and a methyl group is preferred from the viewpoint of preventing intramolecular crosslinking reactions.

[0114] Furthermore, m and n are the numbers of repeating units constituting the linear organohydrogenpolysiloxane (C2-1) represented by formula (C2-1), where m is an integer of 2 to 150 and n is an integer of 2 to 150. Preferably, m is an integer of 2 to 100 and n is an integer of 2 to 100.

[0115] The linear organohydrogenpolysiloxane (C2-1) may be used alone or in combination of two or more.

[0116] Because the branched organohydrogenpolysiloxane (C2-2) has a branched structure, it forms regions with high crosslink density, and is a component that significantly contributes to the formation of a sparsely crosslinked structure within the silicone rubber system. Like the linear organohydrogenpolysiloxane (C2-1), it has a structure in which hydrogen is directly bonded to silicon (≡Si-H), and undergoes a hydrosilylation reaction with the vinyl groups of the vinyl-group-containing organopolysiloxane (C1-2) and with the vinyl groups of the components contained in the raw materials for the release layer 1, forming a polymer that crosslinks these components.

[0117] The specific gravity of the branched organohydrogenpolysiloxane (C2-2) is in the range of 0.9 to 0.95.

[0118] Furthermore, it is generally preferred that the branched organohydrogenpolysiloxane (C2-2) does not contain a vinyl group, which effectively prevents the crosslinking reaction from proceeding within the branched organohydrogenpolysiloxane (C2-2) molecule.

[0119] The branched organohydrogenpolysiloxane (C2-2) is preferably one represented by the following average composition formula (c):

[0120] Average composition formula (c) (Ha(R 7 )3-aSiO 1 / 2 )m(SiO 4 / 2 )n (In formula (c), R 7 is a monovalent organic group, a is an integer ranging from 1 to 3, and m is Ha(R 7 )3-aSiO 1 / 2 The number of units, n, is SiO 4 / 2 (the number of units)

[0121] In formula (c), R 7is a monovalent organic group, preferably a substituted or unsubstituted alkyl group or aryl group having 1 to 10 carbon atoms, or a hydrocarbon group consisting of a combination thereof. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of aryl groups having 1 to 10 carbon atoms include phenyl groups.

[0122] In formula (c), a is the number of hydride groups (hydrogen atoms directly bonded to Si), and is an integer ranging from 1 to 3, preferably 1.

[0123] In addition, in formula (c), m is Ha(R 7 )3-aSiO 1 / 2 The number of units, n, is SiO 4 / 2 The number of units.

[0124] The branched organohydrogenpolysiloxane (C2-2) has a branched structure. The linear organohydrogenpolysiloxane (C2-1) and the branched organohydrogenpolysiloxane (C2-2) differ in their structures, whether they are linear or branched. The number of alkyl groups R bonded to Si (R / Si), where the number of Si is 1, is in the range of 1.8 to 2.1 for the linear organohydrogenpolysiloxane (C2-1) and 0.8 to 1.7 for the branched organohydrogenpolysiloxane (C2-2).

[0125] Because the branched organohydrogenpolysiloxane (C2-2) has a branched structure, for example, when heated to 1000°C at a heating rate of 10°C / min in a nitrogen atmosphere, the amount of residue is 5% or more. In contrast, because the linear organohydrogenpolysiloxane (C2-1) is linear, the amount of residue after heating under the above conditions is almost zero.

[0126] Specific examples of the branched organohydrogenpolysiloxane (C2-2) include those having a structure represented by the following formula (C2-2):

[0127] [ka]

[0128] In formula (C2-2), R 7 R is a substituted or unsubstituted alkyl group or aryl group having 1 to 8 carbon atoms, or a hydrocarbon group combining these, or a hydrogen atom. Examples of alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, and propyl groups, with methyl being preferred. Examples of aryl groups having 1 to 8 carbon atoms include phenyl groups. 7 Examples of the substituent include a methyl group.

[0129] In addition, in formula (C2-2), multiple R 7 are independent of each other and may be different from each other or may be the same.

[0130] In addition, in formula (C2-2), "-O-Si≡" indicates that Si has a branched structure that spreads three-dimensionally.

[0131] The branched organohydrogenpolysiloxane (C2-2) may be used alone or in combination of two or more.

[0132] In addition, the amount of hydrogen atoms (hydride groups) directly bonded to Si in the linear organohydrogenpolysiloxane (C2-1) and the branched organohydrogenpolysiloxane (C2-2) is not particularly limited. However, in the release layer 1, the total amount of hydride groups in the linear organohydrogenpolysiloxane (C2-1) and the branched organohydrogenpolysiloxane (C2-2) is preferably 0.5 to 5 moles, more preferably 1 to 3.5 moles, per mole of vinyl groups in the vinyl group-containing linear organopolysiloxane (C1-1). This ensures the reliable formation of a crosslinked network between the linear organohydrogenpolysiloxane (C2-1) and the branched organohydrogenpolysiloxane (C2-2) and the vinyl group-containing linear organopolysiloxane (C1-1).

[0133] (catalyst, curing accelerator) In the fourth embodiment, the resin composition preferably further contains a catalyst, which can accelerate the curing of the organopolysiloxane (C1) and the organohydrogenpolysiloxane (C2). Examples of the catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, with platinum being preferred. Specific examples of platinum-based catalysts include platinum fine powder, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex, as well as catalysts in which these platinum-based catalysts are dispersed or encapsulated in a thermoplastic resin. The amount of catalyst added is preferably 0.01 to 5 mass %, more preferably 0.02 to 2 mass %, and even more preferably 0.05 to 1 mass %, based on the total amount of the resin composition.

[0134] Other components contained in the resin composition of the fourth embodiment will be described later.

[0135] Although an example of an embodiment of the resin composition of the present invention has been described above, the resin composition of the present invention is not limited to this. Furthermore, the resin composition of each of the above embodiments may further contain a known thermosetting resin and a known curing agent in addition to the above-mentioned thermosetting component, and may also contain other components depending on the application, etc. Hereinafter, other components that may be contained in the resin composition of the present invention will be described.

[0136] [Thermosetting resin] The thermosetting resin of this embodiment may be one or more selected from the group consisting of phenolic resin, epoxy resin, phenoxy resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, melamine resin, silicone resin, cyanate resin, maleimide resin, cyanate resin, and acrylic resin. These thermosetting resins may be any monomer, oligomer, or polymer having two or more reactive functional groups per molecule, and their molecular weight and molecular structure are not particularly limited.

[0137] The epoxy resin may be any monomer, oligomer, or polymer having two or more epoxy groups in one molecule, and there are no particular limitations on the molecular weight or molecular structure. Specific examples of the epoxy resin include novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins; aromatic glycidylamine-type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, and aminophenol-type glycidylamine; hydroquinone-type epoxy resins; biphenyl-type epoxy resins; stilbene-type epoxy resins; triphenolmethane-type epoxy resins; triphenolpropane-type epoxy resins; and alkyl-modified triphenols.

[0033] Examples of the epoxy resin include one or more selected from the group consisting of phenol methane type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene-modified phenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, naphthylene ether type epoxy resins, aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, and naphthol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, and aliphatic epoxy resins such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy adipide.

[0138] The content of the thermosetting resin is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 20% by mass or less, based on the total amount of the resin composition. By setting the content of the thermosetting resin to the above lower limit or more, the flowability and moldability of the resin composition can be more effectively improved, and by setting the content of the thermosetting resin to the above upper limit or less, the curability can be improved and a good cured product can be obtained.

[0139] [Hardening agent] The curing agent of the present embodiment is selected depending on the type of thermosetting resin, and is not particularly limited as long as it reacts with the thermosetting resin. Specific examples of the curing agent include polyaddition type curing agents, catalyst type curing agents, and condensation type curing agents.

[0140] Specific examples of the curing agent include phenolic curing agents, amines, polyoxystyrenes such as polyparaoxystyrene, alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), acid anhydrides including aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA), polymercaptan compounds such as polysulfide, thioester, and thioether, isocyanate compounds such as isocyanate prepolymers and blocked isocyanates, and organic acids such as carboxylic acid-containing polyester resins.

[0141] Specific examples of the phenolic curing agent include one or more selected from novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, naphthol novolac resin, aminotriazine novolac resin, novolac resin, and trisphenylmethane-type phenol novolac resin; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl-type resins such as phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton and naphthol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F; and resol-type phenolic resins. From the viewpoint of curability, the hydroxyl group equivalent of the phenolic resin-based curing agent is preferably, for example, 90 g / eq or more and 250 g / eq or less.

[0142] Specific examples of the amines include one or more selected from aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylenediamine (MXDA); aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS); polyamine compounds including dicyandiamide (DICY) and organic acid dihydralazides; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA); and acid anhydrides including aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA).

[0143] The content of the curing agent is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the thermosetting resin.

[0144] The contents of the thermosetting resin and curing agent are appropriately set depending on the thermosetting resin and curing agent. For example, the phenolic curing agent as the curing agent and the epoxy resin as the thermosetting resin are adjusted so that the equivalent ratio (EP) / (OH) of the number of epoxy groups (EP) in the total thermosetting resin to the number of phenolic hydroxyl groups (OH) in the total phenolic resin is preferably 0.8 to 1.6, more preferably 0.9 to 1.3, and even more preferably 1.0 to 1.2. When the equivalent ratio is within the above range, the curing characteristics of the resulting resin composition of this embodiment can be improved.

[0145] The resin composition of the present embodiment may further contain the following components.

[0146] [Inorganic filler] The resin composition of the present embodiment may contain an inorganic filler. Inorganic fillers are used to increase the mechanical strength and to impart heat resistance, flame retardancy, etc. depending on the intended use of the cured product or structure. Specific examples of inorganic fillers include silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, and silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; and titanates such as strontium titanate and barium titanate. These may be used alone or in combination of two or more.

[0147] The average particle size D50 of the inorganic filler is preferably 0.01 μm or more and 75 μm or less, more preferably 0.05 μm or more and 50 μm or less. By setting the average particle size of the inorganic filler within the above range, the filling property is improved. The average particle size D50 can be the average particle size converted into volume (cumulative 50%) using a commercially available laser particle size distribution analyzer.

[0148] The content of the inorganic filler is appropriately set depending on the application, but is preferably 10 to 98 mass %, more preferably 20 to 95 mass %, and even more preferably 40 to 95 mass %, relative to the total amount of the resin composition. By setting the content of the inorganic filler to the above lower limit or more, the shelf life and curability of the cured product can be improved, while by setting the content of the inorganic filler to the above upper limit or less, good fluidity of the resin composition can be obtained, and moldability can be effectively improved.

[0149] [Coupling agent] When the resin composition of the present embodiment contains an inorganic filler, it may contain a coupling agent, which can suppress aggregation of the inorganic filler and provide good flowability. As the coupling agent, known coupling agents such as various silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane, titanium-based compounds, aluminum chelates, and aluminum / zirconium-based compounds can be used.

[0150] More specifically, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-[bis(β-hydroxyethyl)]aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl) silane coupling agents such as -γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-(β-aminoethyl)aminopropyldimethoxymethylsilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine hydrolysate;Examples of titanate-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl - aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis (dioctyl phosphite) titanate. These may be used alone or in combination of two or more.

[0151] The content of the coupling agent is not particularly limited, but is preferably 0.05% by mass or more and 3% by mass or less, and more preferably 0.1% by mass or more and 2% by mass or less, based on the total resin composition. By making the content of the coupling agent equal to or greater than the lower limit, the dispersibility of the inorganic filler in the resin composition can be improved. Furthermore, by making the content of the coupling agent equal to or less than the upper limit, the flowability of the resin composition can be improved, and moldability can be improved.

[0152] [Curing accelerator] The resin composition of the present embodiment may contain a curing accelerator. A cure accelerator typically accelerates the reaction between a thermosetting resin and a curing agent.

[0153] Specific examples of the curing accelerator include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, or adducts of phosphonium compounds and silane compounds; amidine compounds such as 1,8-diazabicyclo(5,4,0)undecene-7 and imidazole; nitrogen atom-containing compounds such as tertiary amines such as benzyldimethylamine, amidinium salts, or ammonium salts; and phenolic compounds such as phenol, bisphenol A, nonylphenol, and 2,3-dihydroxynaphthalene. Examples of the organic phosphines include triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium tetraphenylborate, triphenylphosphine triphenylborane, 1,2-bis-(diphenylphosphino)ethane, etc. These may be used alone or in combination of two or more.

[0154] The content of the curing accelerator is appropriately set depending on the application, but is preferably 0.1 to 5 mass %, more preferably 0.2 to 3 mass %, based on the total amount of the resin composition. By setting the content of the curing accelerator to be equal to or greater than the above lower limit, the resin composition can be appropriately cured. On the other hand, by setting the content of the curing accelerator to be equal to or less than the above upper limit, the molten state can be prolonged, and the low-viscosity state can be prolonged.

[0155] [Hydroxyl group-containing cyclic compound] When the resin composition of this embodiment contains a curing accelerator, it may contain a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter also referred to as a "hydroxyl group-containing cyclic compound"). This makes it possible to suppress reactions during melt-kneading of the resin composition, even when a phosphorus atom-containing curing accelerator without latency is used as the curing accelerator, and a stable resin composition can be obtained. Furthermore, the hydroxyl group-containing cyclic compound also has the effect of reducing the melt viscosity of the resin composition and improving its flowability.

[0156] The hydroxyl group-containing cyclic compound may be a monocyclic compound represented by the following general formula (5) or a polycyclic compound represented by the following general formula (6). These compounds may have a substituent other than a hydroxyl group.

[0157] [ka]

[0158] In general formula (5), one of R15 and R19 is a hydroxyl group, and the other is a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group. R16, R17, and R18 are each a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group.

[0159] [ka]

[0160] In general formula (6), one of R20 and R26 is a hydroxyl group, and the other is a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group. R21, R22, R23, R24, and R25 are hydrogen atoms, a hydroxyl group, or a substituent other than a hydroxyl group.

[0161] Specific examples of the monocyclic compound represented by the general formula (5) include catechol, pyrogallol, gallic acid, gallic acid esters, and derivatives thereof. Specific examples of polycyclic compounds represented by general formula (6) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, compounds in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring are preferred because of the ease of controlling fluidity and curability. Furthermore, when considering volatilization during the kneading process, it is more preferable to use a compound in which the mother nucleus is a naphthalene ring, which has low volatility and high weighing stability. In this case, the hydroxyl group-containing cyclic compound can be, specifically, a compound having a naphthalene ring, such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. These hydroxyl group-containing cyclic compounds may be used alone or in combination of two or more.

[0162] The content of the hydroxyl group-containing cyclic compound is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, relative to 100% by mass of the total resin composition. When the content of the hydroxyl group-containing cyclic compound is within the above range, the resin composition can be sufficiently reduced in viscosity and has improved flowability. Furthermore, the content of the hydroxyl group-containing cyclic compound is preferably 2% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less, relative to 100% by mass of the total resin composition. When the content of the hydroxyl group-containing cyclic compound is within the above range, there is little risk of a decrease in the curability of the resin composition or a decrease in the physical properties of the cured product.

[0163] Furthermore, the resin composition of the present embodiment may further contain various additives, such as colorants such as carbon black; release agents such as natural waxes, synthetic waxes, higher fatty acids or metal salts thereof, paraffin, and polyethylene oxide; stress reducing agents such as silicone oils and silicone rubbers; flame retardants such as aluminum hydroxide; ion scavengers such as hydrotalcites or hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium; adhesion promoters such as thiazoline, diazole, triazole, triazine, and pyrimidine; and antioxidants.

[0164] Next, a method for producing the resin composition of this embodiment will be described. The method for producing the resin composition of this embodiment is not particularly limited, but may involve, for example, mixing the thermosetting component and any other optional components using a mixer or the like, followed by melt-heating and kneading at approximately 90 to 120°C using a heated kneader, heated roll, extruder, or the like. The resulting kneaded mixture is then cooled and pulverized to obtain a powdery or granular resin composition. If necessary, the resin composition may be compressed into tablets after pulverization, or may be formed into a sheet by, for example, vacuum lamination or compression molding after pulverization.

[0165] Alternatively, for example, the thermosetting component and other optional components may be dissolved, mixed, and stirred in a solvent using various mixers such as those employed in ultrasonic dispersion, high-pressure collision dispersion, high-speed rotation dispersion, bead mill dispersion, high-speed shear dispersion, or rotation-revolution dispersion, to prepare a varnish-like resin composition. Specific examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve-based solvents, carbitol-based solvents, anisole, and N-methylpyrrolidone. The solvents may be used alone or in combination of two or more.

[0166] 2. Structure The structure of this embodiment includes a cured product of the easily dismantlable thermosetting resin composition described above. The cured product can be obtained by thermally curing the resin composition of this embodiment at 100 to 200°C for 10 to 900 seconds. The structures can be widely applied, for example, to composite members for transportation equipment such as automobiles, railways, ships, and aircraft, semiconductor chips, semiconductor elements, and semiconductor devices equipped with printed wiring boards, composite members for factory equipment such as work robots, electronic devices such as electric circuit display devices, information and communication terminals, light-emitting diodes, physical batteries, and chemical batteries, composite members for civil engineering and construction, composite members for sports and recreation, etc. Among these, composite members for transportation equipment such as automobiles, semiconductor devices, etc. are preferred in view of the importance of addressing environmental issues. Specifically, the semiconductor device includes a semiconductor element and an encapsulant that encapsulates the semiconductor element, and the encapsulant is made of a cured product of the resin composition of the present embodiment. The encapsulation method is not particularly limited, and known methods can be used.

[0167] 3.Disassembly method The dismantling method of this embodiment is carried out by immersing the cured product of the easily dismantlable thermosetting resin composition in a solvent, which causes the crosslinks in the cured product to be cleaved and decomposed, solubilizing the cured product or causing a portion of the cured product to become solubilized or gel, allowing the product to be dismantled.

[0168] The immersion temperature of the cured product can be set appropriately depending on the application, but is preferably from -20 to 200°C, and more preferably from 0 to 150°C, for example. For ease of disassembly, the cured product may be immersed at ambient temperature, i.e., room temperature. This eliminates the need for special procedures such as cooling or heating. For example, the solvent temperature can be set to 5 to 30°C. On the other hand, in order to promote disintegration, heating or heat treatment may be added when the hardened material is immersed. The method for immersing the cured product is not particularly limited, as long as the cured product is partially or entirely in contact with the solvent. The immersion time is adjusted appropriately depending on the size of the cured product, etc. Alternatively, the solvent may be poured into a container containing the cured product, or the cured product may be immersed and stirred in the solvent in the container.

[0169] The solvent may be any solvent that liberates an -Si-O- structure from the cured product, and is preferably a solvent containing fluoride ions. The solvent containing fluoride ions may be a solvent that generates fluoride ions.

[0170] The solvent of this embodiment can be, for example, a solvent prepared as follows. (i) A solvent obtained by reacting a fluorine compound such as tetra-n-butylammonium fluoride (n-Bu4NF) with an organic solvent such as tetrahydrofuran. Examples of the fluorine compound include ammonium, organic amines, and organic ammonium fluoride salts, and specifically include one or more selected from ammonium fluoride, hydrofluoric acid, acidic ammonium fluoride, methylamine hydrofluoride, ethylamine hydrofluoride, propylamine hydrofluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, ethanolamine hydrofluoride, methylethanolamine hydrofluoride, dimethylethanolamine hydrofluoride, hydroxylamine hydrofluoride, dimethylhydroxylamine hydrofluoride, triethylenediamine hydrofluoride, etc. Among these, ammonium fluoride and tetra-n-butylammonium fluoride are preferred, and tetra-n-butylammonium fluoride is more preferred. (ii) Solvents obtained by reacting a mineral acid or a strong organic acid in an anhydrous organic solvent or a water-containing organic solvent such as acetonitrile. (iii) A solvent obtained by the action of N-bromosuccinimide (NBS) in dimethyl sulfoxide (DMSO). (iv) A solvent obtained by reacting an alkali metal hydrogen sulfate in a solvent such as water or alcohol. As the hydrogen sulfate, alkali metal salts such as lithium hydrogen sulfate, potassium hydrogen sulfate, and sodium hydrogen sulfate can be used, with potassium salts and sodium salts being preferred. (v) A solvent obtained by treating with an aqueous solution of acetic acid. (vi) A solvent obtained by reacting excess potassium fluoride dihydrate with excess tetrabutylammonium chloride in acetonitrile.

[0171] Among these solvents, it is preferable to use solvent (i) from the viewpoint of decomposition rate and waste liquid treatment.

[0172] 4.Recycling methods The recycling method of the present embodiment is a method for recycling materials constituting the above-described structure, and includes the steps of immersing the structure in a solvent and dismantling the cured product of the easily dismantlable thermosetting resin composition, and recovering the materials from the structure. This allows the materials used in the structure to be reused. The process of dismantling the hardened product is the same as the method described above in the dismantling method.

[0173] The method for recovering the material from the structure is not particularly limited as long as it does not degrade the quality of the material. For example, there is a method in which the material is precipitated in a solvent in which the cured product has been disassembled, and only the material is recovered by filtration, or a method in which the structure is removed from the solvent, and then the structure is destroyed together with the cured product, which has become brittle due to disassembly, and the material is recovered.

[0174] The material is not particularly limited as long as it is not soluble in the solvent and does not cause a chemical reaction, and examples thereof include metals.

[0175] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. [Example]

[0176] Next, the present invention will be described in detail with reference to examples, but the content of the present invention is not limited to the examples.

[0177] 1.Synthesis method Each silyl ether type phenolic resin was synthesized according to the following procedure.

[0178] [Synthesis Example 1] (Method for synthesizing silyl ether type phenol monomer) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 56.1 g of 2-allylphenol, 80 g of toluene, and 10 μL of Karstedt catalyst, and the temperature was raised to 80°C. 28.0 g of 1,1,3,3-tetramethyldisiloxane was then added dropwise. The mixture was then reacted at 80°C for 2 hours, after which the toluene was distilled off from the reaction solution. Through the above procedure, 89.3 g of silyl ether-type phenol monomer (1) represented by the following formula (S1) was obtained.

[0179] [ka]

[0180] [Synthesis Example 2] (Method for synthesizing silyl ether type novolak resin (1)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 25.0 g of the obtained silyl ether-type phenol monomer (1) and 0.11 g of oxalic acid, and the temperature was gradually raised. Then, 4.5 g of 37% formalin solution was added dropwise, and the reaction was carried out at an internal temperature of 100°C for 5 hours. The internal temperature was then raised to 120°C, and dehydration was carried out at atmospheric pressure to remove moisture. Through the above procedure, 27.4 g of silyl ether-type novolak resin (1) represented by the following formula (S2) was obtained. The silyl ether type novolak resin (1) had Mn=780, Mw=2,800, and a hydroxyl group equivalent of 237 g / eq.

[0181] [ka]

[0182] [Synthesis Example 3] (Method for synthesizing silyl ether type novolak resin (2)) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 25.0 g of silyl ether-type phenol monomer (1), 5.8 g of phenol, and 0.22 g of oxalic acid, and the temperature was gradually increased. Then, 9.0 g of 37% formalin solution was added dropwise, and the reaction was carried out at an internal temperature of 100°C for 5 hours. The internal temperature was then increased to 120°C, and dehydration was carried out at atmospheric pressure to remove moisture. Further dehydration reaction was carried out under reduced pressure, yielding 29.5 g of silyl ether-type novolak resin (2) represented by the following formula (S3). The silyl ether type novolak resin (2) had Mn=800, Mw=2,300, and a hydroxyl group equivalent of 198 g / eq.

[0183] [ka] (In formula (S3), x:y is approximately 45:55.)

[0184] 2. Preparation of Resin Composition <Comparative Examples 1 and 2 and Examples 1 to 4> Using the raw material I shown below, each component was mixed at the solid content ratio shown in Table 1 to obtain a mixture. Mixing was performed at room temperature using a Henschel mixer. The obtained mixture was then roll-kneaded at 90 to 120°C to obtain a kneaded product. The obtained kneaded product was cooled and then pulverized to obtain the resin compositions of Comparative Examples 1 and 2 and Examples 1 to 4. [Raw material I] (thermosetting resin) Epoxy resin 1: Orthocresol novolac epoxy resin (DIC Corporation, EPICRON N-670) Epoxy resin 2: BPA bisphenol A resin (Mitsubishi Chemical Corporation, YL6810) (hardening agent) Hardener 1: Novolac phenol compound (Sumitomo Bakelite Co., Ltd., PR-51470) Curing agent 2: Silyl ether type novolak resin (1) obtained in Synthesis Example 2 Curing agent 3: Silyl ether type novolak resin (2) obtained in Synthesis Example 3 (curing accelerator) Curing accelerator 1: Triphenylphosphine (Inorganic filler) Inorganic filler 1: Fused spherical silica (manufactured by Denka Co., Ltd., FB-60) (others) Colorant 1: Carbon black (Mitsubishi Chemical Corporation, Carbon #5) Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (CF-4083, manufactured by Toray Dow Corning Co., Ltd.) Release agent 1: Carnauba wax Additives: Stress reducing agents, ion scavengers and flame retardants

[0185] <Example 5> A silicone rubber-based curable composition was prepared using Raw Material II shown below. First, a mixture of silicone rubber 1 (80 parts by mass), silicone rubber 2 (20 parts by mass), coupling agent 2 (10 parts by mass), coupling agent 3 (0.5 parts by mass), and water (5.25 parts by mass) was pre-kneaded, and then inorganic filler 2 (25 parts by mass) was added to the mixture and further kneaded to obtain a kneaded product (silicone rubber compound). Here, the kneading after adding the inorganic filler 2 was carried out through a first step of kneading for 1 hour under a nitrogen atmosphere at 60 to 90°C for the coupling reaction, and a second step of kneading for 2 hours under a reduced pressure atmosphere at 160 to 180°C for the removal of the by-product (ammonia), followed by cooling and kneading for 20 minutes. Next, silicone rubber 3 and curing accelerator 2 were added to the obtained kneaded product (silicone rubber compound) in the proportions (mass%) shown in Table 1, and the mixture was kneaded with a roll to obtain the silicone rubber-based curable composition of Example 5.

[0186] [Raw material II] (Silicone rubber; organopolysiloxane (C1)) Silicone rubber 1 (low vinyl group-containing linear organopolysiloxane (C1-2'): synthesized according to synthetic scheme 1. Structure represented by formula (C1-2), in which only R1 (terminal) is a vinyl group) Silicone rubber 2 (high vinyl group-containing linear organopolysiloxane (C1-2''): synthesized according to synthetic scheme 2. Structure represented by formula (C1-2), where R1 and R2 are vinyl groups) Silicone rubber 3 (organohydrogenpolysiloxane (C2)) manufactured by Momentive: "TC-25D"

[0187] (Inorganic filler) Inorganic filler 2: Silica fine particles (particle size 7 nm, specific surface area 300 m2 / g), manufactured by Nippon Aerosil Co., Ltd., "AEROSIL300" (catalyst, curing accelerator) Curing accelerator 2: Platinum compound, manufactured by Momentive: "TC-25A" (others) Silane coupling agent 2: Hexamethyldisilazane (HMDZ), manufactured by Gelest, "HEXAMETHYLDISILAZANE (SIH6110.1)" Silane coupling agent 3: Divinyltetramethyldisilazane, manufactured by Gelest, "1,3-DIVINYLTETRAMETHYLDISILAZANE (SID4612.0)"

[0188] <Synthesis of vinyl group-containing organopolysiloxane (C1)> [Synthesis Scheme 1: Synthesis of low-vinyl-group-containing linear organopolysiloxane (C1-2')] A low-vinyl-group-containing linear organopolysiloxane (C1-2') was synthesized according to the following formula (7). Specifically, 74.7 g (252 mmol) of octamethylcyclotetrasiloxane and 0.1 g of potassium siliconate were placed in a 300 mL separable flask equipped with a condenser and stirring blade and purged with Ar gas, and the mixture was heated to 120° C. and stirred for 30 minutes. An increase in viscosity was confirmed during this time. The temperature was then raised to 155°C and stirring was continued for 3 hours, after which 0.1 g (0.6 mmol) of 1,3-divinyltetramethyldisiloxane was added and the mixture was further stirred at 155°C for 4 hours. After 4 hours, the mixture was diluted with 250 mL of toluene and washed three times with water. The washed organic layer was reprecipitated and purified by washing with 1.5 L of methanol several times, separating the oligomer and polymer. The resulting polymer was dried overnight under reduced pressure at 60°C to obtain a low-vinyl-group-containing linear organopolysiloxane (C1-2') (Mn = 2.2 × 105, Mw = 4.8 × 105). The vinyl group content calculated by H-NMR spectroscopy was 0.04 mol%.

[0189] [ka]

[0190] [Synthesis Scheme 2: Synthesis of High-Vinyl-Containing Linear Organopolysiloxane (C1-2'')] A vinyl-rich linear organopolysiloxane (C1-2'') was synthesized as shown in formula (8) below by the same procedure as for (C1-2'), except that 0.86 g (2.5 mmol) of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane was used in addition to 74.7 g (252 mmol) of octamethylcyclotetrasiloxane. (Mn = 2.3 × 10 5 , Mw = 5.0 × 10 5 ). Furthermore, the vinyl group content calculated by H-NMR spectroscopy was 0.93 mol %.

[0191] [ka]

[0192] 3. Confirmation of the structure of the cured resin composition In Comparative Examples 1 and 2 and Examples 1 to 4, the resulting resin compositions were molded at a mold temperature of 175°C for a curing time of 2 minutes to obtain cured products. In Example 5, the resulting resin composition was pressed at 160°C and 10 MPa for 20 minutes to form into a sheet and undergo primary curing, followed by heating at 200°C for 4 hours to undergo secondary curing, to obtain a sheet-like cured silicone rubber product. The following resin composition analysis was performed on each cured product using pyrolysis GC-MS. GC-MS measurements were performed using an FT-NMR device (JNM-ECA400, manufactured by JEOL Ltd.). First, the cured material was heated at 600°C for 1 minute in a helium atmosphere, and all the components generated were introduced into a GC separation column and trapped with liquid nitrogen. After heating, the trap was removed and GC-MS measurement was started immediately. The —Si—O— structure was identified based on the mass spectrum and retention time of each compound, and judged according to the following criteria. The results are shown in Table 1. (standard) OK: The -Si-O- structure was identified. N / A: The -Si-O- structure could not be identified.

[0193] 4. Evaluation of ease of disassembly Dismantling properties were evaluated using the following solvents. Solvent: Tetrabutylammonium fluoride (0.5 mol / L, THF solution) First, in Comparative Examples 1 and 2 and Examples 1 to 4, the resulting resin compositions were molded at a mold temperature of 175°C for a curing time of 2 minutes to obtain cured products (width 10 mm, thickness 4 mm, length 20 mm).In Example 5, the resulting resin composition was pressed at 160°C and 10 MPa for 20 minutes to form into a sheet and undergo primary curing, and then heated at 200°C for 4 hours to undergo secondary curing to obtain a sheet-like silicone rubber cured product (width 10 mm, thickness 4 mm, length 20 mm). Next, the obtained cured product was immersed in 25 ml of solvent in a container and left to stand at 23° C. for 24 hours. The container was then shaken for 1 minute using a shaker (approximately 200 strokes per minute), and all of the solution in the container was then filtered through a 212 μm mesh filter (JIS standard sieve 212 μm, diameter 100 mm). The success of filtration (whether the filter was clogged or not) and the residue on the filter were observed and evaluated according to the following criteria. The less the filter was clogged and the less residue there was, the more the cured product could be dissolved in a solvent and the better the dismantling properties. The results are shown in Table 1. (standard) A: The filter is not clogged and there is no or only a small amount of cured product residue on the filter. B: The filter is not clogged, but there is a noticeable amount of cured residue on the filter. C: The filter is clogged and cannot be filtered.

[0194] [Table 1]

[0195] This application claims priority based on Japanese Patent Application No. 2022-088784, filed on May 31, 2022, the disclosure of which is incorporated herein in its entirety.

Claims

1. An easily dismantlable thermosetting resin composition containing a thermosetting component, The easily dismantlable thermosetting resin composition is used in applications in which, after curing the composition, the resulting cured product is brought into contact with a solution containing fluorine ions to decompose the gel, solubilize it, and dismantle it, the thermosetting component comprises a thermosetting resin and a curing agent; the thermosetting resin contains an epoxy resin, and the epoxy resin does not have an Si—O— structure; The content of the epoxy resin is 1% by mass or more and 10.11% by mass or less, the curing agent includes a phenolic curing agent having an —Si—O— structure, The phenol-based curing agent is a silyl ether-modified novolak resin obtained by reacting a silyl ether represented by the following formula (P1-2), a phenol, and an aldehyde in the presence of an acid catalyst, and has a hydroxyl group equivalent of 198 g / eq or more and 250 g / eq or less: The easily dismantlable thermosetting resin composition is thermally cured at 175°C for 2 minutes, and the cured product obtained has a structure represented by the following formula (1): 【Chemistry 1】 (In formula (1), R １ , R ２ each independently represents a hydrogen atom, a hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. 【Chemistry 2】 (In formula (P1-2), R 9 represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Each R 10 independently represents a hydrogen atom, a monovalent hydrocarbon group or aromatic group having 1 to 30 carbon atoms, a hydroxyl group, or an alkoxyl group having 1 to 30 carbon atoms. z represents an integer of 0 to 10.)

2. The easily dismantlable thermosetting resin composition according to claim 1, an easily dismantlable thermosetting resin composition, wherein the epoxy resin comprises one or more selected from the group consisting of novolac-type epoxy resins, bisphenol-type epoxy resins, aromatic glycidylamine-type epoxy resins, hydroquinone-type epoxy resins, biphenyl-type epoxy resins, stilbene-type epoxy resins, triphenolmethane-type epoxy resins, triphenolpropane-type epoxy resins, alkyl-modified triphenolmethane-type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene-modified phenol-type epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, naphthylene ether-type epoxy resins, and aralkyl-type epoxy resins.

3. The easily dismantlable thermosetting resin composition according to claim 1 or 2, The easily dismantlable thermosetting resin composition further comprises an inorganic filler, and the content of the inorganic filler is 10 to 98 mass% based on the total amount of the easily dismantlable thermosetting resin composition.

4. The easily dismantlable thermosetting resin composition according to claim 1 or 2, The easily dismantlable thermosetting resin composition, wherein the curing agent contains a phenolic resin having a weight average molecular weight (Mw) of 500 to 10,000.

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