Cyclic organosiloxane containing imide bond and polymerizable unsaturated bond, and curable resin composition containing same

Abstract

To provide: a cyclic organosiloxane containing imide bonds and polymerizable unsaturated bonds, which affords a cured material having excellent hardness and flexural resistance; and a curable resin composition comprising the same.SOLUTION: Provided are a cyclic organosiloxane represented by the following formula (1), containing imide bonds and polymerizable unsaturated bonds; and a curable resin composition comprising the same. (In the formula, R1's are each independently a monovalent hydrocarbon group or a hydrogen atom which may be intervened with at least one selected from oxygen, nitrogen, sulfur, and phosphorus atoms; Z's are each independently a monovalent organic group which may be intervened with at least one selected from oxygen, nitrogen, sulfur, and phosphorus atoms and has an imide bond or a polymerizable unsaturated bond; n is an integer of 2-6, m is an integer of 0-4, and a sum of n and m is 4-6; and a sequence of siloxane units in parentheses may be arbitrary.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond, and a curable resin composition containing the same. [Background technology]

[0002] Materials used for electronic component encapsulants, prepregs, metal foil-clad laminates, printed wiring boards, semiconductor packages, and the like are required to have excellent mechanical properties (hardness, crack resistance, bending resistance, etc.).

[0003] The following Patent Documents 1 and 2 report curable resin compositions containing a linear dimethylpolysiloxane having maleimide bonds at both ends and a cyanate ester compound. These aim to obtain a cured product that has a good thermal expansion coefficient, hardness, and bending strength by introducing a dimethylpolysiloxane structure into the material, but there is still room for improvement in the performance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2019 / 39135 [Patent Document 2] International Publication No. 2019 / 230944 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond, which gives a cured product having excellent hardness and bending resistance, and a curable resin composition containing the same. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above object, and as a result have found that a curable resin composition containing an imide bond and a polymerizable unsaturated bond-containing cyclic organosiloxane can achieve both hardness, crack resistance, and bending resistance, and have completed the present invention.

[0007] That is, the present invention provides the following cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond, and a curable resin composition containing the same. 1. A cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond, represented by the following general formula (1): [ka] (In the formula, R 1 each independently represents a monovalent hydrocarbon group optionally interrupted by at least one atom selected from oxygen, nitrogen, sulfur and phosphorus atoms, or a hydrogen atom; Z represents , a group represented by the following formula (4): where n is an integer of 2 to 6, m is an integer of 0 to 4, and the sum of n+m is 4 to 6. The arrangement of the siloxane units in the parentheses may be arbitrary. [ka] (In the formula, the asterisk * represents a bond to a silicon atom.) 2 .The above R 1 is an alkyl group having 1 to 3 carbon atoms, said n is 2, and said m is 2. 1 The imide bond and polymerizable unsaturated bond-containing cyclic organosiloxane described above. 3 (A) The above 1 or 2 The imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane according to the present invention, (B) Cyanate ester compounds A curable resin composition comprising: 4 Further, as component (C), the above-mentioned composition containing a maleimide compound other than component (A) is used. 3 The curable resin composition described above. 5 The above composition further comprising (D) a curing catalyst. 3 or 4 The curable resin composition described above. Effect of the Invention

[0008] By incorporating the imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane of the present invention into a cured matrix, it is possible to obtain a cured product that is capable of achieving both hardness, crack resistance, and bending resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be specifically described below. The imide bond-containing cyclic organosiloxane according to the present invention is represented by the following formula (1).

[0010] [ka] (In the formula, R 1 each independently represents a monovalent hydrocarbon group or a hydrogen atom which may be interrupted by at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus atoms, each Z independently represents a monovalent organic group having an imide bond and a polymerizable unsaturated bond which may be interrupted by at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus atoms, n is an integer of 2 to 6, m is an integer of 0 to 4, and the sum of n+m is 4 to 6. The arrangement of the siloxane units in the parentheses may be arbitrary.

[0011] R 1 Specific examples of the monovalent hydrocarbon group may be linear, branched, or cyclic, but preferably have 1 to 20 carbon atoms, and include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and decyl groups; alkenyl groups such as vinyl, allyl, and butenyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups. Among these, methyl, ethyl, and propyl groups are preferred from the viewpoint of marketability of the raw material used.

[0012] A preferred specific example of the monovalent organic group having an imide bond and a polymerizable unsaturated bond for Z is a group represented by the following formula (2).

[0013] [ka] (In the formula, the asterisk * represents a bond to a silicon atom, and R 2 , R 3 each independently represents a monovalent hydrocarbon group optionally interrupted by at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus atoms, or a hydrogen atom; R 2 and R 3 may be linked to form a ring structure. a is an integer of 3 to 8, and b is an integer of 0 to 2.

[0014] More specific examples of the structure of such a monovalent organic group having an imide bond and a polymerizable unsaturated bond include groups represented by the following formulas (3) and (4), but are not limited thereto.

[0015] [ka] (In the formula, the asterisk * represents a bond to a silicon atom.)

[0016] In the above formula (1), n ​​is preferably 2 to 4, and more preferably n is 2. Meanwhile, in the above formula (1), m is preferably 0 to 2, and more preferably m is 2. These values ​​are based on the market availability of the raw material, a cyclic organosiloxane material containing a primary amino group, and in addition, when n is greater than 6, a structure with too many polymerizable functional groups in one molecule is formed, and when applied to a curable resin composition, the crosslink density becomes too high, and the crack resistance and bending resistance of the obtained cured product may decrease.

[0017] The cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond of the present invention can be obtained, for example, by subjecting a primary amino group-containing cyclic organosiloxane represented by the following formula (5) to an imidization reaction with a compound having a cyclic carboxylic anhydride group and a polymerizable carbon-carbon double bond in the same molecule.

[0018] [ka]

[0019] In the above formula (5), R 1 , n, and m are as defined above, and the arrangement of the siloxane units in the parentheses may be arbitrary. A is a monovalent organic group having a primary amino group, which may be interrupted by at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus atoms. Specific examples of A include a 3-aminopropyl group, a 6-aminohexyl group, and an 8-aminooctyl group.

[0020] The above-mentioned primary amino group-containing cyclic organosiloxane can be obtained, for example, by reacting the Si-H group of a cyclic organohydrogensiloxane with an amine having a polymerizable carbon-carbon double bond to perform hydrosilylation.

[0021] An example of the cyclic organohydrogensiloxane is one represented by the following formula (5'). [ka]

[0022] In the above formula (5'), R 1 , n, and m are as defined above, and the arrangement of the siloxane units in the parentheses may be arbitrary.

[0023] Specific examples of such cyclic organohydrogensiloxanes include 1,3,5,7-tetramethyl-1,3-dipropylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,5-dipropylcyclotetrasiloxane, and 1,3,5,7-tetramethylcyclotetrasiloxane.

[0024] Specific examples of the amine having the polymerizable carbon-carbon double bond include allylamine, 5-hexenylamine, and 7-octenylamine, and at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus may be present in the hydrocarbon portion of these amines.

[0025] The hydrosilylation is usually carried out in the presence of a catalyst.The catalyst can be a known platinum group metal catalyst, such as platinum, palladium and rhodium, and platinum is preferred.The platinum metal catalyst can be platinum black; alumina, silica or other carriers carrying solid platinum; chloroplatinic acid, alcohol-modified chloroplatinic acid, complex of chloroplatinic acid and olefin; complex of platinum and vinylsiloxane, etc.

[0026] The temperature of the hydrosilylation reaction may usually be room temperature to 200° C., preferably in the range of 30 to 120° C. The reaction time can be appropriately determined depending on the production scale and the reaction temperature. In the reaction, a solvent may not be used, or a solvent may be used as necessary within a range that does not adversely affect the reaction.

[0027] On the other hand, the compound having a cyclic carboxylic acid anhydride group and a polymerizable carbon-carbon double bond in the same molecule is not particularly limited, but from the viewpoint of marketability, preferred examples thereof include maleic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0028] Regarding the reaction ratio of the substrates, from the viewpoint of productivity, it is preferable that the amount of the acid anhydride group in the compound having a cyclic carboxylic acid anhydride group and a polymerizable carbon-carbon double bond in the same molecule is 0.8 to 1.5 moles per mole of the primary amino group in the primary amino group-containing cyclic organosiloxane.

[0029] The reaction time of the imidization reaction may be any time that allows the raw materials to be sufficiently consumed as the reaction proceeds, and is preferably 10 minutes to 24 hours, more preferably 1 to 10 hours, and even more preferably 2 to 7 hours, from the viewpoint of production efficiency. The reaction temperature is preferably low, as long as the desired reaction proceeds and the productivity is not impaired.

[0030] In the above imidization reaction process, an organic solvent, a catalyst, or a dehydrating agent may be used as necessary.

[0031] The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve the raw material sufficiently without reacting with the raw material, but examples thereof include aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl 2-imidazolidinone, and N-methylpyrrolidone; sulfones such as tetramethylene sulfone; ether solvents such as tetrahydrofuran, 4-methyltetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether monoacetate, and cyclopentyl methyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene. Among these, ether solvents and aprotic polar solvents are preferred from the viewpoints of reactivity and solubility. The organic solvents can be used alone or in a suitable mixture of two or more.

[0032] The catalyst is not particularly limited, but includes organometallic salts such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; metal chlorides such as zinc chloride, aluminum chloride, and tin chloride; and tertiary amine compounds. Among these, from the viewpoint of reactivity, cobalt naphthenate is preferred in the case of thermal imidization without using a dehydrating agent, and a tertiary amine is preferred in the case of chemical imidization with a dehydrating agent described below. The catalyst can be used alone or in a suitable mixture of two or more types.

[0033] The chemical imidization using a dehydrating agent has an advantage that the reaction temperature of the imidization reaction can be lowered compared to thermal imidization. Examples of the dehydrating agent include carboxylic anhydrides, specifically acetic anhydride, propionic anhydride, succinic anhydride, etc., but are not limited thereto. In addition, when using a carboxylic anhydride, it is preferable to use a tertiary amine in an equimolar amount with the carboxylic anhydride. The tertiary amine is not particularly limited, but triethylamine is preferable from the viewpoint of marketability and ease of removal in a subsequent process.

[0034] From the viewpoint of productivity, the amount of the dehydrating agent used in the chemical imidization is preferably 1 to 2 moles, and more preferably 1.2 to 1.6 moles, per mole of primary amino groups in the primary amino group-containing cyclic organosiloxane.

[0035] The weight average molecular weight of the cyclic organosiloxane containing imide bonds and polymerizable unsaturated bonds of the present invention is not particularly limited, but in consideration of imparting sufficient hardness and flex resistance to the cured product obtained by curing a curable resin composition containing the compound, the weight average molecular weight is preferably 500 to 5,000, more preferably 600 to 3,000. Note that the weight average molecular weight in the present invention is a standard polystyrene-equivalent value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a developing solvent.

[0036] The functional group equivalent of the polymerizable unsaturated bond-containing group of the imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane of the present invention is not particularly limited, but is preferably 200 to 500 g / mol in consideration of imparting sufficient hardness and flex resistance to the cured product obtained by curing the curable resin composition containing the compound.

[0037] The curable resin composition of the present invention comprises the following components (A) and (B): (A) a cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond, and (B) Cyanate ester compounds It includes.

[0038] The (A) imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane contained in the curable resin composition of the present invention is the same as the above-mentioned imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane. The content of the imide bond- and polymerizable unsaturated bond-containing cyclic organosiloxane of the (A) component can be appropriately set according to the desired properties and is not particularly limited, but from the viewpoint of further improving the balance of physical properties of bending strength, heat resistance, and dielectric properties, it is preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 5 to 15 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

[0039] The (B) cyanate ester compound contained in the curable resin composition of the present invention is not particularly limited as long as it is a compound having at least one cyanato group (cyanate ester group), but an aromatic cyanate ester compound is preferred. The curable resin composition using the cyanate ester compound as in the present invention has excellent properties such as heat resistance and low thermal expansion when cured.

[0040] Specific examples of the aromatic cyanate ester compound include cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4-, or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatononylbenzene, 2-(4-cyanatophenyl) ... 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene, cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanato-3-trimethylphenylbenzene, 1-cyanato-4-cyclohexylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-2-methyl-3-chloro ...phenylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene, 1-cyanato-4-vinylbenzene Fluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4-cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6-di-tert-butylbenzene, 1,2-dicyanatobenzene, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethyl Benzene, 1,4-dicyanato-2,3,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyanato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyanato-1,1'-binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatosinaphthalene, 2,2'- or 4,4'-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanatophenyl)ethane, 1,1-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(4-cyanato-3-methylphenyl)propane, 2,2-bis(2-cyanato-5-biphenylyl)propane, 2,2-bis(4-cyanatophenyl)hexafluoropropane, 2,2-bis(4- cyanato-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanatophenyl)butane, 1,1-bis(4-cyanatophenyl)isobutane, 1,1-bis(4-cyanatophenyl)pentane, 1,1-bis(4-cyanatophenyl)-3-methylbutane, 1,1-bis(4-cyanatophenyl)-2-methylbutane, 1,1-bis(4-cyanatophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanatophenyl)butane, 2,2-bis(4-cyanatophenyl)pentane, 2,2-bis(4-cyanatophenyl) 2,2-bis(4-cyanatophenyl)-3-methylbutane, 2,2-bis(4-cyanatophenyl)-4-methylpentane, 2,2-bis(4-cyanatophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanatophenyl)hexane, 3,3-bis(4-cyanatophenyl)heptane, 3,3-bis(4-cyanatophenyl)octane, 3,3-bis(4-cyanatophenyl)-2-methylpentane, 3,3-bis(4-cyanatophenyl)-2-methylhexane, 3,3-bis(4-cyanatophenyl) 3,3-bis(4-cyanatophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanatophenyl)-3-methylheptane, 3,3-bis(4-cyanatophenyl)-2-methylheptane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,4-dimethylhexane, 3,3-bis(4-cyanatophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanatophenyl)phenylmethane, 1,1-bis(4-cyanatophenyl)-1-phenylethane, bis(4-cyanatophenyl)biphenylmethane, 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis(4-cyanatophenyl)cyclohexane, 2,2-bis(4-cyanato-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanatophenyl)cyclohexane, bis(4-cyanatophenyl)diphenylmethane, bis(4-cyanatophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanatophenyl)-2-propyl ]benzene, 1,4-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanatophenyl)methyl]biphenyl, 4,4-dicyanatobenzophenone, 1,3-bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)sulfide, bis(4-cyanatophenyl)sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-methylphenyl). -cyanatobenzoate), bis-(4-cyanatophenyl)carbonate, 1,3-bis(4-cyanatophenyl)adamantane, 1,3-bis(4-cyanatophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanatophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyanato-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate of o-cresolphthalein), 9,9'-bis(4-cyanatophenyl)fluorene, 9,9-bis(4-cyanato- 3-methylphenyl)fluorene, 9,9-bis(2-cyanato-5-biphenylyl)fluorene, tris(4-cyanatophenyl)methane, 1,1,1-tris(4-cyanatophenyl)ethane, 1,1,3-tris(4-cyanatophenyl)propane, α,α,α'-tris(4-cyanatophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4-cyanatophenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N-methyl-4-cyanatoanilino)-1,3,5-triazine, 2,4-Bis(N-methyl-4-cyanatoanilino)-6-(N-methylanilino)-1,3,5-triazine, bis(N-4-cyanato-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanato-4-methylphenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)diphthalimide, tris(3, 5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis(4-cyanatophenyl)phthalimidine, 2-(4-methylphenyl)-3,3-bis(4-cyanatophenyl)phthalimidine, 2-phenyl-3,3-bis(4-cyanato-3-methylphenyl)phthalimidine, 1-methyl-3,3-bis(4-cyanatophenyl)indolin-2-one, and 2-phenyl-3,3-bis(4-cyanatophenyl)indolin-2-one.

[0041] The content of the cyanate ester compound of the component (B) can be appropriately set depending on the desired properties and is not particularly limited, but from the viewpoint of further improving the balance of physical properties including bending strength, dielectric properties, heat resistance, thermal expansion coefficient and thermal conductivity, the content is preferably 1 to 99 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 25 to 70 parts by mass, relative to 100 parts by mass of the solid content in the resin composition.

[0042] The curable resin composition of the present invention may further contain, as necessary, a maleimide compound other than the component (A) as the component (C) and a curing catalyst as the component (D).

[0043] The maleimide compound of the component (C) may be a compound having two or more maleimide bonds in the molecule, which is generally distributed as a bismaleimide resin. For example, a co-condensation product of a bismaleimide and an aldehyde compound may be mentioned, and one or more of these may be used. The bismaleimide may be, for example, 4,4'-diphenylmethane bismaleimide, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, N,N'- Examples of such bismaleimide include p,p'-diphenyldimethylsilyl bismaleimide, N,N'-4,4'-diphenylether bismaleimide, N,N'-methylenebis(3-chloro-p-phenylene) bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-dimethylenecyclohexane bismaleimide, N,N'-m-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide, and N-phenylmaleimide. Examples of the aldehyde compound include formaldehyde, acetaldehyde, benzaldehyde, and hydroxyphenylaldehyde.

[0044] Examples of the curing catalyst for the component (D) include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-methylimidazole; tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, and 1,8-diazabicyclo[5.4.0]undecene-7; triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine·triphenylborate, and tetraphenylphosphine·tetraphenylphosphine. Examples of the organic phosphorus compounds include organophosphonium compounds such as triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, tris(dimethoxyphenyl)phosphine, etc.; phosphonium salts obtained by reacting organophosphonium compounds such as triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, tris(dimethoxyphenyl)phosphine, etc. with hydrogen halides or alkyl halides; organometallic compounds such as aluminum and zirconium; and heterocyclic amine compounds, boron complex compounds, organic ammonium salts, organic sulfonium salts, and organic peroxides. One or more of these can be used. Among these, tetraphenylphosphonium tetra-p-tolylborate is preferred from the viewpoint of further promoting curing.

[0045] The content of the curing catalyst of the above component (D) is not limited as long as it satisfies the desired curing speed, cured physical properties, and appropriate pot life of the composition. In general, however, it is preferably 0.1 to 5 parts by mass per 100 parts by mass of the resin solid content in the resin composition. 。

[0046] The curable resin composition of the present invention may contain an organic solvent as necessary. In this case, at least a part, preferably all, of the various resin components described above may be used in an embodiment in which they are dissolved or compatible with the organic solvent (solution or varnish). The organic solvent may be used alone or in a suitable mixture of two or more kinds.

[0047] As the organic solvent, any known organic solvent can be appropriately used as long as it can dissolve or be compatible with at least a part, preferably all, of the various resin components described above, and the type is not particularly limited.Specific examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester-based solvents such as methyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; polar solvents such as amides such as N-methylpyrrolidinone, dimethylacetamide, and dimethylformamide; and non-polar solvents such as aromatic hydrocarbons such as toluene and xylene.Among these, N-methylpyrrolidinone is preferred from the viewpoint of dissolving power, and methyl ethyl ketone is preferred from the viewpoint of balance with drying property.

[0048] [Method for producing curable resin composition] The curable resin composition of the present invention can be appropriately prepared according to a conventional method, and the preparation method is not particularly limited as long as it is a method that can obtain a curable resin composition that uniformly contains the (A) imide bond and polymerizable unsaturated bond-containing cyclic organosiloxane, the (B) cyanate ester compound, and the other components described above.For example, the curable resin composition of the present embodiment can be easily prepared by sequentially mixing the (A) component, the (B) component, and the other components in an organic solvent and thoroughly stirring them.

[0049] The set temperature for heat-curing the curable resin composition of the present invention is not particularly limited as long as the desired physical properties of the cured product can be expressed, but from the viewpoints of the volatility of the organic solvent and production efficiency, it is preferably 100 to 250° C., more preferably 150 to 200° C. The curing time can be appropriately set.

[0050] The method for producing the cured product of the curable resin composition of the present invention is not particularly limited, and any known production method can be used. For example, a method using a mold, or a film formation method using a casting method in which the composition is coated on a film previously provided with a release layer and cured, etc., can be mentioned, but are not limited to these.

[0051] The material of the mold is not particularly limited as long as it ensures releasability from the cured product obtained after curing. For example, any of metal, glass, plastic, silicone, etc. may be used, but it is preferable to use a mold processed with Teflon (registered trademark). Such a mold processed with Teflon (registered trademark) has excellent releasability, and by using this mold, it is possible to suppress the occurrence of damage to the cured product when removing the cured product of the curable resin composition of the present invention.

[0052] The cured product of the curable resin composition of the present invention can be suitably used as a constituent material for electronic component sealants, prepregs, metal foil-clad laminates, printed wiring boards, and semiconductor packages. For example, a prepreg can be obtained by impregnating or applying the curable resin composition of the present invention to a substrate and drying it. Here, the drying conditions can be, for example, a temperature of 20 to 150 for 1 to 90 minutes. Furthermore, a build-up film or a dry film solder resist can be obtained by using a peelable plastic film as a substrate and applying the curable resin composition of the present invention to the plastic film and drying it. Furthermore, the curable resin composition of the present invention can be used in an uncured state after the organic solvent has been simply dried, or can be used in a semi-cured (B-stage) state as necessary. EXAMPLES

[0053] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively. The viscosity is the value at 25°C using a rotational viscometer, and the kinetic viscosity is the value at 25°C using a Cannon-Fenske viscometer. GPC measurement and proton nuclear magnetic resonance ( 1 The conditions for H-NMR spectroscopy were as follows:

[0054] (1) GPC measurement conditions Equipment: Tosoh Corporation HLC-8320GPC Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N(6.0mmI.D.×15cm×1) TSKgel SuperH2500(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (2.0% by mass in THF solution) Standard: Monodisperse polystyrene

[0055] (2) Proton nuclear magnetic resonance spectrum ( 1 H-NMR) measurement conditions Equipment: BURKER AVANCE III400 Solvent: CDCl3 Internal standard: tetramethylsilane (TMS)

[0056] [1] Synthesis of cyclic organosiloxanes containing primary amino groups [Synthesis Example 1] 240g (4.2 mol) of allylamine was added to a 2L three-neck flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, and heated to 80°C using an oil bath. A toluene solution of platinum complex (1,3-divinyltetramethyldisiloxane complex of Pt(0)) was added to this in an amount equivalent to 0.0001 mol of platinum complex per 1 mol of Si-H group of the cyclic organohydrogensiloxane to be dropped, and mixed with stirring. 650g (2.01 mol) of a mixture of 1,3,5,7-tetramethyl-1,3-dipropylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,5-dipropylcyclotetrasiloxane was dropped into this as the cyclic organohydrogensiloxane to be dropped. The temperature of the reaction liquid rose due to the dropping reaction, and the temperature was controlled by air cooling or water cooling so that the reaction proceeded in the range of 80 to 90°C. After the dropwise addition was completed, the mixture was heated and stirred at 80°C for 4 hours, and the disappearance of the reaction raw materials and the production of the target amino group-containing cyclic organosiloxane were confirmed by gas chromatography. The mixture was then cooled to room temperature, and the unreacted allylamine and toluene derived from the platinum catalyst were distilled off under reduced pressure to obtain a yellow, transparent liquid (A1). The kinetic viscosity of A1 at 25°C was 33mm 2 / s, and the functional amount of primary amino groups was 253 g / mol. 1 1 H-NMR and GPC analyses confirmed that the above A1 was a mixture of a compound represented by the following formula (6) and a compound represented by the following formula (7).

[0057] [ka]

[0058] [Synthesis Example 2] The same procedure was carried out as in Synthesis Example 1 above, except that the mixture of 1,3,5,7-tetramethyl-1,3-dipropylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,5-dipropylcyclotetrasiloxane was replaced with 1,3,5,7-tetramethylcyclotetrasiloxane (1.0 mol), to obtain a brown, transparent liquid (A2). The kinetic viscosity of A2 at 25°C was 41 mm 2 / s, and the functional group amount of the primary amino group was 125 g / mol. 1 By 1 H-NMR and GPC analysis, it was confirmed that the above A2 was a compound represented by the following formula (8).

[0059] [ka]

[0060] [2] Synthesis of cyclic organosiloxane compounds containing imide bonds and polymerizable unsaturated bonds [Example 1] In a 1L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 98.1 parts by mass (1 mole) of maleic anhydride, 300 parts by mass of tetrahydrofuran, and 0.4 parts by mass of bis-t-butylphenol as a polymerization inhibitor were placed and mixed under stirring. After each component was uniformly dissolved, 253 parts by mass (1 mole as amino group) of the amino group-containing cyclic organosiloxane (A1) was dropped. Heat was generated by the dropping reaction, and the temperature of the reaction liquid was controlled using a water bath so that the temperature did not exceed 50°C. After the dropping was completed, stirring was continued at room temperature for 1 hour, and the disappearance of the reaction raw materials was confirmed by GPC. Next, 150 parts by mass (1.5 moles) of acetic anhydride was added thereto and stirred, and then 150 parts by mass (1.5 moles) of triethylamine was dropped therein. As the dropping occurred, slight heat was generated and the appearance changed from orange to deep red. After the dropwise addition was completed, the reaction was carried out at an internal temperature of 50°C for 3 hours, and GPC confirmed the disappearance of the peak derived from the amic acid structural component formed in the middle, and the appearance of a new peak corresponding to a cyclic organosiloxane containing an imide bond. Finally, the unreacted acid anhydride, amine, and tetrahydrofuran were distilled off under reduced pressure to obtain a black oily compound (M1). The viscosity of this compound at 25°C was 10,320 mPa s. 1 H-NMR and GPC analyses confirmed that M1 was a mixture of a compound represented by the following formula (9) and a compound represented by the following formula (10).

[0061] [ka]

[0062] [Example 2] The same procedure as in Example 1 was carried out except that A1 was replaced with A2 (1 mol as amino group), to obtain a black oily compound (M2). The viscosity of this compound at 25°C was 105,000 mPa s. 1 H-NMR and GPC analyses confirmed that M2 was a compound represented by the following formula (11).

[0063] [ka]

[0064] [Example 3] The same procedure as in Example 1 was repeated except that maleic anhydride was replaced with 5-norbornene-2,3-dicarboxylic anhydride (1 mol), to obtain a black oily compound (M3). The viscosity of this compound at 25°C was 52,000 mPa s. 1 H-NMR and GPC analyses confirmed that M3 was a mixture of a compound represented by the following formula (12) and a compound represented by the following formula (13).

[0065] [ka]

[0066] [Comparative Synthesis Example 1] The same procedure was carried out as in Example 1 above, except that A1 was changed to polydimethylsiloxane having a primary amino group amount of 270 g / mol and an aminopropyldimethylsilyl structure at both ends (1 mol as amino groups), to obtain a black oily compound (MR-1). The viscosity of MR-1 at 25°C was 6,320 mPa s. 1 H-NMR and GPC analyses confirmed that MR-1 was a mixture of polysiloxanes represented by the following formula (14).

[0067] [ka]

[0068] [Comparative Synthesis Example 2] The same procedure was carried out as in Example 1 above, except that A1 was changed to polydimethylsiloxane having a primary amino group amount of 430 g / mol and an aminopropyldimethylsilyl structure at both ends (1 mol as amino groups), to obtain a black oily compound (MR-2). The viscosity of MR-2 at 25°C was 2,100 mPa s. 1 H-NMR and GPC analyses confirmed that MR-2 was a mixture of polysiloxanes represented by the following formula (15).

[0069] [ka]

[0070] [Comparative Synthesis Example 3] The same procedure was carried out as in Example 1 above, except that A1 was changed to polydimethylsiloxane having a primary amino group amount of 780 g / mol and an aminopropyldimethylsilyl structure at both ends (1 mol as amino groups), to obtain a black oily compound (MR-3). The viscosity of MR-3 at 25°C was 1,000 mPa s. 1 H-NMR and GPC analyses confirmed that MR-3 was a mixture of polysiloxanes represented by the following formula (16).

[0071] [ka]

[0072] [Comparative Synthesis Example 4] The same procedure was carried out as in Example 1 above, except that A1 was changed to polydimethylsiloxane having a primary amino group amount of 2,130 g / mol and an aminopropyldimethylsilyl structure at both ends (1 mol as amino groups), to obtain a black oily compound (MR-4). The viscosity of MR-4 at 25°C was 150 mPa s. 1 H-NMR and GPC analyses confirmed that MR-4 was a mixture of polysiloxanes represented by the following formula (17).

[0073] [ka]

[0074] [3] Production of curable resin composition [Examples 4 to 5, Comparative Examples 1 to 7] As shown in Table 1 below, the components were mixed in a compounding ratio (mass ratio) in which the molar ratio of the imide bond to the cyanate group was 1:3 and the molar ratio of the imide bond to the curing catalyst was 1:0.03, and the mixture was diluted with N-methylpyrrolidinone (NMP) so that the total amount of the components was 35 mass% of the entire composition, to prepare a thermosetting resin composition.

[0075] [Table 1]

[0076] The abbreviations in Table 1 are as follows. "MR-0": A disiloxane having two maleimide bonds represented by the following formula, synthesized in accordance with "Synthesis Example 2" described in WO 2019 / 39135. "BMI-70": An aromatic compound having two maleimide bonds represented by the following formula (manufactured by K.I. Kasei Co., Ltd., product name "BMI-70") "LECY": 2,2-bis(4-cyanatophenyl)ethane represented by the following formula (manufactured by Lonza Japan, product name "Primaset (registered trademark) LECy") "Curing catalyst": Tetraphenylphosphonium tetraphenylborate (manufactured by Hokko Chemical Industry Co., Ltd., "TPP-K")

[0077] [ka]

[0078] The thermosetting resin composition in Table 1 was poured into a Teflon (registered trademark)-coated mold (depth 0.3 mm × length 15 cm × width 10 cm), and the mold was then placed on a hot plate heated to 200° C. to volatilize the organic solvent N-methylpyrrolidinone (NMP) for 90 minutes at 200° C. The mold was then heated in a dryer at 150° C. for 60 minutes, and further heated in a dryer at 200° C. for 60 minutes to complete the curing, and a sheet molded product was obtained.

[0079] The following evaluations were carried out on the sheet molded products obtained in the above Examples 4 to 8 and Comparative Examples 1 to 7. The results are shown in Table 2. (1) Appearance The sheet molding (test piece) obtained above was visually observed to judge the presence or absence of abnormalities. ○: No abnormalities ×: Abnormalities such as tack, spots, cracks, etc. (2) Formability When the sheet was removed from the mold, it was observed whether it could stand on its own and was judged as follows: ○: It is possible to remove the sheet without any abnormalities. ×: Brittle or soft and impossible to take out as a sheet. (3) Bending resistance The test pieces obtained above were cut to a width of 1 cm, and cut into strips 10 cm long, 1 cm wide, and 0.3 mm thick. Both short sides were picked up with tweezers and folded at 90°. The condition of the sheet was observed and judged as follows: ◯: It can be bent without breaking. △: Some cracks occurred but no fracture. ×: Completely broken and unable to be bent. (4) Storage modulus, Tan δ(max) The test pieces obtained above were cut to a width of 1 cm and made into strips 10 cm long, 1 cm wide, and 0.3 mm thick. Using a viscoelasticity measuring device DMA7100 manufactured by Hitachi High-Tech Science Corporation, the temperature was raised from -50°C to 300°C at a heating rate of 10°C / min in an air atmosphere, and measurements were made in the tensile measurement mode. (5) Durometer hardness The measurement was performed in accordance with JIS K7215 using a TECLOCK hardness tester type D indenter.

[0080] [Table 2]

[0081] As shown in Table 2, the sheets obtained in Examples 4 to 8 were excellent in formability, folding resistance, storage modulus, and durometer hardness.

[0082] On the other hand, the resin composition of Comparative Example 1 did not contain siloxane-based maleimide, and the crosslink density of the sheet was high, so the bending resistance of the obtained test piece was insufficient. The resin composition of Comparative Example 2 had a siloxane structure, which was disiloxane, and did not contribute to the expected improvement in bending resistance, and as a result, the bending resistance was at the same level as that of Comparative Example 1. The resin composition of Comparative Example 3 exhibited bending resistance derived from the linear dimethylpolysiloxane structure, but the hardness was reduced. In relation to Comparative Example 3, the resin composition of Comparative Example 7 used aromatic maleimide in combination, but the test piece was found to be non-uniform due to the lack of compatibility between the siloxane component and the aromatic component due to the volatilization of the organic solvent during molding, and as a result, the appearance and bending resistance were deteriorated. In the resin compositions of Comparative Examples 4 to 6, the compatibility between the blended polysiloxane component and the cyanate component was poor, and a uniform sheet molding was not obtained, and the cured component was of a quality in which tack remained.

[0083] As shown in Table 2, the cured product using the cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond of the present invention has both the desired hardness and excellent bending resistance and can be suitably used as a sealing material for electronic components, a prepreg, a metal foil-clad laminate, a printed wiring board, and a constituent material for semiconductor packages, etc.

[0084] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention.

Claims

1. A cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond, represented by the following general formula (1): 【Chemistry 1】 (In the formula, R 1 each independently represents a monovalent hydrocarbon group or a hydrogen atom which may be interrupted by at least one atom selected from oxygen, nitrogen, sulfur, and phosphorus atoms, Z is a group represented by the following formula (4), n is an integer of 2 to 6, m is an integer of 0 to 4, and the sum of n+m is 4 to 6. The arrangement of the siloxane units in the parentheses may be arbitrary. 【Chemistry 2】 (In the formula, the asterisk * represents a bond to a silicon atom.)

2. The R 1 2. The cyclic organosiloxane having an imide bond and a polymerizable unsaturated bond according to claim 1, wherein: is an alkyl group having 1 to 3 carbon atoms; said n is 2; and said m is 2.

3. (A) the cyclic organosiloxane containing an imide bond and a polymerizable unsaturated bond according to claim 1 or 2, and (B) Cyanate ester compound A curable resin composition comprising:

4. The curable resin composition according to claim 3, further comprising a maleimide compound other than the component (A) as the component (C).

5. The curable resin composition according to claim 3 or 4, further comprising (D) a curing catalyst.

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