Organosilicon additives for resin modification and curable resin compositions containing the same.

Abstract

This invention provides an organosilicon additive for resin modification and a curable resin composition comprising the same, wherein the organosilicon additive for resin modification comprises: an organopolysiloxane (I) containing maleimide groups represented by formula (1) below and an organopolysiloxane (II) containing maleimide groups represented by formula (2) below, (in formula (1), R... 1 Independently representing monovalent hydrocarbon groups with 1 to 12 carbon atoms, all R 1 The proportion of methyl groups is 50 mol% or more, R 2 Independently representing an alkyl group with 1 to 5 hydrogen atoms or carbon atoms, where n represents an integer from 4 to 20. ; (in formula (2), R 1 R 2 , n is the same as above. ) Relative to the total amount of components (I) and (II) above, 100 mol%, the content of component (II) above is 10 mol% to 90 mol%. The object of the present invention is to provide a silicone additive for modifying resins that simultaneously imparts excellent flexibility, heat resistance and dielectric properties, and a curable resin composition using the same.

Description

Technical Field

[0001] This invention relates to organosilicon additives for resin modification and curable resin compositions comprising the same. Background Technology

[0002] In recent years, the integration and miniaturization of semiconductors, widely used in electronic devices, communication devices, personal computers, and other applications, have been accelerating. Along with this, the requirements for the properties of semiconductor packaging laminates used in printed circuit boards have become increasingly stringent. Examples of these required properties include flexibility, heat resistance (glass transition temperature (Tg)), and dielectric properties.

[0003] The insulating layer of printed wiring boards typically uses curable resin compositions containing epoxy resin, phenoxy resin, polyvinyl acetal resin, maleimide resin, polyphenylene ether resin, etc. (Patent Documents 1-4). However, these curable resins have the problem of internal stress accumulation caused by the reduction of free volume during curing. Therefore, if a curable resin is used as the insulating material of a printed wiring board, cracks and warping may sometimes occur in the molded product due to curing shrinkage. In addition, the reliability of the printed wiring board may sometimes be reduced due to the accumulation of internal strain. Therefore, a curable resin composition with low internal stress accumulation and low crack formation during curing is required. At this time, a balance with heat resistance and dielectric properties also becomes important.

[0004] For example, a curable resin composition has been reported in which a material having maleimide groups at both ends of a linear oligomeric siloxane is added to a bismaleimide-triazine resin (hereinafter referred to as BT resin) (Patent Documents 5 and 6). This aims to achieve a balance between the flexibility, heat resistance, and dielectric properties of the cured resin obtained by introducing silicone chains. However, since the silicone chains are short-chain, the effect of imparting flexibility from the silicone is insufficient, and there is still room for improvement in the balance of physical properties.

[0005] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2007-254709 Patent Document 2: Japanese Patent Application Publication No. 2007-254710 Patent Document 3: Japanese Patent Application Publication No. 2018-44065 Patent Document 4: Japanese Patent Application Publication No. 2019-1965 Patent Document 5: International Publication No. 2019 / 39135 Patent Document 6: International Publication No. 2019 / 230944 Summary of the Invention

[0006] The technical problem that the invention aims to solve The present invention was made in view of the above circumstances, and its object is to provide a silicone additive for resin modification that simultaneously imparts excellent flexibility, heat resistance and dielectric properties, and a curable resin composition using the same.

[0007] Technical solutions for solving technical problems In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and found that if an organosiloxane (I) containing maleimide group (represented by formula (1) and organosiloxane (II) containing maleimide group (represented by formula (2)) is used as a silicone additive for resin modification, the resulting curable resin composition can be molded into a uniform sheet and achieves a high level of flexibility, heat resistance and dielectric properties, thereby completing the present invention.

[0008] That is, the present invention provides the following silicone additive for resin modification and a curable resin composition comprising the thereof.

[0009] 1. A silicone additive for resin modification is characterized by containing: The maleimide-containing organopolysiloxane (I) is represented by the following formula (1). [Chemistry 1]

[0010] (In equation (1), R) 1 Independently representing monovalent hydrocarbon groups with 1 to 12 carbon atoms, all R 1 The proportion of methyl groups is 50 mol% or more, R 2 Independently representing an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, where n represents an integer from 4 to 20. The maleimide-containing organopolysiloxane (II) represented by the following formula (2) [Chemistry 2]

[0011] (In equation (2), R) 1 R 2 , n is the same as above. The content of component (II) is 10 mol% to 90 mol% relative to the total amount of components (I) and (II) above.

[0012] 2. The organosilicon additive for resin modification according to claim 1 above, wherein the R 1 It is a methyl group.

[0013] 3. The organosilicon additive for resin modification according to 1 or 2 above, wherein the R 2 It consists entirely of hydrogen atoms.

[0014] 4. A curable resin composition characterized by comprising: (A) Organosilicon resin component, which contains: The maleimide-containing organopolysiloxane (I) is represented by the following formula (1). [Chemistry 3]

[0015] (In equation (1), R) 1 Independently representing monovalent hydrocarbon groups with 1 to 12 carbon atoms, all R 1 The proportion of methyl groups is 50 mol% or more, R 2 Independently representing an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, where n represents an integer from 4 to 20. The maleimide-containing organopolysiloxane (II) represented by the following formula (2) [Chemistry 4]

[0016] (In equation (2), R) 1 R 2 , n is the same as above. The content of component (II) is 10 mol% to 90 mol% relative to the total amount of components (I) and (II) above. (B) Aromatic cyanate compounds having one or more cyanate groups in one molecule; and (C) A maleimide compound having two or more maleimide groups in one molecule and no siloxane bond.

[0017] 5. The curable resin composition according to 4 above, wherein the R 1 It is a methyl group.

[0018] 6. The curable resin composition according to claim 4 above, wherein the R 2 It consists entirely of hydrogen atoms.

[0019] 7. The curable resin composition according to any one of 4 to 6 above, wherein the curable resin composition further comprises a curing catalyst (D).

[0020] 8. The curable resin composition according to 4 above, wherein the content of component (A) is 1 to 25 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0021] Invention Effects By using the organosilicon additive of the present invention, which contains an organopolysiloxane containing a maleimide group, to modify a resin composition, the curable resin composition can be endowed with excellent flexibility, heat resistance, and dielectric properties. Detailed Implementation

[0022] The present invention will now be described in detail.

[0023] The organosilicon additives for resin modification involved in this invention comprise organopolysiloxanes containing maleimide groups as represented by the following formula (1).

[0024] [Chemistry 5]

[0025] In formula (1) above, n represents an integer from 4 to 20. For compatibility reasons, n is preferably 4 to 15, and more preferably 4 to 10. The above-mentioned maleimide-containing organopolysiloxanes can be used in the form of a single compound or in the form of a mixture with different n groups.

[0026] In the above formula (1), R 1 Independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms. As R 1 Examples include alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and biphenyl; and aralkyl groups such as benzyl and phenethyl. Alternatively, the hydrocarbon group may be one in which some or all of these hydrocarbon groups are substituted with halogen atoms such as chlorine or fluorine. Preferably, methyl, ethyl, phenyl, or benzyl is used; more preferably, methyl or phenyl is used; and even more preferably, methyl is used.

[0027] In addition, all R 1 In this mixture, the proportion of methyl groups needs to be 50 mol% or more, preferably 65 mol% or more, more preferably 70 mol% or more, and even more preferably 100 mol%, i.e., all of them are methyl groups. It should be noted that in this invention, when the above-mentioned maleimide-containing organopolysiloxanes are mixtures of different n groups, the proportion of methyl groups in the maleimide-containing organopolysiloxanes contained in the mixture is preferably all within the above-mentioned range.

[0028] In the above formula (1), R 2 Independently represents an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. As R 2 Examples include methyl, ethyl, propyl, butyl, pentyl, etc. Preferably, it is a hydrogen atom, methyl, or ethyl; more preferably, it is a hydrogen atom or methyl; and even more preferably, it is a hydrogen atom.

[0029] The aforementioned maleimide-containing organopolysiloxanes can be manufactured, for example, by the following methods, without particular limitation.

[0030] One manufacturing method involves mixing an acid anhydride compound and an organopolysiloxane containing primary amino groups at both ends in an organic solvent capable of dissolving these raw materials, thereby carrying out an imidization reaction. During the reaction, catalysts and dehydrating agents may be used as needed. The reaction is preferably carried out at low temperatures, provided the desired reaction is achieved without compromising productivity.

[0031] As an organic solvent, there are no particular limitations on any liquid organic compound that does not react with the raw materials and can be fully dissolved. Examples include: aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolinone, 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. From the viewpoint of reactivity and solubility, ether solvents and aprotic polar solvents are preferred. One organic solvent can be used alone or in appropriate mixtures of two or more.

[0032] As catalysts, there are no particular limitations, but examples include: organometallic salts such as tin octoate, zinc octoate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; metal chlorides and tertiary amine compounds such as zinc chloride, aluminum chloride, and tin chloride. From a reactivity point of view, cobalt naphthenate is preferred for thermal imidization without the use of a dehydrating agent, while for chemical imidization using a dehydrating agent (described later), the use of a tertiary amine is preferred. One catalyst can be used alone or in appropriate combinations of two or more.

[0033] In chemical imidization using dehydrating agents, the advantage compared to thermal imidization is the ability to lower the reaction temperature. The dehydrating agent used is designed to react with the generated water rather than the substrate in the reaction system. The chemical compounds generated by the reaction with water do not react with the resulting imide compound and can be removed in subsequent processes.

[0034] Carboxylic anhydrides can be used as dehydrating agents, specifically including acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, etc., but are not limited to these. Furthermore, when using carboxylic anhydrides, it is preferable to use a tertiary amine in an equimolar amount with the carboxylic anhydride. There are no particular limitations on the tertiary amine, but from the viewpoint of market availability and ease of removal in subsequent processes, triethylamine is preferred.

[0035] Regarding the substrate-to-reaction ratio, the anhydride used for imidization is preferably 0.8 to 1.5 moles relative to 1 mole of the primary amino group. If the amount of anhydride relative to 1 mole of the primary amino group is less than 0.8 moles or more than 1.5 moles, unreacted functional groups will remain excessively, and the yield of the desired imide compound may decrease.

[0036] Regarding the amount of dehydrating agent used in chemical imidization, it is preferably 1 to 2 moles relative to 1 mole of the primary amine, and an equal molar amount of tertiary amine should also be used. From a productivity point of view, the amount of tertiary amine used is preferably in the range of 1.2 to 1.6 moles.

[0037] Regarding the method for manufacturing the maleimide-containing organopolysiloxane of formula (1) above, the reaction time of raw materials such as organopolysiloxanes containing primary amino groups and acid anhydride compounds is preferably 10 minutes to 24 hours. The reaction time can be any time sufficient for the raw materials to be consumed through the reaction, preferably 1 hour to 10 hours, more preferably 2 hours to 7 hours. If the reaction time is less than 10 minutes, the raw material consumption may be insufficient; if the reaction time exceeds 24 hours, the raw materials will be completely consumed, becoming an unnecessary step, and sometimes reducing production efficiency.

[0038] The maleimide-containing organopolysiloxane produced by the above method, represented by formula (1), contains, as a byproduct, the maleimide-containing organopolysiloxane represented by formula (2) below.

[0039] [Chemistry 6]

[0040] (In equation (2), R) 1 R 2 (The values ​​of 'n' and 'n' are the same as above.) The organosilicon additive for resin modification of the present invention can impart excellent flexibility, heat resistance and dielectric properties to curable resins by making the amount of the maleimide-containing organopolysiloxane represented by the stated formula (2) in the range of 10 mol% to 90 mol% relative to the total amount of the maleimide-containing organopolysiloxane represented by the stated formula (1) in 100 mol%.

[0041] That is, one of the characteristics of the present invention is that the content of the maleimide-containing organopolysiloxane (I) represented by formula (1) and the maleimide-containing organopolysiloxane (II) represented by formula (2) is in the range of 10 mol% to 90 mol%, and preferably 20 mol% to 90 mol%, relative to the total amount of 100 mol% of the organopolysiloxane (I) containing maleimide groups. In the manufacturing process, in order to make the amount of maleimide-containing organopolysiloxane (II) generated in the range of 10 mol% to 90 mol%, it is important to use a dehydrating agent and a tertiary amine within the above-mentioned preferred usage range.

[0042] It should be noted that the content of the maleimide-containing organopolysiloxane represented by formula (2) is determined based on the following conditions. 1 Quantitative analysis was performed using H-NMR.

[0043] [Measurement Conditions] Device: AVANCE III400 manufactured by Burker Solvent: CDCl3 Internal Standard: Tetramethylsilane (TMS) The weight-average molecular weight of the maleimide-containing organopolysiloxane represented by formula (1) is not particularly limited. However, considering the need to impart sufficient flexibility to the cured product obtained by curing the curable composition containing the compound, the weight-average molecular weight is preferably 500 to 5000, more preferably 1000 to 3500. It should be noted that the weight-average molecular weight in this invention is a value obtained by conversion using polystyrene with a known molecular weight as a standard substance by gel permeation chromatography (GPC) measured under the conditions shown below.

[0044] [Measurement Conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6 mL / min Detector: Differential 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 μ L (0.3% by mass THF solution) The functional group equivalent of the polymerizable unsaturated group of the organopolysiloxane containing maleimide group represented by formula (1) is not particularly limited. If sufficient flexibility is desired in the cured product of the curable composition containing this compound, a value of 200 g / mol to 900 g / mol is preferred. Values ​​below 200 g / mol result in excessively high crosslinking density during the crosslinking reaction at the polymerization site, potentially leading to insufficient flexibility. Conversely, if the functional group equivalent exceeds 900 g / mol, the crosslinking density decreases during the crosslinking reaction at the polymerization site, potentially resulting in insufficient hardness.

[0045] Furthermore, the curable resin composition of the present invention is characterized by containing: (A) Organosilicon resin component, which contains: The maleimide-containing organopolysiloxane (I) is represented by the following formula (1). [Chemistry 7]

[0046] (In equation (1), R) 1 Independently representing monovalent hydrocarbon groups with 1 to 12 carbon atoms, all R 1 The proportion of methyl groups is 50 mol% or more, R 2 Independently representing an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, where n represents an integer from 4 to 20. The maleimide-containing organopolysiloxane (II) represented by the following formula (2) [Chemistry 8]

[0047] (In equation (2), R) 1 R 2 , n is the same as above. The content of component (II) is 10 mol% to 90 mol% relative to the total amount of components (I) and (II) above. (B) Aromatic cyanate compounds having one or more cyanate groups in one molecule; and (C) A maleimide compound having two or more maleimide groups and no siloxane bonds in one molecule. It should be noted that the above-described curable composition preferably includes (D) a curing catalyst.

[0048] The silicone resin composition of component (A) above is the same as that of the silicone additives for resin modification mentioned above.

[0049] The aromatic cyanate compound used as component (B) above is characterized in that it is an aromatic cyanate compound having one or more cyanate groups (cyanate groups) in one molecule. Curable resin compositions using this aromatic cyanate compound exhibit excellent properties such as heat resistance and low thermal expansion when cured.

[0050] Aromatic cyanate compounds that are components of (B) above, specifically, include: cyano-benzene, 1-cyano-2-methylbenzene, 1-cyano-3-methylbenzene, 1-cyano-4-methylbenzene, 1-cyano-2-methoxybenzene, 1-cyano-3-methoxybenzene, 1-cyano-4-methoxybenzene, 1-cyano-2,3-dimethylbenzene, 1-cyano-2,4-dimethylbenzene, 1-cyano-2,5-dimethylbenzene, 1-cyano-2,6-dimethylbenzene, 1-cyano-3,4-dimethylbenzene, 1-cyano-3,5-dimethylbenzene, cyano-ethylbenzene, cyano-butylbenzene, cyano-octylbenzene, cyano-nonylbenzene, 2-(4-cyano-phenyl)-2-phenylpropane (4- α-Cyanate ester of cumylphenol), 1-cyano-4-cyclohexylbenzene, 1-cyano-4-vinylbenzene, 1-cyano-2-chlorobenzene or 1-cyano-3-chlorobenzene, 1-cyano-2,6-dichlorobenzene, 1-cyano-2-methyl-3-chlorobenzene, cyanonitrobenzene, 1-cyano-4-nitro-2-ethylbenzene, 1-cyano-2-methoxy-4-allylbenzene (cyanate ester of eugenol), methyl (4-cyanophenyl) sulfide, 1-cyano-3-trifluoromethylbenzene, 4-cyanobiphenyl, 1-cyano-2-acetylbenzene, 1-cyano-4-acetylbenzene, 4-cyanobenzaldehyde, methyl 4-cyanobenzoate, phenyl 4-cyanobenzoate, 1-cyano-4-acetaminobenzene 4-Cyanobenzophenone, 1-Cyano-2,6-di-tert-butylbenzene, 1,2-Dicyanobenzene, 1,3-Dicyanobenzene, 1,4-Dicyanobenzene, 1,4-Dicyano-2-tert-butylbenzene, 1,4-Dicyano-2,3-dimethylbenzene, 1,4-Dicyano-2,3,5-trimethylbenzene, 1,3-Dicyano-2,4,5-trimethylbenzene, 1,3-Dicyano-5-methylbenzene, 1-Cyanonaphthalene, 2-Cyanonaphthalene, 1-Cyano-4-methoxynaphthalene, 2-Cyano-6-methylnaphthalene, 2-Cyano-7-methoxynaphthalene, 2,2'-Dicyano-1,1'-Binaphthalene, 1,3-Dicyanonaphthalene, 1,4-Dicyanonaphthalene, 1,5-Dicyanonaphthalene, 1 6-Dicyanonaphthalene, 1,7-Dicyanonaphthalene, 2,3-Dicyanonaphthalene, 2,6-Dicyanonaphthalene or 2,7-Dicyanonaphthalene, 2,2'-Dicyanobiphenyl, 4,4'-Dicyanobiphenyl, 4,4'-Dicyanooctafluorobiphenyl, 2,4'-Dicyanodiphenylmethane, 4,4'-Dicyanodiphenylmethane, bis(4-cyano-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanophenyl)ethane, 1,1-bis(4-cyanophenyl)propane, 2,2-bis(4-cyanophenyl)propane, 2,2-bis(4-cyano-3-methylphenyl)propane, 2,2-bis(2-cyano-5-biphenyl)propane, 2,2-bis(4-cyanophenyl)hexachlorobenzene Fluoropropane, 2,2-bis(4-cyano-3,5-dimethylphenyl)propane, 1,1-bis(4-cyano-phenyl)butane, 1,1-bis(4-cyano-phenyl)isobutane, 1,1-bis(4-cyano-phenyl)pentane, 1,1-bis(4-cyano-phenyl)-3-methylbutane, 1,1-bis(4-cyano-phenyl)-2-methylbutane, 1,1-bis(4-cyano-phenyl)-2,2-dimethylpropane, 2,2-bis(4-cyano-phenyl)butane, 2,2-bis(4-cyano-phenyl)pentane, 2,2-bis(4-cyano-phenyl)hexane, 2,2-bis(4-cyano-phenyl)-3-methylbutane, 2,2-bis(4-cyano-phenyl)-4-methylpentane, 2,2-Bis(4-cyanophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanophenyl)hexane, 3,3-bis(4-cyanophenyl)heptane, 3,3-bis(4-cyanophenyl)octane, 3,3-bis(4-cyanophenyl)-2-methylpentane, 3,3-bis(4-cyanophenyl)-2-methylhexane, 3,3-bis(4-cyanophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanophenyl)-3-methylheptane, 3,3-bis(4-cyanophenyl)-2-methylheptane, 3,3-bis(4-cyanophenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanophenyl)-2,4- Dimethylhexane, 3,3-bis(4-cyanophenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanophenyl)-1,1,1,3,3,3-hexafluoropropane, bis(4-cyanophenyl)phenylmethane, 1,1-bis(4-cyanophenyl)-1-phenylethane, bis(4-cyanophenyl)biphenylmethane, 1,1-bis(4-cyanophenyl)cyclopentane, 1,1-bis(4-cyanophenyl)cyclohexane, 2,2-bis(4-cyano-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanophenyl)cyclohexane, bis(4-cyanophenyl)diphenylmethane, bis(4-cyanophenyl)-2,2- Dichloroethylene, 1,3-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,4-bis[2-(4-cyanophenyl)-2-propyl]benzene, 1,1-bis(4-cyanophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4-cyanophenyl)methyl]biphenyl, 4,4-dicyanobenzophenone, 1,3-bis(4-cyanophenyl)-2-propen-1-one, bis(4-cyanophenyl) ether, bis(4-cyanophenyl) sulfide, bis(4-cyanophenyl) sulfone, 4-cyanophenylbenzoate-4-cyanophenyl ester (4-cyanophenyl-4-cyanobenzoate), bis-(4-cyanophenyl) carbonate, 1,3 -bis(4-cyanophenyl)adamantane, 1,3-bis(4-cyanophenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanophenyl)isobenzofuran-1(3H)-one (cyanate ester of phenolphthalein), 3,3-bis(4-cyano-3-methylphenyl)isobenzofuran-1(3H)-one (cyanate ester of o-cresolphthalein), 9,9'-bis(4-cyanophenyl)fluorene, 9,9'-bis(4-cyano-3-methylphenyl)fluorene, 9,9'-bis(2-cyano-5-biphenyl)fluorene, tris(4-cyanophenyl)methane, 1,1,1-tris(4-cyanophenyl)ethane, 1,1,3-tris(4-cyanophenyl)propane, α , α , α'-Tris(4-cyanophenyl)-1-ethyl-4-isopropylbenzene, 1,1,2,2-tetra(4-cyanophenyl)ethane, tetra(4-cyanophenyl)methane, 2,4,6-tris(N-methyl-4-cyanophenylamino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanophenylamino)-6-(N-methylphenylamino)-1,3,5-triazine, bis(N-4-cyano-2-methylphenyl)-4,4'-oxobisphthalimide, bis(N-3-cyano-4-methylphenyl)-4,4'-oxobisphthalimide, bis(N-4-cyanophenyl)-4,4'-oxobisphthalimide Imide, bis(N-4-cyano-2-methylphenyl)-4,4'-(hexafluoroisopropylidene)bisphthalimide, tris(3,5-dimethyl-4-cyano-benzyl)isocyanurate, 2-phenyl-3,3-bis(4-cyano-phenyl)phthalimide, 2-(4-methylphenyl)-3,3-bis(4-cyano-phenyl)phthalimide, 2-phenyl-3,3-bis(4-cyano-3-methylphenyl)phthalimide, 1-methyl-3,3-bis(4-cyano-phenyl)indol-2-one, and 2-phenyl-3,3-bis(4-cyano-phenyl)indol-2-one.

[0051] The maleimide compound described above as component (C) is characterized in that it is a maleimide compound having two or more maleimide groups in one molecule and not having a siloxane bond. Examples of such maleimide compounds include compounds having two or more maleimide groups in their molecules, which are commonly circulated as bismaleimide resins. For example, cocondensates of bismaleimide and aldehyde compounds can be used, and one or more of these compounds can be employed. Examples of the aforementioned bismaleimides include: aliphatic maleimides such as N,N'-ethylidene bismaleimide and N,N'-hexamethylene bismaleimide; 4,4'-diphenylmethane bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, bis[4-(4-maleimidephenoxy)phenyl]methane, and 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-maleimidephenoxy]... Aromatic maleimides include [phenyl]propane, N,N'-p,p'-diphenyldimethylsilyl bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-methylenebis(3-chloro-p-phenylene)bismaleimide, N,N'-4,4'-diphenyl sulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-dimethylenecyclohexane bismaleimide, N,N'-m-phenylenedimethyl bismaleimide, and N,N'-4,4'-diphenylcyclohexane bismaleimide. It should be noted that examples of the above-mentioned aldehyde compounds include, for example, formaldehyde, acetaldehyde, benzaldehyde, and hydroxybenzaldehyde.

[0052] The curable composition described above may include (D) a curing catalyst as needed. Examples of curing catalysts as component (D) include, for example, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-methylimidazole; triethylamine, benzyldimethylamine, etc. αTertiary amine compounds such as methylbenzyldimethylamine and 1,8-diazabicyclo[5.4.0]undec-7-ene; organophosphorus compounds such as triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine-triphenylborate, tetraphenylphosphine-tetraphenylborate, tributylhexylphosphine bromide, and tri(dimethoxyphenyl)phosphine; and phosphonium salts obtained by reacting organophosphorus compounds such as triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, and tri(dimethoxyphenyl)phosphine with hydrogen halides or haloalkanes; organometallic compounds such as aluminum and zirconium; etc.; in addition, heterocyclic amine compounds, boron complexes, organoammonium salts, organosulfonate salts, and organoperoxides can be used, and one or more of them can be used. Among them, from the viewpoint of further promoting curing, tetraphenylphosphine-tetratolylborate is preferred.

[0053] The content of the silicone resin component as component (A) above can be appropriately set according to the desired characteristics and is not particularly limited. From the viewpoint of further improving the balance of physical properties such as flexibility, heat resistance and dielectric properties, it is preferably 1 part to 25 parts by mass relative to 100 parts by mass of the solid resin component in the resin composition, more preferably 2 parts to 20 parts by mass, and even more preferably 5 parts to 15 parts by mass.

[0054] The content of the aromatic cyanate compound as component (B) above can be appropriately set according to the desired characteristics and is not particularly limited. From the viewpoint of further improving the balance of physical properties such as flexibility, heat resistance and dielectric properties, it is preferably 1 part to 99 parts by mass relative to 100 parts by mass of the resin solids in the resin composition, more preferably 10 parts to 80 parts by mass, and even more preferably 25 parts to 70 parts by mass.

[0055] The content of the maleimide compound as component (C) above can be appropriately set according to the desired characteristics and is not particularly limited. From the viewpoint of further improving the balance of physical properties such as flexibility, heat resistance and dielectric properties, it is preferably 1 part to 99 parts by mass relative to 100 parts by mass of the resin solids in the resin composition, more preferably 10 parts to 80 parts by mass, and even more preferably 25 parts to 70 parts by mass.

[0056] It should be noted that in this invention, "resin solids" refers to components (A), (B), and (C) mentioned above. Therefore, the amount of resin solids in the resin composition refers to the total amount of components (A), (B), and (C).

[0057] The amount of the curing catalyst, which is the component (D) above, is not particularly limited as long as it meets the desired curing speed, cured properties, and appropriate usable time of the composition. Generally, it is preferred to be 0.1 to 5 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0058] The curable resin composition of the present invention can include an organic solvent as needed. In this case, it can be used in such a way that at least a portion, preferably all, of the aforementioned resin components is dissolved or miscible with the organic solvent (solution or varnish). Regarding the organic solvent used, one can be used alone or two or more can be used in appropriate mixtures.

[0059] As an organic solvent, any known organic solvent can be used appropriately, and there is no particular limitation on its type. Specific examples of organic solvents include: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as methyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; polar amide solvents such as N-methylpyrrolidone, dimethylacetamide, and dimethylformamide; and non-polar solvents such as toluene and xylene. Among these, from the viewpoint of solubility, N-methylpyrrolidone is preferred, and from the perspective of balancing drying properties, methyl ethyl ketone is preferred.

[0060] The curable resin composition of the present invention can be prepared appropriately by conventional methods. The preparation method is not particularly limited as long as it yields a curable composition uniformly comprising the aforementioned (A) silicone resin component, (B) aromatic cyanate compound, (C) maleimide compound, and the other aforementioned components. For example, the curable composition of the present invention can be readily prepared by sequentially combining the aforementioned (A), (B), (C), and other components in an organic solvent and stirring thoroughly.

[0061] Regarding the set temperature for heating and curing the curable resin composition of the present invention, there are no particular limitations as long as the desired physical properties of the cured product can be exhibited. From the viewpoint of the volatility of the organic solvent and production efficiency, 100°C to 250°C is preferred, and 150°C to 200°C is more preferred. The curing time can be appropriately set.

[0062] There are no particular limitations on the method for producing self-supporting cured molded articles using the curable resin composition of the present invention, and known manufacturing methods can be employed. Examples include, but are not limited to, methods using molds, film-forming methods using casting methods that can coat and cure a film pre-existing with a release layer, etc.

[0063] Regarding the method for producing the self-supporting curing molded article described above, when using a molding master mold, the material of the molding master mold is not particularly limited, as long as it ensures good release properties from the cured article. Examples include metal, glass, plastic, and silicone. Furthermore, the surface of the master mold can be coated with resins such as polytetrafluoroethylene (PTFE) and ethylene-tetrafluoroethylene (ETFE). Molds with PTFE surface coatings are preferred due to their excellent release properties. Using such a mold helps to suppress the breakage of the cured article when removing the curable resin composition of the present invention.

[0064] The cured products of the curable resin compositions of the present invention are particularly suitable for use as sealing materials for electronic components, prepregs, laminates with metal foil coatings, printed wiring boards, and constituent materials for semiconductor packages. For example, prepregs can be obtained by impregnating or coating a substrate with a varnish of the curable composition of the present invention and then drying it.

[0065] Alternatively, by using a peelable plastic film as a substrate, applying the varnish to the plastic film and drying it, a build-up film or dry film solder resist can be obtained. In this case, the organic solvent used can be dried under set conditions of 20°C to 150°C for 1 minute to 90 minutes.

[0066] Furthermore, the curable resin composition of the present invention can also be used in an uncured state with only the organic solvent dried, or it can be used in a semi-cured (B-stage) state as needed.

[0067] Example The present invention will be described in more detail below with examples of synthesis, embodiments, and comparative examples, but the present invention is not limited to these embodiments. It should be noted that in the following examples, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass," respectively. Furthermore, the devices used in the embodiments are described below.

[0068] (1) GPC determination conditions Device: HLC-8320GPC manufactured by Tosoh Corporation Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6 mL / min Detector: Differential 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 μ L (0.3% by mass THF solution) Standard: Monodisperse polystyrene (2) Proton nuclear magnetic resonance spectrum ( 1 H-NMR measurement conditions Device: AVANCE III 400 manufactured by Burker Solvent: CDCl3 Internal Standard: Tetramethylsilane (TMS) [1] Synthesis of organopolysiloxanes containing maleimide groups [Synthesis example 1] In a 1L separable flask equipped with a stirrer, reflux cooler, dropping funnel, and thermometer, 98.1 parts by mass (1 mol) of maleic anhydride, 300 parts by mass of tetrahydrofuran, and 0.4 parts by mass of the polymerization inhibitor bis-tert-butylphenol were added and stirred. After all components were uniformly dissolved, 270 parts by mass (1 mol of amino group) of polydimethylsiloxane (A1) with a terminal aminopropyl dimethylsilyl structure of 270 g / mol were added dropwise. The dropwise addition reaction was exothermic, and a water bath was used for temperature management to ensure that the reaction solution temperature did not exceed 50°C. After the dropwise addition was completed, stirring was continued at room temperature for 1 hour, and the disappearance of the reactants was confirmed by GPC. Next, 150 parts by mass (1.5 mol) of acetic anhydride were added and stirred, followed by the dropwise addition of 150 parts by mass (1.5 mol) of triethylamine. A small amount of exothermic reaction was generated with the dropwise addition, and the appearance changed from orange to dark red. After the addition was complete, the reaction was carried out at an internal temperature of 50°C for 3 hours. GPC was used to confirm the disappearance of the peak from the intermediate ammonium acid structure and the emergence of a new peak corresponding to the maleimide-containing organopolysiloxane. Finally, unreacted residual anhydrides, amines, and tetrahydrofuran were removed by vacuum distillation to obtain a black oily compound (M1). The viscosity of this compound at 25°C was 400 mPa·s. Regarding the obtained organopolysiloxane, according to GPC and... 1 The H-NMR results confirmed it to be a mixture of structures represented by formulas (1-a) and (2-a) below. The content of formula (2-a) below is 86 mol% of the total composition.

[0069] [Chemistry 9]

[0070] [Chemistry 10]

[0071] [Synthesis example 2] The polydimethylsiloxane (A1) with a biterminated aminopropyl dimethylsilyl structure used in Synthesis Example 1 was replaced with a polydimethylsiloxane (A2) with a biterminated aminopropyl dimethylsilyl structure having a primary amino functional group content of 430 g / mol. The reaction ratio was kept consistent, and the same procedures as in Synthesis Example 1 were performed to obtain a black oily compound (M2). The viscosity of this compound at 25°C was 160 mPa·s. Regarding the obtained siloxane, according to GPC and... 1 The H-NMR results confirmed it to be a mixture of structures represented by formulas (1-b) and (2-b) below. The content of formula (2-b) below is 50 mol% of the total composition.

[0072] [Chemistry 11]

[0073] [Chemistry 12]

[0074] [Synthesis example 3] The polydimethylsiloxane (A1) with a biterminated aminopropyl dimethylsilyl structure used in Synthesis Example 1 was replaced with a polydimethylsiloxane (A3) with a biterminated aminopropyl dimethylsilyl structure having a primary amino functional group content of 780 g / mol, and the reaction ratio was kept consistent. All other procedures were performed to obtain a black oily compound (M3). The viscosity of this compound at 25°C was 130 mPa·s. Regarding the obtained siloxane, according to GPC and... 1 The H-NMR results confirmed it to be a mixture of structures represented by formulas (1-c) and (2-c) below. The content of formula (2-c) below is 22 mol% of the total composition.

[0075] [Chemistry 13]

[0076] [Chemistry 14]

[0077] [2] Preparation of Curable Compositions for Self-Supporting Sheet Molding [Examples 1-3, Comparative Examples 1-5] The thermosetting compositions of Examples 1-3 and Comparative Examples 1-5 were prepared by mixing the components according to the proportions shown in Table 1 below. All proportions are expressed by mass. The compositions were designed with a molar ratio of maleimide to cyanate ester groups of 1:3 and a molar ratio of maleimide to curing catalyst of 1:0.03. The compositions were ultimately cleared by dissolving and diluting with N-methylpyrrolidone to achieve an active ingredient content of 35%.

[0078] [Table 1]

[0079] The abbreviations in Table 1 are shown below.

[0080] “MR-0”: a disiloxane with two maleimide groups represented by the following formula (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0081] "BMI-70": An aromatic compound containing two maleimide groups, represented by the following formula (manufactured by KI Chemicals Co., Ltd., trade name "BMI-70"). "LECY": A bisphenol E compound containing two cyanate ester groups, represented by the following formula (manufactured by Lonza Japan, trade name "LECy"). "Cure-up catalyst": Tetraphenylphosphonium tetraphenylborate (manufactured by Hokuko Chemical Industry Co., Ltd., trade name "TPP-K") [Chemistry 15]

[0082] The thermosetting composition in Table 1 was poured into a mold (0.3 mm deep × 15 cm long × 10 cm wide) coated with polytetrafluoroethylene (PTFE) resin. The mold was then placed on a hot plate heated to 200°C for 90 minutes to allow the organic solvent (N-methylpyrrolidone) to evaporate. The mold was then heated in a dryer at 150°C for 60 minutes, followed by another 60 minutes at 200°C to complete curing, yielding a test piece.

[0083] The sheet-shaped articles obtained in Examples 1-3 and Comparative Examples 1-5 were evaluated as follows. The results are shown in Table 2.

[0084] (1) Formability Observe whether the sheet becomes self-supporting when it is removed from the mold, and judge it in the following way.

[0085] It can be removed in the form of a slice without any abnormalities.

[0086] ×: Crispy or soft, cannot be removed in slices.

[0087] (2) 90° bending performance As an evaluation of flexibility, the 90° bending performance is evaluated. The test piece obtained above is cut into strips 1cm wide, 10cm long, 1cm wide, and 0.3mm thick. The two short sides are held with tweezers, and the state of the strip when bent at 90° is observed. The judgment is made in the following manner.

[0088] It can bend without breaking.

[0089] ×: Completely broken, cannot be bent.

[0090] (3) Appearance changes at 150℃ The test piece obtained above was cut into a rectangle with a length of 3cm, a width of 4cm, and a thickness of 0.3mm. The appearance changes of the piece were observed after heating at 150℃ for 1 hour, and the results were judged in the following manner.

[0091] There was almost no change in appearance, and no warping could be detected.

[0092] ×: Obvious changes in appearance, such as warping, have been observed.

[0093] (4) Hardness of the hardness tester According to JISK 7215, the hardness test was performed using a D-type indenter manufactured by TECLOCK.

[0094] (5) Energy storage modulus, Tan δ (max) The test piece obtained above was cut into strips with a length of 10cm × width of 1cm × thickness of 0.3mm. The strips were then measured using a viscoelasticity measuring device DMA 7100 manufactured by Hitachi Advanced Technology & Science Co., Ltd., which heated the strips from -50°C to 300°C in air at a rate of 10°C / min, and the temperature was measured in tensile testing mode.

[0095] (6) Relative permittivity and dielectric loss tangent The test piece obtained above was cut into a rectangular shape with a length of 3cm, a width of 4cm, and a thickness of 0.3mm. A network analyzer ("E5063-2 D5" manufactured by Keysight Corporation) was connected to a stripline (manufactured by KEYCOM Corporation) to measure the relative permittivity and dielectric loss tangent at a frequency of 10GHz.

[0096] [Table 2]

[0097] As can be seen from the results in Table 2, the sheet-formed products including Examples 1 to 3 can achieve high levels of processability, flexibility, hardness (hardness tester, storage modulus), heat resistance and low dielectric properties.

[0098] On the other hand, in the composition of Comparative Example 1, since it did not contain (A) the silicone resin component (organopolysiloxane (I) containing maleimide groups), the resulting test sheet had insufficient flexibility. In the composition of Comparative Example 2, an organopolysiloxane containing maleimide groups was included as the silicone resin component, but the siloxane structure was disiloxane, which did not help to improve the expected flexibility. As a result, the flexibility remained at the same level as Comparative Example 1. The compositions of Comparative Examples 3 to 5 were molded articles composed only of (A) the silicone resin component (organopolysiloxane (I) containing maleimide groups) and a cyanate ester compound (B), but in Comparative Examples 4 and 5, a uniform sheet molded article could not be obtained due to a significant decrease in hardness. Although a sheet molded article was obtained in Comparative Example 3, a deterioration in hardness and dielectric loss tangent was confirmed.

[0099] As shown in Table 2, the curable resin composition of the present invention, which uses an additive containing an organopolysiloxane with maleimide groups, combines flexibility, heat resistance and dielectric properties, and can be suitable for use as a sealing material for electronic components, prepreg, metal foil laminate, printed wiring board and semiconductor package material, etc.

[0100] It should be noted that this invention is not limited to the embodiments described above. The embodiments described above are merely illustrative. Technical solutions that have substantially the same structure as the technical concept described in this invention and achieve the same effect are all included within the technical scope of this invention.

Claims

1. An organosilicon additive for resin modification, characterized in that, contain: Organopolysiloxanes (I) containing maleimide groups, represented by the following formula (1); and The maleimide-containing organopolysiloxane (II) represented by the following formula (2). In equation (1), R 1 Independently representing monovalent hydrocarbon groups with 1 to 12 carbon atoms, all R 1 The proportion of methyl groups is 50 mol% or more, R 2 Independently representing an alkyl group with 1 to 5 hydrogen atoms or carbon atoms, where n represents an integer from 4 to 20. In equation (2), R 1 R 2 The values ​​of and n are the same as those mentioned above. The content of component (II) is 10 mol% to 90 mol% relative to the total amount of components (I) and (II) above.

2. The organosilicon additive for resin modification according to claim 1, wherein, The R 1 All are methyl groups.

3. The organosilicon additive for resin modification according to claim 1 or 2, wherein, The R 2 It consists entirely of hydrogen atoms.

4. A curable resin composition, characterized in that, contain: (A) Organosilicon resin component, which contains: Organopolysiloxanes (I) containing maleimide groups, represented by the following formula (1); and The maleimide-containing organopolysiloxane (II) represented by the following formula (2). In equation (1), R 1 Independently representing monovalent hydrocarbon groups with 1 to 12 carbon atoms, all R 1 The proportion of methyl groups is 50 mol% or more, R 2 Independently representing an alkyl group with 1 to 5 hydrogen atoms or carbon atoms, where n represents an integer from 4 to 20. In equation (2), R 1 R 2 The values ​​of and n are the same as those mentioned above. The content of component (II) is 10 mol% to 90 mol% relative to the total amount of components (I) and (II) above. (B) Aromatic cyanate compounds having one or more cyanate groups in one molecule; and (C) Maleimide compounds having two or more maleimide groups in one molecule but no siloxane bonds.

5. The curable resin composition according to claim 4, wherein, The R 1 All are methyl groups.

6. The curable resin composition according to claim 4, wherein, The R 2 It consists entirely of hydrogen atoms.

7. The curable resin composition according to any one of claims 4 to 6, wherein, The curable resin composition further comprises a curing catalyst (D).

8. The curable resin composition according to claim 4, wherein, The content of component (A) is 1 to 25 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

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