Resin composition, cured object, sheet, layered product, and printed wiring board
Patent Information
- Authority / Receiving Office
- TW · TW
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2022-11-17
- Publication Date
- 2023-09-16
Abstract
Description
[Technical Field]
[0001] This disclosure relates to a resin composition, a cured product, a sheet, a laminate, and a printed circuit board. [Previous Technology]
[0002] Printed circuit boards and multilayer circuit boards using the printed circuit boards are used in mobile communication devices such as mobile phones and smartphones, as well as their base station devices, network-related electronic machines such as servers / routers, mainframe computers and other products.
[0003] In recent years, high-frequency electrical signals have been used in these products for high-speed transmission / processing of large amounts of information. However, high-frequency signals are very easy to attenuate. Therefore, in order to suppress transmission loss, insulating materials with excellent dielectric properties are required as insulating materials used in the above-mentioned printed circuit boards and multilayer circuit boards.
[0004] As the aforementioned insulating material, epoxy resin compositions disclosed in Patent Documents 1 to 3 are known. Patent Document 1 discloses an epoxy resin composition containing epoxy resin, an active ester compound, and a triazine-containing cresol phenolic varnish resin, which is effective for achieving low dielectric loss tangent. Furthermore, Patent Documents 2 and 3 disclose resin compositions with epoxy resin and an active ester compound as essential components that can form cured products with low dielectric loss tangent and are useful as insulating materials. However, it has been found that these epoxy resin compositions are unsuitable for high-frequency band applications.
[0005] On the other hand, Patent Document 4 reports that resin films composed of a resin composition containing a maleic anhydride resin having long-chain alkyl groups and a curing agent as non-epoxy materials have excellent dielectric properties (low relative permittivity and low dielectric loss tangent). However, maleic anhydride resins composed only of long-chain alkyl diamines have problems with low Tg and low elastic modulus.
[0006] [Patent Document 1] Japanese Patent Application Publication No. 2011-132507 [Patent Document 2] Japanese Patent Application Publication No. 2015-101626 [Patent Document 3] Japanese Patent Application Publication No. 2017-210527 [Patent Document 4] International Publication No. WO2016 / 114287 [Summary of the Invention]
[0007] Therefore, the object of this disclosure is to provide a resin composition capable of forming a cured product with high elastic modulus and high Tg while sufficiently maintaining a low dielectric constant and low dielectric loss tangent. Another object of this disclosure is to provide a cured product, sheet, laminate, and printed circuit board using the above-mentioned resin composition.
[0008] As a result of in-depth research conducted by the inventors in order to solve the above-mentioned problems, they discovered that by using the specified components as tetracarboxylic dianhydride (a1) and diamine (a2) in the maleic anhydride (a3) resin (A), which is formed by reacting tetracarboxylic dianhydride (a1), diamine (a2) and maleic anhydride (a3), it is possible to form a cured product with high elastic modulus and high Tg while maintaining a low dielectric constant and low dielectric loss tangent, thereby completing the present invention.
[0009] That is, this disclosure provides the following invention. [1] A resin composition comprising a maleic anhydride resin (A) formed by reacting tetracarboxylic dianhydride (a1), a diamine (a2) and maleic anhydride (a3), wherein the tetracarboxylic dianhydride (a1) comprises at least one of the compounds represented by formula (1), the compounds represented by formula (2) and the compounds represented by formula (6), and the diamine (a2) comprises dimer diamine and a second diamine other than dimer diamine. [Chemical 1][Chemical 2][Chemical 3][2] The resin composition as described above [1], wherein the second diamine comprises at least one selected from the group consisting of 1,3-diaminopropane, norbornene diamine, 4,4'-methylenediphenylamine and 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene. [3] The resin composition as described in [1] or [2] above, wherein the dimer diamine comprises at least one of the compounds represented by the following general formula (3) and the compounds represented by the following general formula (4). [Chemical 4][Chemical 5][In formulas (3) and (4), m, n, p and q respectively represent integers of 1 or more selected in such a way as m+n=6 to 17, p+q=8 to 19, and the bonds represented by dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. In the case where the bonds represented by dashed lines are carbon-carbon double bonds, formulas (3) and (4) are structures obtained by subtracting 1 from the number shown in formulas (3) and (4) for the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond.] [4] The resin composition as described in any one of [1] to [3] above, wherein the weight average molecular weight of the above-described maleic diimide resin (A) is 3000 to 25000. [5] A cured product, which is a cured product of the resin composition described in any one of [1] to [4] above. [6] A sheet comprising the resin composition described in any one of [1] to [4] above and a substrate. [7] The sheet described in [6] above, wherein the substrate is an organic substrate. [8] The sheet described in [6] above, wherein the substrate is an inorganic substrate. [9] A laminate obtained by further hot-pressing a substrate onto the bonding surface of the sheet described in any one of [6] to [8] above.
[10] A printed circuit board made using the sheet described in any one of [6] to [8] above.
[11] A printed circuit board made using the laminate described in [9] above. [Effects of the Invention]
[0010] According to this disclosure, it is possible to provide a resin composition that can form a cured product with high elastic modulus and high Tg while maintaining a low dielectric constant and low dielectric loss tangent, a cured product using the resin composition, a sheet, a laminate and a printed circuit board.
[0011] The resin composition (adhesive composition) disclosed herein can simultaneously reduce the dielectric constant and dielectric loss tangent (hereinafter, both are sometimes collectively referred to as "dielectric properties"), especially exhibiting excellent low dielectric properties in the high-frequency band. Furthermore, the cured product (adhesive layer) obtained from this resin composition has a high elastic modulus and Tg. Therefore, this resin composition is not only useful as an adhesive used in the manufacture of printed circuit boards (additional layer boards, flexible printed circuit boards, etc.) and copper-clad laminates for printed circuit boards, but also as a semiconductor interlayer material, coating agent, resist ink, conductive paste, electrical insulating material, etc.
Implementation Method
[0012] The following describes the implementation of this disclosure in detail.
[0013] <Resin Composition> The resin composition of this embodiment includes a maleic anhydride resin (A) (hereinafter also referred to as "(A1) component") formed by reacting tetracarboxylic dianhydride (a1) (hereinafter also referred to as "(a2) component"), diamine (a2) (hereinafter also referred to as "(a3) component"), and maleic anhydride (a3) (hereinafter also referred to as "(a3) component"). The resin composition of this embodiment may also include a polymerization initiator (B) (hereinafter also referred to as "(B) component"). Furthermore, the resin composition of this embodiment may also include an organic solvent (C) (hereinafter also referred to as "(C) component").
[0014] ((A) component: maleic anhydride resin) Regarding component (A), it can be obtained by reacting components (a1), (a2) and (a3). Component (A) may have a plurality of maleic anhydride groups within the molecule. Component (A) may be a bismaleic anhydride resin.
[0015] (a1) The ingredient contains at least one of the following compounds: the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (6). [Chemical 6][Chemical 7][Chemical 8]
[0016] The compound represented by formula (1) above is 4,4'-(hexafluoroisopropylidene)phthalic anhydride. The compound represented by formula (2) above is 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione. The compound represented by formula (6) above is 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. By using these compounds as component (a1), the elastic modulus and Tg of the cured product can be improved while maintaining the low dielectric constant and low dielectric loss tangent of the cured product.
[0017] (a1) The component may include other tetracarboxylic dianhydrides besides those represented by the compounds of the above general formulas (1), (2) and (6). As other tetracarboxylic dianhydrides, those known as raw materials for polyimide can be used.
[0018] Other tetracarboxylic dianhydrides include, for example, pyrolithic anhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenyltrimethylcarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4 4'-(hexafluoroisopropylidene) phthalic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, 1,2,4,5-cyclohexanetetracarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3, 4-Cyclopentanetetracarboxylic dianhydride, 1,2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3:5,6-dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1 4-Phenylene, 9,9-bis(3,4-dicarboxyphenyl) dianhydride, anhydrous 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl] dianhydride, 4,4'-(acetylene-1,2-diyl)diphthalic anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic anhydride, 3,4'-oxydiphthalic anhydride, 3,4'-diphthalic anhydride, etc. These can be used alone or in combination of two or more.
[0019] In component (a1), from the viewpoint of further improving the elastic modulus and Tg of the cured product, the total content of the compound represented by formula (1), the compound represented by formula (2) and the compound represented by formula (6) above, based on the total amount of component (a1), can be 50 mol% or more, or 70 mol% or more, or 100 mol.
[0020] (a2) The component contains a dimerized diamine (the first diamine) and a second diamine other than the dimerized diamine.
[0021] For example, as described in Japanese Patent Application Publication No. 9-12712, dimer diamine is a compound derived from dimers of unsaturated fatty acids such as oleic acid, i.e. dimer acids. In this embodiment, known dimer diamines can be used without particular limitation, but those represented by, for example, the following general formulas (3) and / or (4) are preferred.
[0022] [Chemical 9][Chemical 10][In formulas (3) and (4), m, n, p, and q represent integers of 1 or higher selected in the manner of m+n=6~17 and p+q=8~19, respectively. The bonds represented by dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. In the case where the bonds represented by dashed lines are carbon-carbon double bonds, formulas (3) and (4) have the following structure: the structure obtained by subtracting 1 from the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond as shown in formulas (3) and (4).]
[0023] As a dimer diamine, from the viewpoint of solubility in organic solvents, heat resistance, heat-resistant adhesion, low viscosity, etc., the compound represented by the above general formula (4) is preferred, and the compound represented by the following formula (5) is particularly preferred. [Chemical 11]
[0024] Commercially available products as dimerized diamines include, for example, PRIAMINE 1075 and PRIAMINE 1074 (both manufactured by Croda Japan KK). These can be used alone or in combination of two or more.
[0025] The second diamine is a diamine that does not correspond to the above-mentioned dimer diamine. Examples of the second diamine include 1,3-diaminopropane, norcamphene diamine, 4,4'-methylenediphenylamine, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)benzene, and 9,9-bis[4-(4-aminophenyl)benzene]. [Oxy)phenyl] fuss, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornene, 4,4'-(hexafluoroisopropylidene)diphenylamine, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,1-bis(4 2,7-Diaminophenoxyphenylcyclohexane, 4,4'-ethylenediphenylamine, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]methane, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]phenyl [Kelp, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, (4,4'-diamino)diphenyl ether, (3,3'-diamino)diphenyl ether, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 2,2'-dimethylbiphenyl-4,4'-diamine, bis[4-(3-aminophenoxy)phenyl] benzoate, bis[4-(4-aminophenoxy)phenyl] benzoate, 2-methyl-1,5-diaminopentane, etc. These can be used alone or in combination of two or more.
[0026] By using a dimerized diamine as the diamine, the dielectric properties of the cured product can be reduced. On the other hand, when only a dimerized diamine is used as the diamine, the elastic modulus and Tg of the cured product decrease. In contrast, by using both a second diamine and a dimerized diamine, the elastic modulus and Tg of the cured product can be increased.
[0027] In component (a2), the molar ratio of the second diamine (molar number of the second diamine / (molar number of the dimer diamine + molar number of the second diamine)) can be 20 to 70 molar%, or 30 to 50 molar%. If the ratio is 20 molar% or more, the elastic modulus and Tg of the cured product can be further improved; if it is 70 molar% or less, the dielectric properties of the cured product can be further reduced.
[0028] Regarding component (A), it can be manufactured by various known methods. For example, firstly, components (a1) and (a2) are subjected to a heavy addition reaction at a temperature of about 60–120°C, preferably 70–90°C, for a period of about 0.1–2 hours, preferably 0.1–1.0 hours. Next, the obtained heavy addition product is subjected to a nitriloimide reaction, i.e., a dehydration ring-closure reaction, at a temperature of about 80–250°C, preferably 100–200°C, for a period of about 0.5–30 hours, preferably 0.5–10 hours. Next, the substance that has undergone the dehydration ring-closure reaction and component (a3) are subjected to a maleic-butenediimidide reaction, i.e., a dehydration ring-closure reaction, at a temperature of about 60–250°C, preferably 80–200°C, for a period of about 0.5–30 hours, preferably 0.5–10 hours, thereby obtaining component (A) as desired.
[0029] Furthermore, in the acetilimation reaction or the maleic diacetilimation reaction, various known reaction catalysts, dehydrating agents, and organic solvents described later can be used. Examples of reaction catalysts include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as pyridine, methylpyridine, and isoquinoline, or organic acids such as methanesulfonic acid and p-toluenesulfonic acid monohydrate. One or more of these can be used alone or in combination. Examples of dehydrating agents include aliphatic anhydrides such as acetic anhydride and aromatic anhydrides such as benzoic anhydride. One or more of these can be used alone or in combination.
[0030] Furthermore, component (A) can be purified by various known methods, thereby increasing its purity. For example, firstly, component (A) dissolved in an organic solvent and pure water are added to a separatory funnel. Then, the separatory funnel is shaken and allowed to stand. Next, after the aqueous layer and organic layer are separated, only the organic layer is recovered, thereby purifying component (A).
[0031] (A) The molecular weight of component A can be controlled by the molar numbers of components (a1) and (a2). The smaller the molar number of component (a1) is compared with the molar number of component (a2), the greater the reduction in molecular weight. In order to easily achieve the effects disclosed herein, the ratio of [molar number of component (a1)] to [molar number of component (a2)] is usually around 0.30 to 0.85, preferably in the range of 0.50 to 0.80.
[0032] Regarding the molecular weight of component (A), from the viewpoint of solubility in solvents and heat resistance, a weight average molecular weight of 3,000 to 25,000 is preferred, and 7,000 to 20,000 is even more preferred. There is a tendency that if the weight average molecular weight is below 25,000, the solubility in organic solvents becomes good, and if it is above 3,000, the effect of improving heat resistance is sufficiently obtained.
[0033] (A) The ingredient can be used alone or in combination of two or more.
[0034] ((B) Component: Polymerization Initiator) Component (B) can specifically include, for example, organic peroxides, imidazole compounds, phosphine compounds, and phosphonium salt compounds. These can be used alone or in combination of two or more. Among them, imidazole compounds are particularly preferred as polymerization initiators due to their excellent performance and superior low dielectric properties.
[0035] Examples of organic peroxides include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetate peroxide, acetyl acetone peroxide, 1,1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexyl peroxide)cyclohexane, 1,1-bis(tert-hexyl peroxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butyl peroxide)cyclohexane, and 2,2-bis(4,4- 2-Tributylperoxycyclohexyl)propane, 1,1-bis(tributylperoxy)cyclododecane, n-butyl-4,4-bis(tributylperoxy)valerate, 2,2-bis(tributylperoxy)butane, 1,1-bis(tributylperoxy)-2-methylcyclohexane, tributyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, trihexyl hydroperoxide, diisophenylpropyl peroxide (Dicumyl) peroxide), 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane, α,α'-bis(tert-butylperoxide)diisopropylbenzene, tert-butylisophenylpropylperoxide, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane-3, isobutylperoxide, 3,5,5-trimethylhexylperoxide, octylperoxide, laurylperoxide, cinnamic acid peroxide, m-toluene (toluoyl) peroxide, benzoyl peroxide, diisopropyl peroxide, bis(4-tert-butylcyclohexyl) peroxide, di-3-methoxybutyl peroxide, di-2-ethylhexyl peroxide, di-dibutyl peroxide, di(3-methyl-3-methoxybutyl) peroxide, di(4-tert-butylcyclohexyl) peroxide, α,α'-bis(neodecanyl) (oyl) peroxide) diisopropylbenzene, isophenylpropyl peroxide neodecanoate, 1,1,3,3'-tetramethylbutyl peroxide neodecanoate, 1-cyclohexyl-1-methylethyl peroxide neodecanoate, trihexyl peroxide neodecanoate, tributyl peroxide neodecanoate, trihexyl peroxide trimethyl acetate, tributyl peroxide trimethyl acetate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxide)hexane, 1,1,3,3-tetramethylbutyl peroxide 2-Ethylhexanoate, 1-cyclohexyl-1-methylethylperoxide-2-ethylhexanoate, trihexylperoxide-2-ethylhexanoate, tributylperoxide-2-ethylhexanoate, tributylperoxide isobutyrate, tributylperoxide maleic acid, tributylperoxide laurylate, tributylperoxide-3,5,5-trimethylhexanoate, tributylperoxide isopropyl monocarbonate, tributylperoxide-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-Di(benzoylperoxide)hexane, tert-butylperoxide acetate, tert-hexylperoxide benzoate, tert-butylperoxide-m-toluene benzoate, tert-butylperoxide benzoate, bis(tert-butylperoxide)isophthalate, tert-butylperoxide allyl monocarbonate, 3,3',4,4'-tetra(tert-butylperoxide carbonyl)benzophenone, etc. These can be used alone or in combination of two or more. Among these organic peroxides, diisophenylpropylperoxide, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane, and α,α'-bis(tert-butylperoxide)diisopropylbenzene are preferred.
[0036] Examples of imidazole compounds include 2-ethyl-4-methylimidazolium, 2-methylimidazolium, 2-ethylimidazolium, 2,4-dimethylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 1-vinyl-2-methylimidazolium, 1-propyl-2-methylimidazolium, 2-isopropylimidazolium, 1-cyanomethyl-2-methylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, and 1-cyanoethyl-2-phenylimidazolium. Among these, 1-cyanoethyl-2-phenylimidazolium and 2-ethyl-4-methylimidazolium exhibit high solubility with the composition of this embodiment. These can be used alone or in combination of two or more.
[0037] Examples of phosphine compounds include, for example, primary phosphine, secondary phosphine, and tertiary phosphine. Specifically, examples of primary phosphine include alkylphosphine such as ethylphosphine and propylphosphine, and phenylphosphine. Specifically, examples of secondary phosphine include dialkylphosphine such as dimethylphosphine and diethylphosphine, diphenylphosphine, methylphenylphosphine, and ethylphenylphosphine. Examples of tertiary phosphine include trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, trialkylphosphine, tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, trimethylstyrylphosphine, tri-p-styrylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, and tri-2-cyanoethylphosphine. Tertiary phosphines are preferred. These compounds can be used alone or in combination of two or more.
[0038] Examples of phosphonium salt compounds include those having tetraphenylphosphonium salts, alkyltriphenylphosphonium salts, and tetraalkylphosphonium. Specifically, examples include tetraphenylphosphonium-isothiocyanate, tetraphenylphosphonium-tetra-p-methylphenylborate, butyltriphenylphosphonium-isothiocyanate, tetraphenylphosphonium-phthalic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, tetrabutylphosphonium-1,2-cyclohexyldicarboxylic acid, and tetrabutylphosphonium-lauric acid. These compounds can be used alone or in combination of two or more.
[0039] The content of component (B) is not particularly limited, but it is preferred to be 0.1 to 10.0 parts by mass relative to 100 parts by mass of component (A), more preferably 0.5 to 5.0 parts by mass, and even more preferably 0.7 to 3.0 parts by mass.
[0040] ((C) component: organic solvent) As for component (C), there are no particular limitations as long as it is used to dissolve component (A). As component (C), for example, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; alcohol solvents such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol, and phenolic resins; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanol, hexanol, cyclopentanol, cyclohexanol, isophorone, and acetophenone; cellosolves such as methyl cellosolve and ethyl cellosolve; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate; and glycol ether solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol mono-n-butyl ether, and tetraethylene glycol mono-n-butyl ether. One or more of these solvents can be used simultaneously. Among these, aromatic hydrocarbons such as toluene or symmetrical trimethylbenzene with high solubility of component (A) are preferred.
[0041] (C) There is no particular limitation on the amount of the component used, but it is generally acceptable to use the non-volatile component of the composition in this embodiment in the range of about 20 to 65% by mass.
[0042] The composition of this embodiment is prepared according to commonly used methods. Examples of preparation methods include melt mixing, powder mixing, and solution mixing. Furthermore, at this time, other than the necessary components of this embodiment, such as release agents, flame retardants, ion trapping agents, antioxidants, adhesion promoters, stress-reducing agents, colorants, coupling agents, and inorganic fillers, can be incorporated without impairing the effects of this disclosure. Furthermore, the composition of this embodiment may include resins other than those in component (A) above, such as epoxy resins, acrylate compounds, vinyl compounds, benzo[a]azine compounds, and dicis-butenediamine compounds.
[0043] (Mold Release Agent) Regarding the mold release agent, it is added to improve the release properties from the mold. As a mold release agent, for example, palm wax, rice bran wax, candelilla wax, polyethylene, polyethylene oxide, polypropylene, lignite acid, esters of lignite acid with saturated alcohols, 2-(2-hydroxyethylamino)ethanol, ethylene glycol, glycerin, etc., i.e., lignite wax, stearic acid, stearate esters, stearylamine, etc., are all known. One of these can be used alone or in combination of two or more.
[0044] (Flame retardant) Regarding flame retardants, all known types can be used to impart flame retardancy, and there are no particular limitations. Examples of flame retardants include phosphazene compounds, silica compounds, zinc molybdate-supported talc, zinc molybdate-supported zinc oxide, aluminum hydroxide, magnesium hydroxide, molybdenum oxide, etc. One of these can be used alone or in combination of two or more.
[0045] (Ion Scavenger) An ion scavenger is added to capture ionic impurities contained in a liquid resin composition to prevent thermal and hygroscopic degradation. All known ion scavengers can be used, and there are no particular limitations. Examples of ion scavengers include hydrotalcites, bismuth hydroxide compounds, and rare earth oxides. One of these can be used alone, or two or more can be used in combination.
[0046] (Inorganic Filler) Regarding inorganic fillers, various known fillers can be used without particular limitation, as long as they are inorganic fillers that can be used in resin compositions. Examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, boron nitride, silicon dioxide, graphite powder, boehmite, etc. Among these, silicon dioxide is particularly preferred due to its excellent low dielectric loss tangent. One inorganic filler can be used alone or in combination of two or more.
[0047] The average particle size of the inorganic filler can be 50 nm or more, 100 nm or more, or 200 nm or more, or it can be less than 10 μm, 5.0 μm or less, 3.0 μm or less, or 1.0 μm or less. An average particle size of 100 nm to 10 μm or 50 nm to 5.0 μm is preferred, 100 nm to 3.0 μm is more preferred, and 200 nm to 1.0 μm is even more preferred. If the average particle size of the inorganic filler is within the above range, the surface roughness of the sheet can be reduced, thereby improving adhesion to substrates such as polyimide films and copper foils.
[0048] The average particle size of the aforementioned inorganic filler can be taken as the median particle size (d50) of the total particle size distribution calculated by volume. The average particle size can be measured using a particle size distribution measuring device based on laser diffraction scattering.
[0049] It is preferable to treat the inorganic filler with a surface-treated material, preferably a surface-treated material based on a coupling agent, and even more preferably a surface-treated material based on a silane coupling agent. By treating the inorganic filler with the above-mentioned surface-treated material, not only can the dispersibility of the inorganic filler in organic solvents be improved, but the surface roughness of the sheet surface is further reduced, thereby improving the adhesion to substrates such as polyimide films and copper foils.
[0050] Examples of the aforementioned coupling agents include silane coupling agents, titanium coupling agents, and aluminum coupling agents. Examples of the aforementioned silane coupling agents include methacrylic silane, acrylonitrile silane, amino silane, phenylamino silane, imidazole silane, phenyl silane, vinyl silane, and epoxy silane. These can be used alone or in combination of two or more.
[0051] When the resin composition contains inorganic fillers, the content of inorganic fillers is based on the total amount of solid components (non-volatile components) of the resin composition (100% by mass), and can be 5-75% by mass, 5-50% by mass, 5-35% by mass, or 10-30% by mass. If the content of inorganic fillers is 75% by mass or less, there is a tendency to suppress the reduction of adhesion. If the content of inorganic fillers is 5% by mass or more, there is a tendency to fully obtain the effect of reducing dielectric loss tangent and improving heat resistance.
[0052] <Cure> The cured product of this embodiment is obtained by curing the composition of this embodiment. Specifically, it can be obtained by heat treatment of the composition at about 150 to 250°C for about 10 minutes to about 3 hours.
[0053] The shape of the cured product in this embodiment is not particularly limited, but when used for bonding to a substrate, it can be set as a sheet with a film thickness of about 1 to 200 μm, preferably about 3 to 100 μm, and the film thickness can be adjusted appropriately according to the application.
[0054] <Sheet> The sheet of this embodiment includes the composition and substrate of this embodiment. The sheet of this embodiment is obtained, for example, by coating the composition of this embodiment onto a substrate (sheet substrate) and drying it. Examples of such substrates include organic substrates made from polyimide, polyimide-silica mixtures, polyimide, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polystyrene resin (PSt), polycarbonate resin (PC), acrylonitrile-butadiene-styrene resin (ABS), polyethylene terephthalate, phenolic resin, phthalic acid, hydroxynaphthalic acid, and p-hydroxybenzoic acid, such as aromatic polyester resins (so-called liquid crystal polymers; manufactured by KURARAY CO., LTD., "Vexter", etc.). Among these, from the viewpoint of heat resistance and dimensional stability, polyimide films, especially polyimide-silica mixture films, are preferred. Furthermore, the aforementioned substrates can be made of metals such as glass, iron, aluminum, alloy 42, and copper, or inorganic substrates such as ITO, silicon, and silicon carbide. The thickness of the aforementioned substrates can be appropriately set according to the application.
[0055] <Laminated Body> The laminated body of this embodiment is obtained by further hot-pressing a substrate onto the bonding surface (the side of the layer formed using the composition of this embodiment) of the above-mentioned sheet. As such a substrate, organic substrates such as polyimide, polyimide-silica mixture, polyimide, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate resin (PMMA), polystyrene resin (PSt), polycarbonate resin (PC), acrylonitrile-butadiene-styrene resin (ABS), polyethylene terephthalate, phenolic resin, phthalic acid, hydroxynaphthalic acid, and p-hydroxybenzoic acid are used. Furthermore, as the aforementioned substrate, metals such as glass, iron, aluminum, 42 alloy, and copper, as well as inorganic substrates such as ITO, silicon, and silicon carbide are preferred. The thickness of the aforementioned substrate can be appropriately set according to the application. Additionally, this laminate can be further subjected to heat treatment.
[0056] <Printed Substrate and Printed Circuit Board> The printed substrate of this embodiment uses either the sheet material described above or the multilayer material described above. The printed substrate of this embodiment is obtained, for example, by further bonding the bonding surface of the sheet material to the inorganic substrate surface of the multilayer material. It is preferable to use a polyimide film as the organic substrate and a metal foil (especially copper foil) as the inorganic substrate. Furthermore, a circuit is formed by soft etching the metal surface of the printed substrate, and the sheet material is further bonded thereon and hot-pressed to obtain a printed circuit board. [Example]
[0057] Hereinafter, the present disclosure will be specifically described by way of examples and comparative examples, but the present disclosure is not limited to these. Furthermore, in each example, unless otherwise stated, parts and percentages are based on quality.
[0058] [Molecular Weight] The molecular weight of the maleic anhydride resin was determined by GPC (gel permeation chromatography). 50 μL of sample was injected into columns heated to 30°C (one GL-R420 (manufactured by Hitachi High-Tech Fielding Corporation), one GL-R430 (manufactured by Hitachi High-Tech Fielding Corporation), and one GL-R440 (manufactured by Hitachi High-Tech Fielding Corporation). The sample was obtained by dissolving the maleic anhydride resin in tetrahydrofuran (THF) to a concentration of 3% by mass. THF was used as the developing solvent, and the determination was performed at a flow rate of 1.6 mL / min. Furthermore, as a detector, an L-3350 RI detector (manufactured by Hitachi, Ltd.) was used, and the weight-average molecular weight (Mw) was calculated by using a molecular weight / dissolution time curve prepared using standard polystyrene (manufactured by TOSOH CORPORATION) from the dissolution time.
[0059] <Synthesis of maleic diacetylimine resin> (Synthesis Example 1) 29.67 parts by mass of 4,4'-(hexafluoroisopropylidene) phthalic anhydride (manufactured by DAIKIN INDUSTRIES, LTD., the compound represented by formula (1)), 129.37 parts by mass of T-SOL 100 (manufactured by ENEOS Corporation, an aromatic high-boiling solvent) and 27.81 parts by mass of Solmix A-11 (manufactured by JAPAN ALCOHOL TRADING COMPANY LIMITED, an alcohol solvent) were added to a 1L flask equipped with a cooler, a nitrogen inlet pipe, a thermocouple, and a stirrer. After addition, the temperature was raised to 80°C and held for 0.5 hours, and 33.50 parts by mass of dimerized diamine (product name "PRIAMINE1075", manufactured by Croda Japan KK) were added dropwise. After dropwise addition, 5.30 parts by weight of 4,4'-methylenediphenylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) were added. Following this, 1.71 parts by weight of an aqueous solution of methanesulfonic acid (manufactured by BASF, product name "Lutropur MSA") was added. The temperature was then raised to 160°C. After heating, 40.00 parts by weight of toluene (manufactured by Yamaichi Chemical Industries Co., Ltd.) were added, and a dehydration and ring-closing reaction was carried out at 160°C for 1 hour to remove water and alcohol from the reaction solution, thereby obtaining the intermediate polyimide resin. Next, the obtained polyimide resin was cooled to 130°C, and 6.56 parts by weight of maleic anhydride (manufactured by Fuso Chemical Co., Ltd.) were added. The temperature was then raised to 160°C, and a dehydration and ring-closing reaction was carried out at 160°C for 4 hours to remove water from the reaction solution, thereby obtaining maleic anhydride resin (bismaleic anhydride resin).
[0060] The obtained bis(cis-butenediamide) resin was added to a separatory funnel, and 500 parts by weight of pure water were added. The separatory funnel was shaken and allowed to stand. After standing, the aqueous layer and the organic layer separated, and only the organic layer was recovered. The recovered organic layer was placed into a 1L glass container equipped with a cooler, a nitrogen inlet pipe, a thermocouple, a stirrer, and a vacuum pump. The temperature was raised to 88-93°C and the water was removed. Then, the temperature was raised to 100°C, and the solvent was removed for 0.5 hours under a pressure reduction of 0.1 MPa from atmospheric pressure, thereby obtaining the bis(cis-butenediamide) resin of component (A) (A-1).
[0061] (Synthesis Example 2) The proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene)diimid resin (A-2) was obtained in the same manner as in Synthesis Example 1.
[0062] (Synthesis Examples 3 to 4) 4,4'-methylenediphenylamine was replaced with norbornenediamine (manufactured by MITSUI FINE CHEMICALS,INC Co.,Ltd.), and the proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butenediamide) resins (A-3) to (A-4) were obtained in the same manner as in Synthesis Example 1.
[0063] (Synthesis Example 5) 4,4'-methylenediphenylamine was replaced with 1,3-diaminopropane (manufactured by FUJIFILM Wako Pure Chemical Corporation), and the proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene)diimid resin (A-5) was obtained in the same manner as in Synthesis Example 1.
[0064] (Synthesis Examples 6 to 7) 4,4'-methylenediphenylamine was replaced with 2-methyl-1,5-diaminopentane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene)diimid resins (A-6) to (A-7) were obtained in the same manner as in Synthesis Example 1.
[0065] (Synthesis Examples 8 to 9) 4,4'-methylenediphenylamine was replaced with norbornenediamine (manufactured by MITSUI FINE CHEMICALS,INC Co.,Ltd.) and 4,4'-(hexafluoroisopropylidene) phthalic anhydride was replaced with 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (manufactured by New Japan Chemical Co., Ltd., product name "TDA-100", compound represented by formula (2)). The proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene)diimid resins (A-8) to (A-9) were obtained in the same manner as in Synthesis Example 1.
[0066] (Synthesis Examples 10 to 11) 4,4'-methylenediphenylamine was replaced with 2-methyl-1,5-diaminopentane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4,4'-(hexafluoroisopropylidene) phthalic anhydride was replaced with 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (manufactured by New Japan Chemical Co., Ltd., product name "TDA-100", compound represented by formula (2)). The proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene)diimid resins (A-10) to (A-11) were obtained in the same manner as in Synthesis Example 1.
[0067] (Synthesis Example 12) Instead of using 4,4'-methylenediphenylamine, 4,4'-(hexafluoroisopropylidene) phthalic anhydride was replaced with pyrolithic anhydride (manufactured by Daicel Corporation, product name "PMDA"), and the proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene diimide) resin (A-12) was obtained in the same manner as in Synthesis Example 1.
[0068] (Synthesis Example 13) 4,4'-methylenediphenylamine was replaced with 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene (manufactured by Tokyo Chemical Industry Co., Ltd., also known as "bisphenylamine M") and 4,4'-(hexafluoroisopropyl)diphthalic anhydride was replaced with 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (manufactured by New Japan Chemical Co., Ltd., product name "TDA-100", compound represented by formula (2)). The proportions of each component were changed as shown in Table 1. Otherwise, bis-cis-butene diimide resin (A-13) was obtained in the same manner as in Synthesis Example 1.
[0069] (Synthesis Example 14) 4,4'-methylenediphenylamine was replaced with norbornenediamine (manufactured by MITSUI FINE CHEMICALS, INC Co., Ltd.) and 4,4'-(hexafluoroisopropylidene) phthalic anhydride was replaced with 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Zhejiang Alpha Chemical Technology Co., Ltd., product name "AMC-550", compound represented by formula (6)). The proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene)diimid resin (A-14) was obtained in the same manner as in Synthesis Example 1.
[0070] (Synthesis Example 15) 4,4'-methylenediphenylamine was replaced with norbornenediamine (manufactured by MITSUI FINE CHEMICALS, INC Co., Ltd.) and 4,4'-(hexafluoroisopropylidene) phthalic anhydride was replaced with 4,4'-oxyphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., also known as "ODPA"). The proportions of each component were changed as shown in Table 1. Otherwise, bis(cis-butene)diimide resin (A-15) was obtained in the same manner as in Synthesis Example 1.
[0071] [Table 1] bis(cis-butene)diimid resin A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 (a1) Ingredients Compound of formula (1) 29.67 33.94 29.70 33.94 31.82 31.82 36.06 - - - - - - - - Compound (2) - - - - - - - 24.35 25.79 24.35 27.22 - 27.46 - - Compound of formula (6) - - - - - - - - - - - - - 27.34 - ODPA - - - - - - - - - - - - - - 27.16 Pyrolithic anhydride - - - - - - - - - - - 17.36 - - - (a2) Components Dimeric diamine 33.50 27.35 33.50 27.35 35.89 35.89 29.06 40.68 30.76 40.68 32.47 56.97 32.76 37.03 43.87 4,4'-Methylenediphenylamine 5.30 10.10 - - - - - - - - - - - - - Norbornenediamine - - 4.13 7.86 - - - 5.01 8.84 - - - - 10.64 5.40 1,3-Diaminopropane - - - - 2.12 - - - - - - - - - - 2-Methyl-1,5-diaminopentane - - - - - 3.33 6.29 - - 3.77 7.03 - - - - Bisphenylamine M - - - - - - - - - - - - 21.02 - - (a3) Components maleic anhydride 6.56 7.49 6.56 7.49 7.02 7.02 7.96 7.96 8.43 7.96 8.90 7.80 8.97 10.15 8.58 catalyst methane tannic acid aqueous solution 1.71 1.96 1.71 1.96 1.84 1.84 2.08 2.08 2.20 2.08 2.33 2.04 2.35 2.65 2.24 solvent T-SOL 100 129.37 135.04 127.18 130.87 132.00 134.24 135.23 132.69 124.21 130.40 126.83 140.61 113.94 104.43 104.95 Solmix A-11 27.81 29.45 27.41 28.70 28.59 29.00 29.79 29.33 28.10 28.92 28.88 30.67 20.72 18.99 19.08 Toluene 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 Mw 14500 10300 15100 12000 12300 15100 13700 10900 9200 11400 9100 16800 6,900 8,600 13,400 (a1) Mole number of component / (a2) mole count of component 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75
[0072] [Examples 1-13 and Comparative Examples 1-2] <Preparation of Resin Composition and Cured Sheet> A maleic anhydride resin composition was prepared by mixing the components shown in Table 2 with the compositions shown below. Next, using an applicator, the above-mentioned maleic anhydride resin composition was applied to a Cu foil (manufactured by FURUKAWA ELECTRIC CO., LTD., product name: FZ-WS-18) to a thickness of 100 μm after drying, and dried at 130°C for 30 minutes using a dryer. Then, it was cured at 200°C for 2 hours using a dryer. After curing, it was cooled to room temperature, and the copper foil was removed by etching with an ammonium persulfate aqueous solution, and then dried at 110°C for 30 minutes to produce a cured sheet.
[0073] (A) Composition: maleic diimide resin The maleic diimide resin (A-1) to (A-15) prepared in Synthesis Examples 1 to 12 above (B) Composition: Polymerization initiator (B-1) DCP (manufactured by NOF CORPORATION, product name "PERCUMYL D", diisophenylpropyl peroxide) (C) Composition: Organic solvent (C-1) Toluene (manufactured by Yamaichi Chemical Industries Co., Ltd.)
[0074] [Determination of Elastic Modulus and Tg] Test specimens with a sample size of 20 mm × 10 mm were prepared using cured sheets. The elastic modulus and Tg (tanδ peak) at 20 °C were measured using a dynamic viscoelasticity measuring device (manufactured by SII NanoTechnology Inc., product name "DMS6100") under the conditions of a frequency of 1 Hz, a measurement temperature of -40 °C to 220 °C, and a heating rate of 10 °C / min. The results are shown in Table 2.
[0075] [Coefficient of Linear Expansion (CTE)] A test piece with dimensions of 30 mm × 4 mm was prepared from the cured sheet. Using this test piece, the coefficient of linear expansion (CTE) was determined using a thermomechanical analysis apparatus (product name "TMA / SS7100", manufactured by Hitachi High-Tech Science Corporation). The measurement mode was set to tensile mode, the measurement load was set to 50 mN, the measurement environment was set to atmospheric environment, the heating rate was set to 5 °C / min, and the measurement results at 110–160 °C in the second round were set as CTE. The results are shown in Table 2.
[0076] [5% Weight Loss Temperature] 6.0–10.0 mg of cured sheet was weighed into an open sample container (manufactured by Seiko Instruments Inc., product name "P / N SSC000E030"), and the 5% weight loss temperature (Td5) was determined under nitrogen flow rate of 300 mL / min and heating rate of 10 °C / min. The measuring apparatus used was a TG / DTA7200 (manufactured by Hitachi High-Tech Science Corporation). The results are shown in Table 2.
[0077] [Evaluation of Dielectric Properties] Test pieces with a sample size of 50mm × 100mm were prepared using cured sheets, and the relative permittivity (Dk) and dielectric loss tangent (Df) at 10GHz were measured using an SPDR dielectric resonator (manufactured by Agilent Technologies, Inc.). Based on the measurement results, an evaluation was performed according to the following criteria. A result of A or B indicates very low dielectric properties. The results are shown in Table 2. <Criteria for Dk> A: Less than 2.5 B: 2.5 or higher but less than 2.8 C: 2.8 or higher <Criteria for Df> A: Less than 0.0030 B: 0.0030 or higher but less than 0.0050 C: 0.0050 or higher
[0078] [Table 2] project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 1 Comparative Example 2 (A) Ingredients maleic diimide resin (A-1) 100 - - - - - - - - - - - - - - (A-2) - 100 - - - - - - - - - - - - - (A-3) - - 100 - - - - - - - - - - - - (A-4) - - - 100 - - - - - - - - - - - (A-5) - - - - 100 - - - - - - - - - - (A-6) - - - - - 100 - - - - - - - - - (A-7) - - - - - - 100 - - - - - - - - (A-8) - - - - - - - 100 - - - - - - - (A-9) - - - - - - - - 100 - - - - - - (A-10) - - - - - - - - - 100 - - - - - (A-11) - - - - - - - - - - 100 - - - - (A-12) - - - - - - - - - - - - - 100 - (A-13) - - - - - - - - - - - 100 - - - (A-14) - - - - - - - - - - - - 100 - - (A-15) - - - - - - - - - - - - - - 100 (B) Components Polymerization initiator DCP 0.74 0.81 0.80 0.74 0.78 0.85 0.76 0.88 0.77 0.82 0.74 0.77 0.80 0.83 0.85 (C) Components organic solvents Toluene - 8.4 6.2 - 4.2 13.0 1.8 17.6 3.0 8.8 - 2.6 6.6 10.4 13.6 Evaluation Project elastic modulus (GPa) 1.1 2.1 1.8 1.2 1.0 1.2 1.3 1.4 1.7 1.3 1.4 1.3 1.4 0.4 0.8 Tg (°C) 69.9 121.6 77.7 113.8 66.8 68.3 87.5 72.7 114.7 64.8 88.6 116.0 93.0 38.8 46.0 CTE (ppm / ℃) 94 134 123 84 69 44 81 74 102 103 97 97 110 200 112 T d5 (℃) 418 425 412 418 414 410 421 399 405 394 396 408 397 402 405 Dk A B A A A A A A A A A A A A B Df A A A A B B B A B B B A A A A
[0079] As clearly shown in Table 2, the maleic anhydride resin composition of the embodiments exhibits excellent low dielectric properties (low Dk and low Df), high elastic modulus, high Tg, and low CTE as a cured product. Therefore, by using the maleic anhydride resin composition disclosed herein, it is expected that the properties of sealing materials for multilayer boards such as printed circuit boards and electronic components such as semiconductors can be significantly improved.
Claims
1. A resin composition comprising a maleic anhydride resin (A) formed by reacting tetracarboxylic dianhydride (a1), a diamine (a2) and maleic anhydride (a3), wherein the tetracarboxylic dianhydride (a1) comprises at least one of the compounds represented by formula (1), the compounds represented by formula (2) and the compounds represented by formula (6), and the diamine (a2) comprises a dimer diamine and a second diamine other than the dimer diamine, [Chemical 1][Chemical 2][Chemical 3].
2. The resin composition as claimed in claim 1, wherein the aforementioned second diamine comprises at least one selected from the group consisting of 1,3-diaminopropane, norbornene diamine, 4,4'-methylenediphenylamine and 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene.
3. The resin composition as claimed in claim 1, wherein the aforementioned dimer diamine comprises at least one of the compounds represented by the following general formula (3) and the compounds represented by the following general formula (4), [Chemical 4][Chemical 5] In formulas (3) and (4), m, n, p and q respectively represent integers of 1 or more selected in such a way as m+n=6~17, p+q=8~19, and the bonds represented by dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. In the case where the bonds represented by dashed lines are carbon-carbon double bonds, formulas (3) and (4) have the following structure: the structure obtained by subtracting 1 from the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond.
4. The resin composition as claimed in claim 1, wherein the aforementioned maleic diimide resin (A) has a weight average molecular weight of 3,000 to 25,000.
5. A cured product, which is a cured product of the resin composition described in any one of claims 1 to 4.
6. A sheet comprising the resin composition and substrate described in any one of claims 1 to 4.
7. The sheet as described in claim 6, wherein the aforementioned substrate is an organic substrate.
8. The sheet as described in claim 6, wherein the aforementioned substrate is an inorganic substrate.
9. A laminate obtained by further heat-pressing a substrate onto the bonding surface of the sheet described in claim 6.
10. A printed circuit board made using the sheet described in claim 6.
11. A printed circuit board formed using the laminate described in claim 9.