Resin composition for electronic component, cured product, and sheet

Abstract

To provide a resin composition for electronic components, capable of forming a cured product layer which has high heat resistance and exhibits a low dielectric dissipation factor.SOLUTION: The present disclosure relates to a resin composition for electronic components that comprises a reaction product of (A) a polyester polyol, which is a polymer of reaction components including an aromatic polycarboxylic acid (a1) and a polyol (a2), (B) a polyisocyanate, and (C) an amine, and also relates to a cured product of the resin composition and to a sheet formed from the cured product.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition for electronic components, a cured product, and a sheet. [Background technology]

[0002] Information terminals for mobile phones and smartphones, and electronic substrates such as flexible printed wiring boards and rigid printed circuit boards, are becoming smaller, more powerful, and more functional, leading to an increased use of signals with high frequencies. As these frequencies increase, a decrease in output signal that can lead to the recognition of erroneous information, i.e., transmission loss, becomes more likely. For this reason, resin compositions with low dielectric loss tangents are often used in such terminals and substrates.

[0003] As such a resin composition, for example, an aromatic polyester having a plurality of specified repeating structural units is known (Patent Document 1). Because of the aromatic structure, this resin is characterized by a low dielectric loss tangent and high heat resistance. However, in cases where higher heat resistance is required, this resin does not achieve both a low dielectric loss tangent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-002296 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin composition for electronic parts that provides a cured layer having high heat resistance and a low dielectric loss tangent. [Means for solving the problem]

[0006] The present inventors have conducted extensive research and have found a solution to the above problems, thereby completing the present invention. That is, the present invention relates to the following resin composition for electronic components, a cured product, and a sheet.

[0007] 1. A resin composition for electronic components, comprising a reaction product of a polyester polyol (A), which is a polymer of reaction components including a polycarboxylic acid (a1) including an aromatic polycarboxylic acid (a1-1) and a polyol (a2), a polyisocyanate (B), and an amine (C).

[0008] 2. A cured product of the resin composition for electronic parts described in the preceding paragraph 1.

[0009] 3. A sheet formed from the cured product described in the preceding paragraph 2. [Effects of the Invention]

[0010] The resin composition for electronic parts of the present invention gives a cured layer or sheet having high heat resistance and a low dielectric loss tangent. DETAILED DESCRIPTION OF THE INVENTION

[0011] The resin composition for electronic components of the present invention contains a reaction product of polyester polyol (A) (hereinafter referred to as component (A)), which is a polymer of polycarboxylic acid (a1) containing aromatic polycarboxylic acid (a1-1) (hereinafter referred to as component (a1-1)) and reaction components containing polyol (a2) (hereinafter referred to as component (a2)), polyisocyanate (B) (hereinafter referred to as component (B)), and amine (C) (hereinafter referred to as component (C)).

[0012] Component (A) is a polyester polyol that allows the cured product to exhibit a low dielectric tangent. In the present invention, it is a polymer of reaction components including components (a1) and (a2).

[0013] The component (a1) contains the component (a1-1). By using the component (a1-1), the cured product tends to exhibit a low dielectric tangent.

[0014] Examples of the component (a1-1) include aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, diphenylmethane-4,4'-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic anhydride, and 2,3-naphthalenedicarboxylic anhydride; Aromatic tricarboxylic acids such as trimellitic acid, trimellitic anhydride, 1,2,3-benzenetricarboxylic acid, and 1,3,5-benzenetricarboxylic acid; aromatic tetracarboxylic acids such as 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic dianhydride), 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride; Examples include esters of these carboxylic acids (monoesters, diesters, triesters, tetraesters), etc. These may be used alone or in combination of two or more.

[0015] Among these, aromatic dicarboxylic acids are preferred because the cured product is likely to have a low dielectric loss tangent, and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, phthalic acid esters, isophthalic acid esters, and terephthalic acid esters are more preferred.

[0016] The molar ratio of the (a1-1) component relative to 100 mol % of the (a1) component is preferably 60 mol % or more, more preferably 70 mol % or more, and even more preferably 80 mol % or more, since the cured product is likely to have a low dielectric tangent.

[0017] As the component (a1), a polycarboxylic acid (a1-2) other than the component (a1-1) (hereinafter referred to as the component (a1-2)) can also be used.

[0018] Examples of the component (a1-2) include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, undecanoic acid, dodecanedioic acid, tridecanedioic acid, and hydrogenated dimer acid; Alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydrophthalic anhydride, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; Unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, and dimer acid; Aliphatic tricarboxylic acids such as 1,2,3-propanetricarboxylic acid and 1,3,5-pentanetricarboxylic acid; Alicyclic tricarboxylic acids such as cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic anhydride, and cyclohexane-1,3,5-tricarboxylic acid; Examples include esters (monoesters, diesters, triesters) of these carboxylic acids, which may be used alone or in combination of two or more.

[0019] Among these, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids are preferred, and aliphatic dicarboxylic acids are more preferred, since the cured product is likely to have low dielectric properties.

[0020] The molar ratio of the (a1-2) component relative to 100 mol % of the (a1) component is preferably 40 mol % or less, more preferably 30 mol % or less, and even more preferably 20 mol % or less, since the cured product is likely to have a low dielectric tangent.

[0021] The component (a2) is a compound having two or more hydroxy groups.

[0022] Examples of the component (a2) include: alkanediols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; Alkylalkanediols such as neopentyl glycol, 1,2-propanediol (propylene glycol), 2-methyl-1,3-propanediol, butylethylpropanediol, and 3-methyl-1,5-pentanediol; alkanetriols such as trimethylolethane, trimethylolpropane, glycerin, 1,2,4-butanetriol, and 1,2,6-hexanetriol; tetraols such as pentaerythritol and diglycerin; cycloalkanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and ethylene oxide adducts of hydrogenated bisphenol A; Aryl diols such as catechol, xylylene glycol, and ethylene oxide adducts of bisphenol A; Dimer polyols such as dimer diol and hydrogenated dimer diol; Polyalkylene polyols such as polyethylene glycol, polypropylene glycol, and polypropylene triol; Examples include polyolefin polyols such as polybutadiene polyol, polyisoprene polyol, polyhexadiene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and hydrogenated polyhexadiene polyol; castor oil polyol, etc. These may be used alone or in combination of two or more.

[0023] Commercially available products of component (a2) include, for example, "Pripol2033" (manufactured by Equus Japan Co., Ltd.), "SOVERMOL908" (manufactured by BASF), "PEG300", "PEG400", "PEG600", "PEG1000", and "PEG1500" (all manufactured by Sanyo Chemical Industries, Ltd.), "SANNIX PP-400", "SANNIX PP-600", "SANNIX PP-950", and "SANNIX PP-1000" (all manufactured by Sanyo Chemical Industries, Ltd.), "SANNIX GP-400", "SANNIX GP-600", "SANNIX GP-1000", and "SANNIX GP-1500" (all manufactured by Sanyo Chemical Industries, Ltd.), "NISSO-PB G-1000", "NISSO-PB G-2000", "NISSO-PB G-3000", "NISSO-PB GI-1000", "NISSO-PB GI-2000", and "NISSO-PB GI-3000" (all manufactured by Nippon Soda Co., Ltd.), "Poly bd", "Poly ip", and "EPOL" (all manufactured by Idemitsu Kosan Co., Ltd.).

[0024] Among these, alkanediols and alkylalkanediols are preferred, and alkylalkanediols are more preferred, since the cured product is likely to exhibit a low dielectric loss tangent.

[0025] The molar ratio of the (a1) component and the (a2) component is preferably (a1) component / (a2) component=25 / 75 to 50 / 50, and more preferably 33 / 67 to 45 / 55, where the total molar ratio of the (a1) component and the (a2) component is 100 mol %, in order to convert the molecular terminals of the polyester resin (A) into hydroxy groups and to facilitate reaction with the polyisocyanate (B) described below.

[0026] Component (A) is obtained by reacting components (a1) and (a2). These components may be reacted all at once or sequentially. Regarding reaction conditions, for example, the temperature is usually 150 to 270°C, preferably 150 to 250°C. The reaction time can be freely set as long as the reaction proceeds sufficiently and component (A) is obtained.

[0027] In the reaction, for example, a catalyst such as zinc acetate, tetrabutyl titanate, antimony trioxide, or dibutyltin oxide; an organic solvent as described below; and the like may be used.

[0028] The physical properties of the component (A) obtained by the reaction include, for example, a glass transition temperature (Tg) of preferably 0 to 100° C., more preferably 10 to 100° C., and even more preferably 20 to 100° C., because the cured product is likely to exhibit excellent heat resistance. The glass transition temperature (Tg) of the component (A) refers to a value measured with a commercially available differential scanning calorimeter (DSC).

[0029] The hydroxyl value of component (A) is preferably 10 to 125 mgKOH / g, more preferably 15 to 120 mgKOH / g, and even more preferably 20 to 115 mgKOH / g, in order to facilitate reaction with component (B), which will be described later. The hydroxyl value of component (A) is the value measured in accordance with JIS K-0070.

[0030] Furthermore, from the viewpoint of facilitating reaction with component (B), which will be described later, the number average molecular weight of component (A) is preferably 250 to 10,000, more preferably 500 to 8,000, and even more preferably 1,000 to 5,000. The number average molecular weight of component (A) refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0031] The molar ratio of component (A), relative to the total of components (A), (B), and (C) being 100 mol %, is preferably 10 to 70 mol %, more preferably 10 to 50 mol %, and even more preferably 10 to 30 mol %, because the cured product is likely to exhibit a low dielectric tangent and excellent heat resistance.

[0032] Component (B) is a compound with two or more isocyanate groups in its molecule. When component (B) is used, the hydroxyl groups at the terminals of component (A) are consumed through a reaction, making the cured product more likely to exhibit a low dielectric tangent.

[0033] Examples of component (B) include: aliphatic polyisocyanates such as methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer diisocyanate in which the carboxyl group of a dimer acid is substituted with an isocyanate group; Alicyclic polyisocyanates such as cyclohexane-1,2-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,2-di(isocyanatomethyl)cyclohexane (hydrogenated o-xylylene diisocyanate), 1,3-di(isocyanatomethyl)cyclohexane (hydrogenated m-xylylene diisocyanate), 1,4-di(isocyanatomethyl)cyclohexane (hydrogenated p-xylylene diisocyanate), and methylcyclohexane diisocyanate; Aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-diphenyltetramethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, 1,2-di(isocyanatomethyl)benzene (o-xylylene diisocyanate), 1,3-di(isocyanatomethyl)benzene (m-xylylene diisocyanate), 1,4-di(isocyanatomethyl)benzene (p-xylylene diisocyanate), m-tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, and 4,4'-dibenzyl isocyanate; Examples include amino acid polyisocyanates such as lysine diisocyanate. Furthermore, as the component (B), the nurate, adduct, biuret, and allophanate forms of the component (B) can also be used, either alone or in combination of two or more.

[0034] Among these, alicyclic polyisocyanates are preferred, and isophorone diisocyanate is more preferred, since the cured product is likely to exhibit a low dielectric loss tangent.

[0035] The molar ratio of component (B), relative to the total of components (A), (B), and (C) being 100 mol %, is preferably 30 to 60 mol %, more preferably 35 to 55 mol %, and even more preferably 45 to 50 mol %, since the cured product is likely to exhibit excellent heat resistance.

[0036] Component (C) is a compound with one or more amino groups in its molecule. When component (C) is used, a urea bond is formed through a reaction, and the strong hydrogen bonds form, which tends to increase the melting temperature (heat resistance) of the cured product.

[0037] Examples of component (C) include: Monoalkyl monoamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine (amylamine), isopentylamine, n-hexylamine, isohexyl monoamine, n-heptylamine, isoheptylamine, n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, isodecylamine, n-undecylamine, n-dodecylamine (laurylamine), tridecylamine, tetradecylamine (myristylamine), pentadecylamine, hexadecylamine (cetylamine), heptadecylamine, octadecylamine (n-stearylamine), and isooctadecylamine (isostearylamine); Monoalkenyl monoamines such as vinylamine, allylamine, butenylamine, pentenylamine, hexenylamine, heptenylamine, octenylamine, nonenylamine, decenylamine, undecenylamine, dodecenylamine, tridecenylamine, tetradecenylamine, pentadecenylamine, hexadecenylamine, heptadecenylamine, octadecenylamine (oleylamine, etc.), nonadecenylamine, icosenylamine, and dodecenylamine; Dimethylamine, N-ethylmethylamine, diethylamine, N-ethyl-N-(n-propyl)amine, di-n-propylamine, diisopropylamine, methylisopropylamine, n-propylisopropylamine, di-n-butylamine, diisobutylamine, di-s-butylamine, di-t-butylamine, Nn-butylethylamine, Ns-butylethylamine, Nt-butylethylamine, Nn-butylpropylamine, Ns-butylpropylamine, Nt-butylpropylamine, Nt-butylisopropylamine, di-n-pentene dialkyl monoamines such as diethylamine (diamylamine), diisopentylamine (diisoamylamine), di-n-hexylamine, di-n-heptylamine, di-n-octylamine, bis(2-ethylhexylamine), dinonylamine, didecylamine, diundecylamine, didodecylamine (dilaurylamine), ditridecylamine, ditetradecylamine (dimyristylamine), dipentadecylamine, dihexadecylamine (dipalmitylamine), diheptadecylamine, and dioctadecylamine (distearylamine); Dialkenylamines such as divinylamine, diallylamine, dibutenylamine, dipentenylamine, dihexenylamine, diheptenylamine, dioctenylamine, dinonenylamine, didecenylamine, diundecenylamine, didodecenylamine, ditridecenylamine, ditetradecenylamine, dipentadecenylamine, dihexadecenylamine, diheptadecenylamine, dioctadecenylamine, dinonadecenylamine, diicosenylamine, and didodecenylamine; cycloalkyl monoamines such as cyclopentylamine, N-methylcyclopentylamine, N-ethylcyclopentylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, cycloheptylamine, cyclooctylamine, isophorone amine, and N-methylisophorone amine; Aryl monoamines such as aniline, methylaniline, dimethylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, isobutylaniline, n-pentylaniline, n-hexylaniline, nonylaniline, dodecylaniline, benzylamine, and phenethylamine; alkylene diamines such as ethylenediamine, 1,3-propanediamine, propane-1,2-diamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,2-pentamethylenediamine, 1,3-pentamethylenediamine, 1,4-pentamethylenediamine, 1,5-pentamethylenediamine, 1,2-hexamethylenediamine, 1,3-hexamethylenediamine, 1,4-hexamethylenediamine, 1,5-hexamethylenediamine, 1,6-hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine; cycloalkanediamines such as 1,2-cyclopentanediamine, 1,3-cyclopentanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-dimethyl-3,3'-diaminodicyclohexylmethane, 4,4-diaminodicyclohexylpropane, isophoronediamine, diaminonorbornane, bis(aminomethyl)norbornane, and 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0.2.6]decane; Alkylenetriamines such as diethylenetriamine, dipropylenetriamine, and dibutylenetriamine; Alkylenetetramines such as triethylenetetramine and tripropylenetetramine; Monoalkanol monoamines such as methanolamine, ethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-propylethanolamine, N-isopropylethanolamine, Nn-butylethanolamine, N-isobutylethanolamine, Ns-butylethanolamine, Nt-butylethanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 3-amino-1-butanol, 4-amino-1-butanol, N-methylbutanolamine, N-ethylbutanolamine, Nn-propylbutanolamine, N-isopropylbutanolamine, Nn-butylbutanolamine, N-isobutylbutanolamine, 5-amino-1-pentanol, 6-aminohexanol, 7-aminoheptanol, 8-aminooctanol, N-phenylethanolamine, N-benzylethanolamine, etc. Dialkanol monoamines such as 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, diethanolamine, diisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-isobutyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, and N-butyldiisopropanolamine; Hydroxyalkyl alkylenediamines such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)propylenediamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, N-(2-hydroxypropyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)propylenediamine, N,N'-bis(2-hydroxypropyl)ethylenediamine, and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine trialkanolamines such as triethanolamine and triisopropanolamine; Monoalkanoldiamines such as 1,3-diamino-2-hydroxypropane and N-(β-aminoethyl)ethanolamine; Hexaalkanoldiamines such as 1,3-bis[tris(hydroxymethyl)methylamino]propane; Hydrazine or its derivatives (adipic acid hydrazide, etc.) can be mentioned. These can be used alone or in combination of two or more.

[0038] Of these, cycloalkanediamines are preferred, and isophoronediamine is more preferred, as they tend to increase the heat resistance of the cured product.

[0039] The molar ratio of component (C), relative to the total of components (A), (B), and (C) being 100 mol %, is preferably 10 to 45 mol %, more preferably 15 to 40 mol %, and even more preferably 20 to 35 mol %, since this tends to increase the heat resistance of the cured product.

[0040] The reaction components may further contain a monoalcohol (D) (hereinafter referred to as component (D)).

[0041] Examples of the component (D) include methanol, ethanol, n-propanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, t-butyl alcohol, etc. These may be used alone or in combination of two or more.

[0042] When the (D) component is used, the molar ratio of the (D) component is preferably 15 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less, relative to 100 mol % of the total of the (A), (B), (C), and (D) components.

[0043] The polymer of the present invention is obtained by reacting components (A), (B), and (C), and optionally, component (D). These components may be reacted all at once or sequentially, and the order and method of addition may be freely selected. Regarding reaction conditions, for example, the temperature is usually 50 to 180°C, preferably 80 to 140°C. The reaction time is usually 3 to 10 hours, preferably 5 to 8 hours.

[0044] The reaction may be carried out continuously after the aforementioned component (A) is produced, or may be carried out after the obtained component (A) is cooled and removed.

[0045] The reaction may involve the use of an organic solvent.

[0046] Examples of organic solvents include aromatic hydrocarbons such as T-SOL100 and T-SOL150 (both manufactured by ENEOS Corporation), toluene, and xylene; alkanes such as hexane, heptane, octane, and decane; cycloalkanes such as cyclohexane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, methoxypropyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl cellosolve, and butyl cellosolve; ethers such as dioxane and tetrahydrofuran; and aprotic polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, and dimethylformamide. These may be used alone or in combination of two or more.

[0047] The content of the organic solvent is preferably adjusted so that the reaction concentration is 20 to 95% by weight, more preferably 30 to 80% by weight.

[0048] As for the physical properties of the obtained polymer, for example, the number average molecular weight is preferably 5,000 to 100,000, more preferably 8,000 to 100,000, and even more preferably 10,000 to 100,000, from the viewpoint that the heat resistance of the cured product is likely to be enhanced. The number average molecular weight of the polymer refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC method).

[0049] The resin composition for electronic components of the present invention may contain the organic solvent described above, and is adjusted so that the non-volatile content of the resin composition for electronic components is preferably 0.1% by mass to 85% by mass, more preferably 0.5% by mass to 75% by mass, and even more preferably 1% by mass to 70% by mass.

[0050] The resin composition for electronic parts of the present invention may further contain additives such as resins such as acrylic resins, urethane resins, and epoxy resins; metal compounds such as metal oxides, metal nitrides, and metal carbides; alloy powders, curing agents, surface conditioners, pigments, fillers, mold release agents, flame retardants, viscosity modifiers, plasticizers, antibacterial agents, ultraviolet absorbers, antifungal agents, antifoaming agents, colorants, and stabilizers. These may be used alone or in combination of two or more.

[0051] The resin composition for electronic parts of the present invention can be obtained by mixing the polymer and, if necessary, an organic solvent and additives. The method and order of adding the components are not particularly limited.

[0052] A cured product of the resin composition for electronic components is also an embodiment of the present invention. For example, the cured product may be produced by heating the resin composition for electronic components to melt it and then molding it.

[0053] Examples of molding methods include injection molding, blow molding (hollow molding, blow molding), extrusion molding, thermoforming (sheet molding), calendar molding, rotational molding, lamination molding, transfer molding, compression molding, and vacuum molding.

[0054] In addition to the cured product layer of the present invention, an anchor layer, a pattern ink layer, an easy-adhesion layer, a substrate layer, a functional layer, an adhesive layer, etc. may be provided during molding.

[0055] Examples of the substrate used for the substrate layer include metal, plastic film, release film, glass, etc. These may be used alone or in combination of two or more.

[0056] Examples of metals include iron, copper, silver, aluminum, aluminum-plated steel sheet, tin-free steel sheet, stainless steel sheet, zinc phosphate-treated sheet, zinc / zinc alloy-plated steel sheet (bonded steel sheet), and the like.

[0057] Examples of plastic films include polyesters such as acetonitrile-butadiene-styrene (ABS), polycarbonate, polyethylene, polypropylene, polyethylene terephthalate, and polyethylene naphthalate; acrylics such as polymethyl methacrylate; fluorine-based resins such as polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), and polyvinylidene fluoride (PVDF); polyimide, polyamide, polyphenylene ether, polyphenylene sulfide, polystyrene, polycarbonate, liquid crystal polymer, and cycloolefin polymer. Plastic films that have a metal pattern printed on the surface or that have a metal or metal oxide vapor-deposited on them can also be used.

[0058] A release film is a film in which a release agent is applied to the surface of a substrate, and is classified into heavy release films, medium release films, and light release films depending on the force required to release the film.

[0059] The sheet of the present invention is formed from the cured product, and the forming method is the same as that described in the previous paragraph.

[0060] Regarding the physical properties of the cured product or sheet of the present invention, for example, the melting temperature is preferably 100 to 200° C., more preferably 120 to 200° C., and even more preferably 135 to 180° C. The melting temperature refers to a value measured using a dynamic viscoelasticity measuring device.

[0061] The dielectric loss tangent of the cured product or sheet is preferably 0.006 or less, and more preferably 0.0045 or less.

[0062] The resin composition for electronic parts of the present invention, when cured or when a sheet formed from the cured product exhibits high heat resistance and a low dielectric loss tangent, can be applied to, for example, semiconductors, circuit boards (e.g., printed wiring boards), televisions, personal computers, mobile phones, smartphones, etc.

[0063] Examples of electronic components include passive components such as resistors, capacitors, inductors, and transformers; connecting components such as switches, touch panels, and connectors; converting components such as sensors and actuators; coils, diodes, transistors, SCRs (silicon-controlled rectifiers), integrated circuits, relays, switching power supplies, high-frequency components, and cables. The resin composition, cured product, or sheet for electronic components of the present invention can be suitably used for bonding electronic components or suppressing noise (electronic, electromagnetic, magnetic, etc.), and more suitably for suppressing noise in electronic components. [Example]

[0064] The present invention will be specifically described below through examples and comparative examples. However, the technical scope of the present invention is not limited thereto. In the examples, "parts" and "%" are by weight unless otherwise specified.

[0065] (number average molecular weight) The number average molecular weight of the polyester polyol (A) or the reaction product was measured in terms of polystyrene by gel permeation chromatography (measuring device: HCL-8320 (manufactured by Tosoh Corporation), columns: TSKgel G2000H, TSKgel G4000H (manufactured by Tosoh Corporation)).

[0066] (glass transition temperature) 5 mg of polyester polyol (A) was placed in an aluminum container with a lid, sealed, and cooled to −80° C. using liquid nitrogen. Using a commercially available differential scanning calorimeter (product name: “EXSTAR6000 DSC 6200”, manufactured by Seiko Instruments Inc.), the temperature was raised to 150° C. at a rate of 20° C. / min. In the obtained endothermic curve, the temperature at the intersection of an extension of the baseline before the endothermic peak (below the glass transition temperature) and a tangent to the endothermic peak (a tangent showing the maximum slope from the rising part of the peak to the peak top) was determined as the glass transition temperature (Tg, unit: ° C).

[0067] (Hydroxyl value) The hydroxyl value of the polyester polyol (A) was measured in accordance with JIS K-0070.

[0068] Manufacturing Example 1 A reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, and reflux dehydration device was charged with 309.22 parts of dimethyl terephthalate, 127.88 parts of 2-methyl-1,3-propanediol, 531.79 parts of butyl ethyl propanediol, 139.72 parts of 1,6-hexanediol, and 0.02 parts of tetrabutyl titanate. The mixture was heated to melt and gradually heated to 220°C while removing the by-product methanol, and stirred for an additional 3 hours. Next, 491.39 parts of isophthalic acid was added, and the reaction system was gradually heated to 250°C while removing the by-product water, and stirred for an additional 3 hours. A vacuum pressure reduction device was then connected, and a polycondensation reaction was carried out at 250°C under 1 kPa or less for 10 hours to obtain polyester polyol (A-1). The number average molecular weight, glass transition temperature, and hydroxyl value of the resulting polyester resin (A-1) are shown in Table 1 (the same applies below).

[0069] Manufacturing Examples 2 to 6, Comparative Manufacturing Example 1 The same method as in Production Example 1 was carried out, except that the compositions and molar ratios (mol %) were changed to those shown in Table 1, to obtain polyester resins (A-2) to (A-6) and (AC-1).

[0070] [Table 1]

[0071] Example 1 In a reactor similar to that used in Production Example 1, 500.0 parts of polyester polyol (A-1), 106.6 parts of isophorone diisocyanate, and 107.0 parts of ethyl acetate were charged and stirred at 120°C for 6 hours. The mixture was then cooled to 70°C and 152.9 parts of ethyl acetate was added to dissolve the mixture. Next, 44.0 parts of isophorone diamine and 5.6 parts of 2-ethylhexylamine were added and reacted. The mixture was then dissolved in 382.8 parts of isopropyl alcohol and 888.3 parts of ethyl acetate to obtain a reaction product. The number average molecular weight of the reaction product is shown in Table 2 (the same applies below).

[0072] Examples 2 to 10, Comparative Examples 1 to 4 The same method as in Example 1 was carried out, except that the compositions and molar ratios (mol %) were changed to those shown in Table 2, and reaction products were obtained.

[0073] The resulting reaction product was used as it was as a resin composition for electronic parts.

[0074] (Preparation of cured product (sheet)) Each composition for electronic devices was coated on a release paper so that the thickness after curing would be 100 μm, and then dried for 5 minutes in a circulating air dryer at 120° C. The release paper was peeled off to obtain each sheet.

[0075] (melting temperature) The sheet was cut into strips 6 mm wide and 40 mm long, and a tensile load was repeatedly applied at a frequency of 1 Hz using a dynamic viscoelasticity measuring device (model name: "RSAIII", manufactured by TA Instruments Japan Co., Ltd.). The peak temperature of tan δ due to melting, which occurs in a temperature range above the glass transition temperature, was measured as the melting temperature. A higher melting temperature indicates better heat resistance. The results are shown in Table 2.

[0076] (dielectric loss tangent) Using a network analyzer (Keysight Technologies, device name: "P5003A") and a split post dielectric resonator (QWED) with a measurement frequency of 10.124 GHz, the resonant frequency and peak Q value of the resonator alone with nothing inserted were measured. Next, the sheet was inserted into a resonator, and the resonance frequency and Q value were measured when the test piece was inserted. The dielectric loss tangent (Df) was calculated from the difference in the Q value and the difference in the resonant frequency between the resonator alone and when the test piece was inserted. The results are shown in Table 2.

[0077] [Table 2]

[0078] The symbols and abbreviations shown in Table 2 represent the following components. (Polyol) A-1 to A-6: Polyester polyols of Production Examples 1 to 6 (combined in the same order) AC-1: Polyester polyol of Comparative Production Example 1 AC-2: Aliphatic polyester polyol, reaction product of adipic acid and 3-methyl-1,5-pentanediol, product name: "Kuraray P-5010", manufactured by Kuraray Co., Ltd. AC-3: Aliphatic polyester polyol, reaction product of adipic acid and 3-methyl-1,5-pentanediol, product name: "Kuraray P-2010", manufactured by Kuraray Co., Ltd. AC-4: Polycarbonate diol, reaction product of 3-methyl-1,5-pentanediol and 1,6-hexanediol, product name: Kuraray P-2090 (manufactured by Kuraray Co., Ltd.) and product name: Kuraray P-1090 (manufactured by Kuraray Co., Ltd.) 1:1 (weight ratio) mixture (Polyisocyanate) IPDI: Isophorone diisocyanate MDI: m-xylylene diisocyanate H-MDI: Hydrogenated m-xylylene diisocyanate (amine) IPD: Isophoronediamine TMD: 2,4,4-trimethylhexamethylenediamine 2EHA: 2-Ethylhexylamine DBA: Di-n-butylamine EA: N-(β-aminoethyl)ethanolamine (product name: "Aminoalcohol EA", manufactured by Nippon Nyukazai Co., Ltd.)

Claims

1. A resin composition for electronic components, comprising a reaction product of a polyester polyol (A), which is a polymer of reaction components including a polycarboxylic acid (a1) including an aromatic polycarboxylic acid (a1-1) and a polyol (a2), a polyisocyanate (B), and an amine (C).

2. A cured product of the resin composition for electronic parts according to claim 1.

3. A sheet formed from the cured product according to claim 2.

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