Thermosetting resin composition, cured product, semiconductor sealant, semiconductor device, insulating material for printed wiring board, and printed wiring board

Abstract

The present invention addresses the problem of providing a thermosetting resin composition which contains a modified resin having low viscosity and which is capable of achieving low thermal expansion and low elastic modulus. The present invention provides a thermosetting resin composition characterized by containing a thermosetting resin (A), a curing agent (B), a modified resin (C), and at least one filler (D) selected from inorganic fine particles and fibers, the modified resin (C) containing a modified resin having an ether concentration of 11.5-23 mol / kg. Also provided are: a cured product of the thermosetting resin composition; and a semiconductor sealant, a semiconductor device, an insulating material for a printed wiring board, and a printed wiring board, each of which contains the thermosetting resin composition.

Description

Technical Field

[0001] This invention relates to thermosetting resin compositions, cured products, semiconductor sealants, semiconductor devices, insulating materials for printed wiring boards, and printed wiring boards. Background Technology

[0002] Thermosetting resins are widely used in a wide range of fields, including semiconductor components such as capacitors, diodes, transistors, and thyristors; sealing materials for integrated circuits such as ICs and LSIs; and insulating materials used in printed circuit boards. On the other hand, molded articles using these thermosetting resins form composites with various materials. During the manufacturing of these composites, warping can occur due to the different coefficients of thermal expansion of the materials, leading to dimensional accuracy issues. Furthermore, when exposed to temperature variations in their operating environment, defects can sometimes arise due to differences in thermal expansion coefficients, often becoming significant manufacturing problems (see, for example, Patent Document 1). In addition, in recent years, there has been a strong demand for thermosetting resin compositions to have lower viscosity, particularly for modified resins that contribute to this.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2003-82241 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] The problem to be solved by the present invention is to provide a thermosetting resin composition comprising a modified resin having low viscosity and capable of achieving low thermal expansion and low elastic modulus.

[0008] Methods for solving problems

[0009] The present invention provides a thermosetting resin composition comprising a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from inorganic microparticles and fibers, wherein the modified resin (C) contains a modified resin with an ether concentration of 11.5 to 23 mol / kg.

[0010] In addition, the present invention provides a cured product of the above-mentioned thermosetting resin composition, as well as a semiconductor sealant, a semiconductor device, an insulating material for printed wiring boards, and a printed wiring board comprising the above-mentioned thermosetting resin composition.

[0011] That is, the present invention includes the following embodiments.

[0012] [1] A thermosetting resin composition, characterized in that it comprises a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from inorganic microparticles and fibers.

[0013] The modified resin (C) mentioned above contains a modified resin with an ether concentration of 11.5 to 23 mol / kg.

[0014] [2] According to the thermosetting resin composition described in [1] above, wherein the modified resin (C) is one or more selected from polyether polyol, urethane resin made from polyether polyol, and urethane resin made from polyether polyol.

[0015] [3] The thermosetting resin composition according to [1] or [2] above, wherein the modified resin (C) is a capped polyether oligomer and / or a capped polyether ester oligomer.

[0016] [4] The thermosetting resin composition according to [3] above, wherein the hydroxyl value of the above-terminated polyether oligomer and / or the terminated polyether ester oligomer is 0 or more and 10 or less.

[0017] [5] According to the thermosetting resin composition described in [3] or [4] above, wherein the terminated polyether oligomer is a reaction product of a monofunctional alcohol (IA) and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB), or a reaction product of a monofunctional alcohol (IA) and a polyester and / or polyether ester (IC) having a carboxyl group at one or both ends.

[0018] [6] The thermosetting resin composition according to any one of [3] to [5] above, wherein the terminated polyether ester oligomer is a reaction product of a monofunctional alcohol (IA) containing monofunctional polypropylene glycol and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB).

[0019] [7] According to the thermosetting resin composition described in [3] or [4] above, wherein the above-terminated polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (II-A) having one or more ether groups and a monofunctional carboxylic acid (II-B).

[0020] [8] The thermosetting resin composition according to [3] or [4] above, wherein the capped polyether oligomer and / or capped polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups and a monofunctional isocyanate (III-B).

[0021] [9] The thermosetting resin composition according to any one of [1] to [8] above, wherein the number average molecular weight of the modified resin (C) is 500 to 50,000.

[0022]

[10] The thermosetting resin composition according to any one of [1] to [9] above, wherein the content of the modified resin (C) is 5 to 45 by mass.

[0023]

[11] A cured product, which is a cured product of the thermosetting resin composition described in any one of [1] to

[10] above.

[0024]

[12] A semiconductor sealing material comprising the thermosetting resin composition described in any one of [1] to

[11] above.

[0025]

[13] A semiconductor device comprising the semiconductor sealing material described in

[12] above.

[0026]

[14] An insulating material for printed wiring boards comprising the thermosetting resin composition described in any one of [1] to

[10] above.

[0027]

[15] A printed wiring board comprising the insulating material for printed wiring boards described above

[14] .

[0028]

[16] An epoxy resin modifier, which is a capped polyether oligomer and / or a capped polyether ester oligomer.

[0029]

[17] According to the epoxy resin modifier described in

[16] above, wherein the above-mentioned end-capped polyether oligomer is a reaction product of a monofunctional alcohol (IA) and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB), or a reaction product of a monofunctional alcohol (IA) and a polyester and / or polyether ester (IC) having a carboxyl group at one or both ends.

[0030]

[18] According to the epoxy resin modifier described in

[16] above, wherein the end-capped polyester oligomer is a reaction product of a monofunctional alcohol (IA) containing monofunctional polypropylene glycol and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB).

[0031]

[19] According to the epoxy resin modifier described in

[16] above, wherein the above-mentioned capped polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (II-A) having one or more ether groups and a monofunctional carboxylic acid (II-B).

[0032]

[20] According to the epoxy resin modifier described in

[16] above, wherein the capped polyether oligomer and / or capped polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups and a monofunctional isocyanate (III-B).

[0033] Invention Effects

[0034] Regarding the thermosetting resin composition of the present invention, the modified resin is of low viscosity, resulting in a thermosetting resin composition containing the modified resin also being of low viscosity, and further exhibiting excellent low thermal expansion and low elastic modulus. Detailed Implementation

[0035] [Thermosetting resin composition]

[0036] The thermosetting resin composition of the present invention contains a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from inorganic microparticles and fibers as essential components.

[0037] As the aforementioned thermosetting resin (A), examples include epoxy resins, resins containing benzoxazine structures, maleimide resins, vinyl benzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, etc. These resins can be used alone or in combination of two or more. Among these, epoxy resins and / or maleimide resins are preferred from the viewpoint that they can easily form a phase-separated structure with the modified resin (C) described later, and that the effects of the present invention are more easily obtained. Epoxy resins are more preferred.

[0038] For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, diglycidoxynaphthalene compounds (1,6-diglycidoxynaphthalene, 2,7-diglycidoxynaphthalene, etc.), phenol linear phenolic epoxy resin, cresol linear phenolic epoxy resin, bisphenol A linear phenolic epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, and dicyclopentadiene-phenol addition reaction type epoxy resin can be used. Epoxy resins containing a naphthalene skeleton include phenol aralkyl type epoxy resins, naphthol linear phenolic type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensation linear phenolic type epoxy resins, naphthol-cresol co-condensation linear phenolic type epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resins, biphenyl linear phenolic type epoxy resins, 1,1-bis(2,7-diglycidoxy-1-naphthyl)alkanes, and phosphorus-modified epoxy resins obtained by introducing phosphorus atoms into these various epoxy resins.

[0039] Among these epoxy resins, from the perspective of obtaining cured products with excellent heat resistance, cresol linear phenolic epoxy resin, phenol aralkyl type epoxy resin, biphenyl linear phenolic epoxy resin, naphthol linear phenolic epoxy resin containing a naphthalene skeleton, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensation linear phenolic epoxy resin, naphthol-cresol co-condensation linear phenolic epoxy resin, crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, xanthine type epoxy resin, and aromatic ring modified linear phenolic epoxy resin containing alkoxy groups (a compound obtained by linking an aromatic ring containing glycidyl groups and an aromatic ring containing alkoxy groups with formaldehyde).

[0040] As the maleimide resin described above, for example, a resin shown in any of the following structural formulas can be used.

[0041] [Chemical Formula 1]

[0042]

[0043] In equation (1), R 1 R represents an organic group with an a1 valence. 2 and R 3 Each of these elements independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms; a1 represents an integer greater than 1.

[0044] [Chemical Formula 2]

[0045]

[0046] In equation (2), R 4 R 5 and R 6 Each of the following independently represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, a halogen atom, a hydroxyl group, or an alkoxy group with 1 to 20 carbon atoms, L 1 and L 2 Each of these groups independently represents a saturated hydrocarbon group with 1 to 5 carbon atoms, an aromatic hydrocarbon group with 6 to 10 carbon atoms, or a group with 6 to 15 carbon atoms formed by combining a saturated hydrocarbon group and an aromatic hydrocarbon group. a3, a4, and a5 each independently represent an integer from 1 to 3, and n represents an integer from 0 to 10.

[0047] In the above-mentioned thermosetting resin (A), the total content of the above-mentioned epoxy resin and the above-mentioned maleimide resin is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and the upper limit is 100% by mass.

[0048] Regarding the content of the thermosetting resin (A) mentioned above, among the non-volatile components of the components after excluding the filler (D) from the thermosetting resin composition, it is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0049] The curing agent (B) described above can be any substance capable of curing the thermosetting resin composition, such as amine compounds, amide compounds, reactive ester resins, acid anhydrides, phenolic resins, cyanate ester resins, etc. Preferably, it is selected from at least one of amine compounds, reactive ester resins, phenolic resins, and cyanate ester resins, and more preferably, it is an amine compound or a phenolic resin.

[0050] Examples of amine compounds that can be used include diethyltoluene diamine, diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophorone diamine, imidazole, BF3-amine complex, guanidine derivatives, etc.

[0051] As the aforementioned amide compound, dicyandiamide, polyamide resin synthesized from linolenic acid dimer and ethylenediamine, etc., can be used.

[0052] As the aforementioned reactive ester resin, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds, are preferably used. The aforementioned reactive ester resin is preferably a substance obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, reactive ester resins obtained from carboxylic acid compounds or their halides with hydroxyl compounds are preferred, and reactive ester resins obtained from carboxylic acid compounds or their halides with phenolic compounds and / or naphthol compounds are more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or their halides. As phenolic or naphthol compounds, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-phenol addition-type resins, etc., can be used.

[0053] Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., can be used as the above-mentioned anhydrides.

[0054] As the aforementioned phenolic resin, linear phenolic resin, linear cresol phenolic resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition-type resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, tris(hydroxyphenyl)methane resin, tetra(hydroxyphenyl)ethane resin, naphthol linear phenolic resin, naphthol-phenol cocondensed linear phenolic resin, naphthol-cresol cocondensed linear phenolic resin, biphenyl modified phenolic resin (a compound containing polyphenolic hydroxyl groups formed by linking phenol cores with dimethylene groups), phenolic resin containing naphthalene skeleton, and biphenyl modified naphthol resin (a compound containing polyphenolic hydroxyl groups formed by linking phenol cores with dimethylene groups) can be used. Resins containing polyphenolic hydroxyl groups, such as naphthol compounds, aminotriazine-modified phenolic resins (compounds containing polyphenolic hydroxyl groups formed by linking the phenol core with melamine, benzoguanamine, etc.), alkoxy-containing aromatic ring-modified linear phenolic resins (compounds containing polyphenolic hydroxyl groups formed by linking the phenol core with an alkoxy-containing aromatic ring using formaldehyde), bisphenol compounds such as bisphenol A and bisphenol F, biphenyl compounds such as biphenyl and tetramethylbiphenyl, tris(hydroxyphenyl)methane and tetra(hydroxyphenyl)ethane, dicyclopentadiene-phenol addition reaction resins, and phosphorus-modified phenolic compounds formed by introducing phosphorus atoms into these various compounds containing phenolic hydroxyl groups.

[0055] As the aforementioned cyanate resin, one or more types can be used, such as bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin, bisphenol sulfide type cyanate resin, phenylene ether type cyanate resin, naphthylene ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol linear phenolic type cyanate resin, cresol linear phenolic type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin, dicyclopentadiene-phenol addition reaction type cyanate resin, phenol aralkyl type cyanate resin, naphthol linear phenolic type cyanate resin, naphthol aralkyl type cyanate resin, naphthol-phenol cocondensation linear phenolic type cyanate resin, naphthol-cresol cocondensation linear phenolic type cyanate resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type cyanate resin, biphenyl modified linear phenolic type cyanate resin, anthracene type cyanate resin, etc.

[0056] Regarding the content of the curing agent (B) mentioned above, among the non-volatile components of the components after excluding the filler (D) from the above thermosetting resin composition, it is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 90% by mass or less, and more preferably 80% by mass or less.

[0057] The thermosetting resin composition of the present invention may further include a curing accelerator (B1). Examples of the curing accelerator (B1) include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, and amine complex salts. The content of the curing accelerator (B1) is, for example, 0.005% by mass or more and 5% by mass or less of the non-volatile components after excluding filler (D) from the thermosetting resin composition.

[0058] Regarding the modified resin (C) described above, in order to obtain the effects of the present invention, it must contain a modified resin with an ether concentration of 11.5 to 23 mol / kg. Furthermore, a concentration of 13 to 20 mol / kg is more preferred. It should be noted that, regarding the ether concentration of the modified resin (C), when a single resin is used, it represents the concentration of ether groups relative to the total mass of its raw materials; when multiple resins (mixtures) are used in the modified resin (C), it represents the concentration of ether groups in the modified resin with the highest ether concentration among the contained resins.

[0059] In this invention, by using the specific modified resin (C) described above to form a phase-separated structure with the thermosetting resin (A) (especially epoxy resin), a lower coefficient of thermal expansion and a lower modulus of elasticity than a fully compatible system can be obtained. Therefore, warping during manufacturing can be suppressed, and low viscosity can also be achieved.

[0060] Regarding the importance of low viscosity mentioned above, the following points should be added. For example, in semiconductor packaging manufacturing, when connecting chips to the wiring substrate, there are thin wire connections using gold wires, narrow connection gaps through bump electrodes, and narrow gaps between chips when multiple chips are mounted. To ensure the reliability of the connection after packaging, it is essential to inject various sealing materials, such as solid sealing materials, liquid sealing materials, and underfill materials, into these tiny gaps in a high-temperature liquid state within a short time, and then allow them to solidify for bonding and strengthening. To suppress defects such as voids and incomplete filling after filling narrow gaps with sealing material, it is necessary to significantly reduce the viscosity of the sealing material at the time of injection. Generally, sealing materials containing resin components with a high coefficient of thermal expansion need to reduce the difference in thermal expansion between the sealing material and the chip with a low coefficient of thermal expansion. On this basis, a large amount of inorganic filler with a low coefficient of thermal expansion needs to be filled into the sealing material. Therefore, the resin material used in the sealing material is strongly required to be low in viscosity so that the viscosity at high temperature melting can be kept low even when a large amount of inorganic filler is filled. In addition, it would be even more ideal if the coefficient of thermal expansion could be reduced even by reducing the amount of inorganic filler. Furthermore, in insulating materials such as build-up films and prepregs that constitute packaging substrates formed from fine circuit patterns, the viscosity at melt time needs to be sufficiently low from the perspective of circuit embedding during vacuum lamination and high-temperature pressing. On the other hand, these insulating resin materials require the addition and dispersion of modified resins with phase separation properties to impart properties such as toughness, crack resistance, low warpage, and low elasticity. However, additives with phase separation properties are usually high molecular weight, which leads to an increase and deterioration in melt viscosity as mentioned above. In contrast, the present invention provides a modified resin material that, in terms of the properties that can be imparted by a modified resin material, exhibits an effect of reducing the coefficient of thermal expansion that is unimaginable except for inorganic fillers. Although it is a resin material, it exhibits low thermal expansion with a significant effect no less than that of inorganic materials. Furthermore, by setting a reaction-induced type in which the modified resin, which is compatible with the low viscosity modified resin, forms an island structure before the thermosetting resin (A) as the matrix resin is cured, it serves as the phase separation mechanism for the modified resin used to form phase separation. Although it has a low molecular weight and low viscosity, it can still form island phase separation after curing. The resulting phase separation structure exhibits a low coefficient of thermal expansion and low elasticity, and can reduce the warpage of the molded article. It is an extremely rare modified resin.

[0061] Specifically, the modified resin (C) described above can be polyether polyol, polyether ester polyol, urethane resin made from polyether polyol, or urethane resin made from polyether ester polyol. These resins can be used alone or in combination of two or more. Among these, polyether ester polyol and / or urethane resin made from polyether polyol are preferred from the perspective of further obtaining the effects of the present invention, and more preferably polyether ester polyol.

[0062] As the aforementioned polyether ester polyols, for example, reaction products of polyether polyols with polybasic acids, reaction products of polyether polyols with lactone compounds, etc., can be used. These polyols can be used alone or in combination of two or more.

[0063] As the aforementioned polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., can be used. Among these, polypropylene glycol is preferred from the perspective of further obtaining the effects of the present invention.

[0064] Regarding the aforementioned polycarboxylic acids, one or more can be used. For example, aliphatic polycarboxylic acids such as malonic acid, adipic acid, succinic acid, azelaic acid, octanoic acid, sebacic acid, glutaric acid, dodecanoic acid, eicosanoic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride can be used; alicyclic polycarboxylic acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and 1,4-cyclohexanedicarboxylic acid can be used; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid can be used.

[0065] Examples of lactone compounds that can be used include γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε-propylcaprolactone, 3-penten-4-lactone, 12-dodecanolide, and γ-dodecanolide. Among these, ε-caprolactone is preferred.

[0066] The polyether polyol used as the raw material in the above-mentioned urethane resin can be the same substance as the polyether polyol, preferably polypropylene glycol.

[0067] The polyether polyol used in the above-mentioned urethane resin made from polyether polyol can be the same substance as the polyether polyol.

[0068] Regarding the aforementioned urethane resins, in addition to the polyether polyols, polyisocyanates can also be used as raw materials. For example, aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenyl diisocyanate, toluene diisocyanate, naphthalene diisocyanate, phenylmethylene diisocyanate, and tetramethylphenylmethylene diisocyanate can be used; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate can be used; and polyisocyanates containing alicyclic structures such as cyclohexane diisocyanate, hydrogenated phenylmethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate can be used.

[0069] Furthermore, as the modified resin (C) described above that can exhibit a specific ether concentration, one or more end-capped polyether oligomers or end-capped polyether ester oligomers can be used. End-capped polyether oligomers or end-capped polyether ester oligomers refer to compounds containing ether groups and substantially lacking acid groups such as hydroxyl or carboxyl groups at least at the ends along the main chain length. Preferably, the end-capped polyether oligomers or end-capped polyether ester oligomers are compounds that substantially lack acid groups such as hydroxyl or carboxyl groups within the molecule. "Substantially lacking" means that the hydroxyl value and acid value are within the range described later.

[0070] As the modified resin (C) described above, one or more compounds selected from those shown in chemical formulas (I) to (III) below may be used. Specifically, as the end-capped polyether ester oligomer described above, one or more compounds selected from those shown in chemical formulas (I) to (III) below may be used. Furthermore, as the end-capped polyether oligomer described above, one or more compounds shown in chemical formula (III) below may be used.

[0071] [Chemical Formula 3]

[0072]

[0073] (In the above chemical formula (I), R1 and R2 are each independently any functional group containing one or more combinations of hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups, and amino groups selected from carbons 1 to 30, and at least one of R1 and R2 is a functional group containing an ether group. n1 is a real number in the range of 1 to 6.)

[0074] Wherein, n1 is preferably a real number in the range of 1 to 3, and more preferably a real number in the range of 1 to 2.

[0075] [Chemical Formula 4]

[0076]

[0077] (In the above chemical formula (II), R3 and R4 are each independently any functional group containing one or more combinations of hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups, and amino groups selected from carbons 1 to 30, and at least one of R3 and R4 is a functional group containing an ether group. n2 is a real number in the range of 1 to 6.)

[0078] Wherein, n2 is preferably a real number in the range of 1 to 3, and more preferably a real number in the range of 1 to 2.

[0079] [Chemical Formula 5]

[0080]

[0081] (In the above chemical formula (III), R5 is any functional group containing one or more combinations of hydrocarbon groups, ether groups, ester groups, and sulfonyl groups selected from carbons 1 to 20; R6 is any functional group containing one or more combinations of hydrocarbon groups, ether groups, ester groups, carbamate groups, urea groups, amide groups, and amino groups selected from carbons 1 to 30; and at least one of R5 and R6 is a functional group containing an ether group. n3 is a real number in the range of 1 to 6.)

[0082] Wherein, n3 is preferably a real number in the range of 1 to 3, and more preferably a real number in the range of 1 to 2.

[0083] The hydroxyl value of the capped polyether oligomer or capped polyether ester oligomer (e.g., the compounds shown in chemical formulas (I) to (III) above) is preferably 0 or more and 10 or less, more preferably 0 or more and 5 or less, further preferably 0 or more and 2 or less, and particularly preferably 0. Furthermore, the acid value of the capped polyether oligomer or capped polyether ester oligomer (e.g., the compounds shown in chemical formulas (I) to (III) above) is preferably 0 or more and 10 or less, more preferably 0 or more and 5 or less, further preferably 0 or more and 2 or less, and particularly preferably 0. The hydroxyl value and acid value of the capped polyether oligomer or capped polyether ester oligomer (the compounds shown in chemical formulas (I) to (III) above) can be adjusted by the type of raw material and the reaction ratio (molar ratio) of the capped polyether oligomer or capped polyether ester oligomer (the compounds shown in chemical formulas (I) to (III) above).

[0084] Examples of compounds (terminated polyether oligomers) represented by the above chemical formula (I) include: reaction products of monofunctional alcohols (IA) with monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB); reaction products of monofunctional alcohols (IA) with polyesters and / or polyether esters (IC) having carboxyl groups at one or both ends. "Two ends" refers to the ends along the main chain length.

[0085] The monofunctional alcohol (IA) used as a raw material for the compound shown in the above chemical formula (I) is a substance having one hydroxyl group in the compound. Preferably, the monofunctional alcohol (IA) does not have functional groups other than one hydroxyl group that can react with monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB), and polyesters and / or polyether esters (IC) having carboxyl groups at one or both ends.

[0086] For monofunctional alcohols (IA), having one hydroxyl group is sufficient. Examples include aliphatic alcohols, monofunctional polyethylene glycol, monofunctional polypropylene glycol, monofunctional polyoxybutylene, monofunctional polycaprolactone, and monofunctional polyesters. One or more of these can be used in combination. It should be noted that when the compound reacting with the monofunctional alcohol (IA) is a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB), the aliphatic alcohol used as the monofunctional alcohol (IA) is preferably a long-chain aliphatic alcohol. Furthermore, when the compound reacting with the monofunctional alcohol (IA) is a polyester and / or polyether ester (IC) having carboxyl groups at one or both ends, the aliphatic alcohol used as the monofunctional alcohol (IA) can be either a long-chain aliphatic alcohol or a short-chain aliphatic alcohol.

[0087] From the viewpoint that it is easy to form a phase-separated structure, the above-mentioned monofunctional alcohol (IA) is preferably a compound selected from monofunctional polyethylene glycol, monofunctional polypropylene glycol and long-chain aliphatic alcohols.

[0088] The aforementioned long-chain aliphatic alcohols preferably have 5 to 25 carbon atoms, more preferably 6 to 23. Examples of such long-chain aliphatic alcohols include: pentanol, hexanol, octanol, decanol, dodecanol, tetradecylol, hexadecylol, octadecanol, eicosylol, dodecyl alcohol, 2-methyl-decane-1-ol, 2-ethyl-decane-1-ol, 2-hexyl-octane-1-ol, etc., which are straight-chain or branched long-chain aliphatic saturated alcohols; and hexenol, 2-hexen-1-ol, 1-hexen-3-ol, pentenol, 2-methyl-1-pentenol, etc., which are straight-chain or branched long-chain aliphatic unsaturated alcohols. These can be used alone or in combination of two or more. From the viewpoint of easily becoming liquid and reducing crystallinity, branched aliphatic saturated alcohols are preferred.

[0089] Examples of monofunctional polyethylene glycols include polyethylene glycol monobutyl ether, polyethylene glycol monododecyl ether, and other polyethylene glycol monoalkyl ethers, as well as polyethylene glycol monoacetate and other polyethylene glycol monoesters. These can be used alone or in combination of two or more.

[0090] As a monofunctional polypropylene glycol, examples include compounds with one end capped on each side of the polypropylene glycol, such as: polypropylene glycol monoalkyl ethers such as polypropylene glycol monobutyl ether; polyoxypropylene glycol monoalkyl ethers such as polyoxypropylene methyl ether, polyoxypropylene ethyl ether, polyoxypropylene butyl ether, polyoxypropylene-2-ethylhexyl ether, polyoxypropylene oleyl ether, and polyoxypropylene-2-octyldodecyl ether; and polypropylene glycol monoesters such as polypropylene glycol monoacetate and polypropylene glycol monoacetate.

[0091] The molecular weight of the monofunctional alcohol (IA) is preferably in the range of 100 to 20,000, more preferably in the range of 150 to 10,000. The above molecular weight is calculated based on the hydroxyl value according to the potentiometric titration method of JIS K 0070:1992.

[0092] There are no particular limitations on the monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB) that serve as raw materials for the compounds shown in the above chemical formula (I). Preferably, the compounds and / or their anhydrides exemplified in the monofunctional carboxylic acids (II-B) described below, as well as dicarboxylic acids and / or their anhydrides such as aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids are preferred.

[0093] For the aforementioned aliphatic dicarboxylic acids and their anhydrides, it is preferable to have a carboxyl group at least at one end, and more preferably at both ends. Examples include malonic acid, adipic acid, succinic acid, azelaic acid, octanoic acid, sebacic acid, glutaric acid, dodecanoic acid, eicosanoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc. For the aforementioned alicyclic dicarboxylic acids and their anhydrides, it is preferable to have a carboxyl group at least at one end, and more preferably at both ends. Examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, 1,4-cyclohexanedicarboxylic acid, etc. Examples of aromatic dicarboxylic acids and / or their anhydrides include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid. These can be used alone or in combination.

[0094] Among the above-mentioned monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB), straight-chain aliphatic dicarboxylic acids are more preferred from the perspective of easily forming phase separation at low viscosity, and adipic acid, azelaic acid, sebacic acid, and dodecanoic acid are preferred.

[0095] The molecular weight of the aforementioned monofunctional or polyfunctional carboxylic acids and / or their anhydrides (IB) is preferably in the range of 110 to 400, more preferably in the range of 140 to 350. The above molecular weights are calculated based on acid value according to the potentiometric titration method of JIS K 0070:1992.

[0096] Regarding the compound represented by the above chemical formula (I), the reaction between the monofunctional alcohol (IA) and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB) is preferably carried out in a molar equivalence ratio (hydroxyl / carboxyl group) of 0.5 to 2, more preferably in a range of 0.7 to 1.4, and even more preferably in a range of 0.9 to 1.1. By setting the above molar equivalence ratio within the above range, the carboxyl group of the monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB) can be capped by the monofunctional alcohol (IA).

[0097] Polyesters and / or polyether esters (ICs) having carboxyl groups at one or both ends, which serve as raw materials for compounds represented by the above chemical formula (I), may, for example, be reaction products of polyether polyols and polyacids. These polyols may be used alone or in combination of two or more.

[0098] As the aforementioned polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., can be used. Among these, polypropylene glycol is preferred from the perspective of further obtaining the effects of the present invention.

[0099] Regarding the aforementioned polycarboxylic acids, one or more can be used. For example, aliphatic polycarboxylic acids such as malonic acid, adipic acid, succinic acid, azelaic acid, octanoic acid, sebacic acid, glutaric acid, dodecanoic acid, eicosanoic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride can be used; alicyclic polycarboxylic acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and 1,4-cyclohexanedicarboxylic acid can be used; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid can be used.

[0100] In addition, regarding polyesters and / or polyether esters (ICs) having carboxyl groups at one or both ends as raw materials for compounds represented by the above chemical formula (I), examples include: polyesters (IC-1) or polyether esters (IC-2) obtained by reacting a polyol with a polycarboxylic acid; polyesters obtained by copolymerizing the above polyester (IC-1) with a polyester obtained by ring-opening polymerization of a cyclic ester compound, etc.

[0101] Regarding the polyols used as raw materials for the aforementioned polyester (IC-1), one or more may be used, such as: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol. -Aliphatic polyols such as propylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,4-diethyl-1,5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol, etc.; polyols with alicyclic structures such as cyclopentanediol, cyclohexanediol, cyclohexanediol, hydrogenated bisphenol A, and their epoxide adducts; polyols with aromatic structures such as bisphenol A and bisphenol F; and polyols obtained by modifying the above-mentioned polyols with aromatic structures with epoxides, etc.

[0102] The molecular weight of the polyol used as a raw material for the aforementioned polyester (IC-1) is preferably 50 or more, preferably 1500 or less, more preferably 1000 or less, and even more preferably 700 or less. The above molecular weight is calculated based on the hydroxyl value using potentiometric titration according to JIS K 0070:1992.

[0103] Furthermore, regarding the polyols used as raw materials for the aforementioned polyether ester (IC-2), for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., can be used. One or more of these can be used.

[0104] The molecular weight of the polyol used as a raw material for the above-mentioned polyether ester (IC-2) is preferably 400 or more, more preferably 700 or more, and preferably 4000 or less, more preferably 2000 or less. The above molecular weight is a value calculated based on the hydroxyl value according to the potentiometric titration method of JIS K 0070:1992.

[0105] Regarding the polycarboxylic acids used as raw materials for the aforementioned polyesters and / or polyether esters (IC), one or more can be used, such as: aliphatic polycarboxylic acids such as malonic acid, adipic acid, succinic acid, azelaic acid, octanoic acid, sebacic acid, glutaric acid, dodecanoic acid, eicosanoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.; alicyclic polycarboxylic acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, 1,4-cyclohexanedicarboxylic acid, etc.; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, pyromellitic acid, etc.

[0106] The aforementioned polyesters and / or polyether esters (ICs) having carboxyl groups at one or both ends can be obtained, for example, by reacting the aforementioned polyols with polycarboxylic acids under conditions where the equivalent amount of carboxyl groups in the reactants is greater than the equivalent amount of hydroxyl groups.

[0107] The molecular weight of the aforementioned polyesters and / or polyether esters (ICs) having carboxyl groups at one or both ends is preferably in the range of 140 to 40,000, more preferably in the range of 140 to 20,000. The above molecular weights are calculated based on acid value using potentiometric titration according to JIS K 0070:1992.

[0108] Regarding the compound represented by chemical formula (I) above, the reaction between the monofunctional alcohol (IA) and the polyester and / or polyether ester (IC) having carboxyl groups at one or both ends is preferably carried out in a molar equivalence ratio (hydroxyl / carboxyl) of the molar equivalent number of hydroxyl groups in the monofunctional alcohol (IA) to the molar equivalent number of carboxyl groups in the polyester and / or polyether ester (IC) having carboxyl groups at one or both ends, more preferably in a range of 0.7 to 1.4, and even more preferably in a range of 0.9 to 1.1. By setting the above equivalence ratio within the above range, the carboxyl groups at both ends of the polyester and / or polyether ester (IC) having carboxyl groups can be capped by the monofunctional alcohol (IA).

[0109] Examples of compounds (terminated polyether oligomers) represented by the above chemical formula (II) include, for instance, the reaction product of a compound having one or more hydroxyl groups (II-A) and a monofunctional carboxylic acid (II-B).

[0110] Regarding monofunctional or polyfunctional alcohols (II-A) having one or more ether groups that serve as raw materials for compounds represented by the above chemical formula (II), examples include monofunctional alcohols, polyether polyols, polyether ester polyols, urethane resins containing hydroxyl groups made from polyether polyols, and urethane resins containing hydroxyl groups made from polyether ester polyols. These can be used alone or in combination of two or more. The above-mentioned monofunctional or polyfunctional alcohols (II-A) having one or more ether groups have one or more hydroxyl groups, preferably having hydroxyl groups at at least one end along the length direction of the main chain, and more preferably having hydroxyl groups at both ends.

[0111] The molecular weight of the aforementioned monofunctional or polyfunctional alcohols (II-A) having an ether group is preferably in the range of 300 to 20,000, more preferably in the range of 600 to 10,000, and even more preferably in the range of 800 to 5,000. The above molecular weights are calculated based on the hydroxyl value using potentiometric titration according to JIS K0070:1992.

[0112] Regarding the monofunctional carboxylic acid (II-B) used as a raw material for the compound represented by the above chemical formula (II), examples include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. One of these can be used alone, or two can be used together. Among these, aliphatic monocarboxylic acids are preferred for reasons such as ease of phase separation and ease of esterification reaction. The number of carbon atoms in aliphatic monocarboxylic acids is preferably 5 to 20.

[0113] Aliphatic monocarboxylic acids can be linear or branched.

[0114] In addition, aliphatic monocarboxylic acids can be either saturated or unsaturated aliphatic monocarboxylic acids, but from the perspective of preservation stability, saturated aliphatic monocarboxylic acids are preferred.

[0115] Examples of aliphatic monocarboxylic acids include: hexanoic acid, 2-ethylhexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, icosanoic acid, etc. One of these can be used alone, or two or more can be used in combination.

[0116] The molecular weight of the monofunctional carboxylic acid (II-B) is preferably in the range of 100 to 400, more preferably in the range of 120 to 350. The above molecular weight is calculated based on the acid value according to the potentiometric titration method of JIS K 0070:1992.

[0117] Regarding the compound represented by chemical formula (II) above, the reaction between the monofunctional or polyfunctional alcohol (II-A) having an ether group and the monofunctional carboxylic acid (II-B) is preferably carried out in a molar equivalence ratio (hydroxyl / carboxyl) of the hydroxyl group in the monofunctional or polyfunctional alcohol (II-A) to the carboxyl group in the monofunctional carboxylic acid (II-B) in the range of 0.5 to 2, more preferably in the range of 0.7 to 1.4, and even more preferably in the range of 0.9 to 1.1. By setting the above equivalence ratio within the above range, the hydroxyl group of the monofunctional or polyfunctional alcohol (II-A) having an ether group can be capped by the monofunctional carboxylic acid (II-B).

[0118] Examples of compounds represented by the above chemical formula (III) (terminated polyether oligomers and / or terminated polyether ester oligomers) include: the reaction products of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups with a monofunctional isocyanate (III-B).

[0119] Examples of monofunctional or polyfunctional alcohols (III-A) having one or more ether groups that serve as raw materials for compounds represented by the above chemical formula (III) include compounds exemplified in the monofunctional alcohols (IA), polyether polyols, polyether ester polyols, urethane resins containing hydroxyl groups made from polyether polyols, and urethane resins containing hydroxyl groups made from polyether ester polyols. The above-mentioned monofunctional or polyfunctional alcohol compounds (III-A) have one or more hydroxyl groups, preferably having hydroxyl groups at at least one end along the length of the main chain, and more preferably having hydroxyl groups at both ends.

[0120] The molecular weight of the aforementioned monofunctional or polyfunctional alcohols (III-A) having one or more ether groups is preferably in the range of 300 to 40,000, more preferably in the range of 800 to 20,000. The above molecular weights are calculated based on the hydroxyl value using potentiometric titration according to JIS K 0070:1992.

[0121] Examples of monofunctional isocyanates (III-B) that serve as raw materials for compounds represented by the above chemical formula (III) include, for example, aliphatic isocyanates such as ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, and octadecyl isocyanate; alicyclic isocyanates such as cyclohexyl isocyanate; and aromatic isocyanates such as phenyl isocyanate, benzyl isocyanate, and p-toluenesulfonyl isocyanate.

[0122] The molecular weight of the monofunctional isocyanate (III-B) is preferably in the range of 70 to 500, more preferably in the range of 90 to 300. The above molecular weight is calculated by the dibutylamine method according to the potentiometric titration method of JIS K-1603-1:2007.

[0123] Regarding the compounds represented by chemical formula (III) above, the reaction between a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups and a monofunctional isocyanate (III-B) is preferably carried out in a manner where the equivalence ratio (OH / NCO) of the hydroxyl groups (OH) in the monofunctional or polyfunctional alcohol (III-A) having one or more ether groups to the equivalence ratio (NCO) of the isocyanate groups (NCO) in the monofunctional isocyanate (III-B) is in the range of 2 to 0.8, more preferably in the range of 1.5 to 0.9, and even more preferably in the range of 1.1 to 1. By setting the above equivalence ratio (OH / NCO) within the above range, the hydroxyl groups of the monofunctional or polyfunctional alcohol (III-A) having one or more ether groups can be capped by the monofunctional isocyanate (III-B).

[0124] Regarding the number-average molecular weight of the modified resin (C) with an ether concentration of 11.5 to 23 mol / kg, it is preferably 500 to 50,000, more preferably 1,000 to 30,000, to further achieve the effects of the present invention. It should be noted that the number-average molecular weight of the modified resin (C) is a value obtained by gel permeation chromatography (GPC) under the following conditions.

[0125] Measurement apparatus: High-speed GPC device (Tosoh Corporation "HLC-8220GPC")

[0126] Tube column: The following tube columns manufactured by Tosoh Corporation are connected in series for use.

[0127] "TSKgel G5000" (7.8mm I.D. × 30cm) × 1 stick

[0128] "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 stick

[0129] "TSKgel G3000" (7.8mm I.D. × 30cm) × 1 stick

[0130] "TSKgel G2000" (7.8mm I.D. × 30cm) × 1 stick

[0131] Detector: RI (Differential Refractometer)

[0132] Column temperature: 40℃

[0133] Eluent: Tetrahydrofuran (THF)

[0134] Flow rate: 1.0 mL / min

[0135] Injection volume: 100 μL (0.4% by mass tetrahydrofuran solution containing the sample)

[0136] Standard test specimen: A calibration curve was prepared using the following standard polystyrene.

[0137] (Standard polystyrene)

[0138] TSKgel Standard Polystyrene A-500 manufactured by Tosoh Corporation

[0139] TSKgel Standard Polystyrene A-1000 manufactured by Tosoh Corporation

[0140] TSKgel Standard Polystyrene A-2500 manufactured by Tosoh Corporation

[0141] TSKgel Standard Polystyrene A-5000 manufactured by Tosoh Corporation

[0142] TSKgel Standard Polystyrene F-1 manufactured by Tosoh Corporation

[0143] TSKgel Standard Polystyrene F-2 manufactured by Tosoh Corporation

[0144] TSKgel Standard Polystyrene F-4 manufactured by Tosoh Corporation

[0145] TSKgel Standard Polystyrene F-10 manufactured by Tosoh Corporation

[0146] TSKgel Standard Polystyrene F-20 manufactured by Tosoh Corporation

[0147] TSKgel Standard Polystyrene F-40 manufactured by Tosoh Corporation

[0148] TSKgel Standard Polystyrene F-80 manufactured by Tosoh Corporation

[0149] TSKgel Standard Polystyrene F-128 manufactured by Tosoh Corporation

[0150] TSKgel Standard Polystyrene F-288 manufactured by Tosoh Corporation

[0151] TSKgel Standard Polystyrene F-550 manufactured by Tosoh Corporation

[0152] Regarding the content of the modified resin with an ether concentration of 11.5 to 23 mol / kg, the content of the non-volatile component in the above-mentioned thermosetting resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less.

[0153] Regarding the modified resin (C) described above, other modified resins besides the modified resin with an ether concentration of 11.5 to 23 mol / kg may also be used. Examples include polyethylene glycol, polypropylene glycol, polybutane glycol, polyolefin polyols, polybutadiene polyols, polyester polyols, polycarbonate polyols, and other polyols, or hydroxyl-containing urethane resins, acrylic resins, styrene-butadiene copolymers, etc., using one or more of these polyols as raw materials. Regarding the content of the modified resin with an ether concentration of 11.5 to 23 mol / kg in the modified resin (C) described above, it is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably substantially 100% by mass.

[0154] One or more fillers (D) selected from inorganic microparticles and fibers are essential components in terms of reducing the thermal expansion of the insulating layer to a predetermined level. Examples of such inorganic microparticles include silica (fused silica, crystalline silica, etc.), silicon nitride, alumina, clay minerals (talc, clay, etc.), mica powder, aluminum hydroxide, magnesium hydroxide, magnesium oxide, aluminum titanate, barium titanate, calcium titanate, titanium oxide, etc., preferably silica, and more preferably fused silica. Furthermore, the silica can be either fragmented or spherical in shape; from the viewpoint of increasing the amount incorporated while suppressing the melt viscosity of the thermosetting resin composition, spherical shape is preferred.

[0155] The volume average particle size of the aforementioned inorganic particles is, for example, 0.01 μm or more, more preferably 0.03 μm or more, and preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less. The volume average particle size of the aforementioned inorganic particles can be determined by laser diffraction.

[0156] Examples of the aforementioned fibers include inorganic fibers such as glass fibers and carbon fibers, as well as organic fibers. The inorganic fibers can be long or short fibers. The carbon fibers can be either polyacrylonitrile-based or pitch-based. The diameter of the inorganic fibers is, for example, 1 μm or more, preferably 3 μm or more, and for example, 30 μm or less, preferably 20 μm or less, and more preferably 15 μm or less.

[0157] Furthermore, the aforementioned fibers can be dispersed in a thermosetting resin composition, arranged in a unidirectional direction, or made into woven or nonwoven fabrics. The thickness of the woven or nonwoven fabric is preferably 100 μm or less, more preferably 2 μm or more, and even more preferably 5 μm or more.

[0158] Regarding the content of the filler (D) mentioned above, it is 40% by mass or more in the non-volatile components of the thermosetting composition, preferably 60% by mass or more, and more preferably 99% by mass or less, and more preferably 95% by mass or less.

[0159] The thermosetting resin composition of the present invention contains the above-mentioned components (A) to (D) as essential components, but other additives may also be used as needed.

[0160] Other additives mentioned above may include flame retardants, organic solvents, conductive particles, rubber, fillers, silane coupling agents, mold release agents, pigments, emulsifiers, etc.

[0161] The thermosetting resin composition of the present invention can be obtained by mixing the above-mentioned components and can be cured by heat curing to form a cured product. Examples of the shape of the cured product include laminates, injection molded products, adhesive layers, coatings, films, etc.

[0162] Examples of applications for the thermosetting resin composition of the present invention include semiconductor sealing materials, printed circuit board materials, resin injection molding materials, adhesives, interlayer insulating materials for add-on substrates, and adhesive films for add-on layers. Among these applications, in the use of printed circuit boards, insulating materials for electronic circuit boards, and adhesive films for add-on layers, it can be used as an insulating material for so-called electronic component embedded substrates where passive components such as capacitors and active components such as IC chips are embedded within the substrate. Among these, those with properties such as high heat resistance, low thermal expansion, low viscosity, low elastic modulus, and solvent solubility are preferred for use in printed circuit board materials and adhesive films for add-on layers.

[0163] As a method for preparing a semiconductor sealing material from the thermosetting composition of the present invention, the above-mentioned thermosetting resin composition can be fully melted and mixed to homogeneity using, for example, an extruder, a kneader, a roller, etc.

[0164] When the thermosetting resin composition of the present invention is used as a semiconductor sealing material, semiconductor encapsulation molding can be performed. Specifically, the composition is injection molded or molded using a transfer molding machine, injection molding machine, etc., and then heated at 50 to 200°C for 2 to 10 hours, thereby obtaining a semiconductor device as a molded product.

[0165] Furthermore, in order to manufacture a printed circuit board using the thermosetting resin composition of the present invention, a method can be described as impregnating a reinforcing substrate with the thermosetting resin composition, overlapping copper foil, and then heat-pressing it. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass pads, and glass roving. More specifically, firstly, by heating the thermosetting resin composition (preferably 50 to 170°C, depending on the type of organic solvent (F), a prepreg as a cured product can be obtained. In the prepreg, the resin content is preferably 20% by mass or more and 60% by mass or less. Next, the prepreg is layered, copper foil is overlapped, and the substrate is heat-pressed at 170 to 300°C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, thereby obtaining the desired printed circuit board.

[0166] When the thermosetting resin composition of the present invention is used as a conductive paste, examples include: a method for dispersing conductive particles (fine conductive particles) in the thermosetting resin composition to prepare a composition for preparing anisotropic conductive films; a method for preparing a circuit connection paste resin composition that is liquid at room temperature; and a method for preparing anisotropic conductive adhesives.

[0167] As a method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting resin composition of the present invention, for example, the thermosetting resin composition is applied to a wiring substrate on which a circuit is formed using a spraying method or a curtain coating method, and then cured. Then, predetermined through-holes are made as needed, and the surface is treated with a roughening agent, washed with warm water to create an uneven surface, and then plated with metals such as copper. As the above plating method, electroless plating or electrolytic plating is preferred. Examples of roughening agents include oxidants, alkalis, and organic solvents. This operation is repeated sequentially as needed, and a resin insulating layer and a conductor layer with a predetermined circuit pattern are formed by alternating layers to obtain a build-up substrate. However, the through-holes are made after the outermost resin insulating layer is formed. Alternatively, the thermosetting resin composition can be semi-cured on a copper foil, and the resulting copper foil with resin can be heated and pressed onto a wiring substrate with circuitry formed at 170-300°C. This can create a roughened surface, eliminating the need for plating and also enabling the fabrication of an additive substrate.

[0168] Regarding the method of manufacturing a laminated film from the thermosetting resin composition of the present invention, for example, a method of coating the thermosetting resin composition of the present invention onto a support film and forming a resin composition layer to produce a laminated film for a multilayer printed wiring board.

[0169] When using the thermosetting resin composition of the present invention for a laminated film, it is important to soften the film under the lamination temperature conditions of a vacuum lamination process (typically 70°C to 140°C) and to exhibit fluidity (resin fluidity) so that the resin can fill the vias or holes present in the circuit board while laminating the circuit board. It is preferable to combine the above-mentioned components to exhibit such characteristics.

[0170] Here, the diameter of the vias in the multilayer printed wiring board is typically 0.1–0.5 mm, and the depth is typically 0.1–1.2 mm. It is generally preferred that the resin can fill within this range. It should be noted that when laminating both sides of the circuit board, it is desirable to fill to about 1 / 2 of the via.

[0171] Specifically, the method for manufacturing the above-mentioned adhesive film can be as follows: after preparing a varnish-like thermosetting resin composition of the present invention, the varnish-like composition is applied to the surface of a support film (Y), and the organic solvent is dried by heating or blowing hot air to form a layer (X) of the thermosetting composition.

[0172] The thickness of the formed layer (X) is usually set to be greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer in the circuit board is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer is preferably 10 to 100 μm.

[0173] It should be noted that layer (X) in this invention can also be protected by the protective film described later. By protecting it with a protective film, it is possible to prevent dust and other contaminants from adhering to or scratching the surface of the resin composition layer.

[0174] Examples of the aforementioned support films and protective films include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate; polyimide; and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that, in addition to matte treatment and corona treatment, support films and protective films can also undergo release treatment.

[0175] The thickness of the support film is not particularly limited, and is typically 10–150 μm, preferably in the range of 25–50 μm. Furthermore, the thickness of the protective film is preferably set to 1–40 μm.

[0176] The aforementioned support film (Y) is peeled off after being laminated onto the circuit board or after forming an insulating layer through heat curing. Peeling off the support film (Y) after the adhesive film has been heat-cured prevents the adhesion of dust and other contaminants during the curing process. In cases where peeling is performed after curing, the support film is typically pre-treated with a demolding process.

[0177] Next, regarding the method of manufacturing a multilayer printed wiring board using the adhesive film obtained as described above, for example, after peeling off layer (X) while it is protected by a protective film, it is laminated onto one or both sides of a circuit board by, for example, vacuum lamination, so that layer (X) is in direct contact with the circuit board. The lamination method can be intermittent or continuous using rollers. In addition, the adhesive film and the circuit board can be heated (preheated) as needed before lamination.

[0178] Regarding lamination conditions, it is preferred to set the lamination temperature to 70–140°C and the lamination pressure to 1–11 kgf / cm². 2 (9.8×10 4 ~107.9×10 4 N / m 2 Lamination is preferably performed under reduced pressure below 20 mmHg (26.7 hPa).

[0179] Regarding the method for obtaining the cured product of the present invention, a general curing method for thermosetting resin compositions can be used. For example, the heating temperature can be appropriately selected according to the type and purpose of the curing agent, and the composition obtained by the above method can be heated in a temperature range of about 20 to 300°C.

[0180] Modifiers for epoxy resins

[0181] The epoxy resin modifier of the present invention is a capped polyether oligomer and / or a capped polyether ester oligomer. The above-mentioned capped polyether oligomer and / or capped polyether ester oligomer can be compounds represented by any of the following chemical formulas (I) to (III).

[0182] [Chemical Formula 6]

[0183]

[0184] R1, R2, and n1 in the above chemical formula (I) are the same as defined above.

[0185] [Chemical Formula 7]

[0186]

[0187] R3, R4, and n2 in the above chemical formula (II) are the same as defined above.

[0188] [Chemical Formula 8]

[0189]

[0190] R5, R6, and n3 in the above chemical formula (III) are the same as defined above.

[0191] The epoxy resin modifier of the present invention forms a phase-separated structure by mixing with epoxy resin, which can reduce the thermal expansion coefficient and elastic modulus of the mixture and suppress warping during curing.

[0192] Examples of end-capped polyether oligomers represented by the above chemical formula (I) include: reaction products of a monofunctional alcohol (IA) with a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB); or reaction products of a monofunctional alcohol (IA) with a polyester and / or polyether ester (IC) having a carboxyl group at one or both ends. Preferably, the monofunctional alcohol (IA) comprises monofunctional polypropylene glycol.

[0193] Examples of end-capped polyester oligomers represented by the above chemical formula (II) include: reaction products of monofunctional or polyfunctional alcohols (II-A) having one or more ether groups and monofunctional carboxylic acids (II-B).

[0194] Examples of end-capped polyether oligomers and / or end-capped polyether ester oligomers represented by the above chemical formula (III) include, for example, the reaction products of a monofunctional or polyfunctional alcohol (III-A) having one or more ether groups with a monofunctional isocyanate (III-B).

[0195] Details regarding the end-capped polyether oligomers and / or end-capped polyether ester oligomers used as modifiers for epoxy resins in this invention are omitted here because they can be set to be the same as the details of the end-capped polyether oligomers and / or end-capped polyether ester oligomers used in the modified resin (C) in the thermosetting resin composition of this invention described above.

[0196] This invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any manner having a substantially the same structure and producing the same effect as the technical concept described in the scope of this invention is included within the technical scope of this invention.

[0197] Example

[0198] The present invention will be described in more detail below with examples.

[0199] [Example 1]

[0200] In a mixing container, 6.55 parts by weight of epoxy resin 1 (EPICLON 830CRP, manufactured by DIC Corporation), 6.55 parts by weight of epoxy resin 2 (jER 630, manufactured by Mitsubishi Chemical Corporation), 6.90 parts by weight of amine curing agent (KAYAHARD AA, manufactured by Nippon Kayaku Co., Ltd.), and 5 parts by weight of polyether ester polyol 1 (a reaction product of difunctional polypropylene glycol, isophthalic acid, and sebacic acid with a number average molecular weight of 1000, a number average molecular weight of 2000, and an ether concentration of 14.9 mol / kg) were stirred at an internal temperature of 100°C until compatible. Next, 37.5 parts by weight of fused silica 1 (FB-5SDC, manufactured by DENKA Corporation) and 37.5 parts by weight of fused silica 2 (FB-5604FC, manufactured by DENKA Corporation) were uniformly mixed to obtain a thermosetting resin composition.

[0201] [Example 2]

[0202] Except for changing the amount of epoxy resin 1 from 6.55 parts by weight to 7.37 parts by weight, the amount of epoxy resin 2 from 6.55 parts by weight to 7.37 parts by weight, the amount of amine curing agent from 6.90 parts by weight to 7.76 parts by weight, and the amount of polyether ester polyol 1 from 5 parts by weight to 2.5 parts by weight, the process was carried out in the same manner as in Example 1 to obtain a thermosetting resin composition.

[0203] [Example 3]

[0204] Except for changing the amount of epoxy resin 1 from 6.55 parts by weight to 5.74 parts by weight, the amount of epoxy resin 2 from 6.55 parts by weight to 5.74 parts by weight, the amount of amine curing agent from 6.90 parts by weight to 6.02 parts by weight, and the amount of polyether ester polyol 1 from 5 parts by weight to 7.5 parts by weight, the process was carried out in the same manner as in Example 1 to obtain a thermosetting resin composition.

[0205] [Example 4]

[0206] Except for replacing the above-mentioned polyether ester polyol 1 with polyether ester polyol 2 (a reaction product of difunctional polypropylene glycol and ε-caprolactone with a number average molecular weight of 3000, a number average molecular weight of 3300, and an ether concentration of 15.3 mol / kg), the process was carried out in the same manner as in Example 1 to obtain a thermosetting resin composition.

[0207] [Example 5]

[0208] In a mixing container, 6.55 parts by weight of epoxy resin 1 (DIC Corporation's "EPICLON 830CRP"), 6.55 parts by weight of epoxy resin 2 (Mitsubishi Chemical Corporation's "jER 630"), 6.90 parts by weight of amine curing agent (Nippon Kayaku Co., Ltd.'s "KAYAHARD AA"), and 5 parts by weight of end-capped polyether ester oligomer (a reaction product obtained by reacting polypropylene glycol monobutyl ether (Sanyo Chemical Industry Co., Ltd.'s "NEWPOL LB-285", a monofunctional polypropylene glycol with a molecular weight of 1170) and sebacic acid (molecular weight of 202.25) at a specified molar ratio of 2:1, with a number average molecular weight of 2500, a hydroxyl value of 2.7, an acid value of 3.3, and an ether concentration of 15.1 mol / kg) were stirred at an internal temperature of 100°C until compatible. Next, 37.5 parts by weight of fused silica 1 (manufactured by DENKA Corporation, “FB-5SDC”) and 37.5 parts by weight of fused silica 2 (manufactured by DENKA Corporation, “FB-5604FC”) were uniformly mixed to obtain a thermosetting resin composition.

[0209] It should be noted that the above-mentioned capped polyether ester oligomers are compounds equivalent to those in the above chemical formula (I) where R1 is represented by formula (3), R2 by formula (4), and n1=2. Specifically, they are compounds represented by the following chemical formula (5).

[0210] [Chemical Formula 9]

[0211]

[0212] [Chemical Formula 10]

[0213]

[0214] (In the above formulas (3) to (5), one of R7 and R8 is a hydrogen atom and the other is a methyl group, and the average value of n4 is 18.9.)

[0215] [Example 6]

[0216] In a mixing container, 9.34 parts by weight of epoxy resin 3 (“EPICLON HP-4700” manufactured by DIC Corporation), 3.11 parts by weight of epoxy resin 4 (“jER YX-4000H” manufactured by Mitsubishi Chemical Corporation), 7.55 parts by weight of phenolic linear phenolic curing agent (“PHENOLITE TD-2131” manufactured by DIC Corporation), and 5 parts by weight of polyether ester polyol 1 were mixed and stirred at an internal temperature of 130°C until compatible. Next, 37.5 parts by weight of fused silica 1 (“FB-5SDC” manufactured by DENKA Corporation), 37.5 parts by weight of fused silica 2 (“FB-5604FC” manufactured by DENKA Corporation), and 0.125 parts by weight of triphenylphosphine were uniformly mixed to obtain a thermosetting resin composition.

[0217] [Comparative Example 1]

[0218] Except for changing the amount of epoxy resin 1 from 6.55 parts by weight to 8.19 parts by weight, the amount of epoxy resin 2 from 6.55 parts by weight to 8.19 parts by weight, the amount of amine curing agent from 6.90 parts by weight to 8.62 parts by weight, and the amount of polyether ester polyol 1 from 5 parts by weight to 0 parts by weight, the process was carried out in the same manner as in Example 1 to obtain a thermosetting resin composition.

[0219] [Comparative Example 2]

[0220] Except that a polyester polyol (the reaction product of ethylene glycol and adipic acid, number average molecular weight 2000, ether concentration: 0 mol / kg) was used instead of the above-mentioned polyether ester polyol 1, the process was carried out in the same manner as in Example 1 to obtain a thermosetting resin composition.

[0221] [Comparative Example 3]

[0222] Except for changing the amount of epoxy resin 3 from 9.34 parts by weight to 11.67 parts by weight, the amount of epoxy resin 4 from 3.11 parts by weight to 3.89 parts by weight, the amount of phenol linear phenolic curing agent from 7.55 parts by weight to 9.44 parts by weight, and the amount of polyether ester polyol 1 from 5 parts by weight to 0 parts by weight, the process was carried out in the same manner as in Example 6 to obtain a thermosetting resin composition.

[0223] [Methods for determining the coefficient of thermal expansion]

[0224] After the thermosetting resin compositions obtained in Examples 1-5 and Comparative Examples 1-2 were heat-cured at 100°C for 1 hour and at 175°C for 2 hours, and the thermosetting resin compositions obtained in Example 6 and Comparative Example 3 were heat-cured at 175°C for 5 hours, the linear thermal expansion coefficient in the range of 40-60°C was measured using a TMA6200 (manufactured by Seiko Instruments) as a thermal analysis device with a heating rate of 3°C / min.

[0225] “○”: Less than 16 ppm / ℃

[0226] “×”:16ppm / ℃ or above

[0227] [Methods for determining elastic modulus]

[0228] The flexural modulus of the thermosetting resin compositions obtained in Examples 1-5 and Comparative Examples 1-2 were measured according to JIS K7171 after being heat-cured at 100°C for 1 hour and at 175°C for 2 hours, and the thermosetting resin compositions obtained in Example 6 and Comparative Example 3 were heat-cured at 175°C for 5 hours.

[0229] “○”: Less than 14000MPa

[0230] "×": 14000MPa or above

[0231] Methods for measuring viscosity

[0232] The viscosity of the modified resin (C) used in the examples and comparative examples was measured at 75°C using a cone-plate viscometer.

[0233] “◎”: Less than 200 mPa·s

[0234] “○”: Above 200 mPa·s but less than 1000 mPa·s

[0235] "×": Above 1000 mPa·s

[0236] [Table 1]

[0237]

[0238] [Table 2]

[0239]

[0240] It can be seen that the thermosetting resin composition of the present invention exhibits excellent low thermal expansion, low elastic modulus, and low viscosity. On the other hand, Comparative Examples 1 and 3, which did not use the modified resin (C), have poor low thermal expansion and low elastic modulus. In addition, Comparative Example 2, which used a polyester polyol without ether groups instead of the modified resin (C), has poor low thermal expansion.

Claims

1. A thermosetting resin composition, characterized in that, It comprises a thermosetting resin (A), a curing agent (B), a modified resin (C), and one or more fillers (D) selected from inorganic microparticles and fibers. The modified resin (C) contains a modified resin with an ether concentration of 11.5 mol / kg to 23 mol / kg.

2. The thermosetting resin composition according to claim 1, wherein, The modified resin (C) is selected from one or more of polyether polyols, urethane resins made from polyether polyols, and urethane resins made from polyether polyols.

3. The thermosetting resin composition according to claim 1, wherein, The modified resin (C) is a capped polyether oligomer and / or a capped polyether ester oligomer.

4. The thermosetting resin composition according to claim 3, wherein, The hydroxyl value of the terminated polyether oligomer and / or terminated polyether ester oligomer is greater than 0 and less than 10.

5. The thermosetting resin composition according to claim 3 or 4, wherein, The terminated polyether oligomer is a reaction product of a monofunctional alcohol (IA) and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB), or a reaction product of a monofunctional alcohol (IA) and a polyester and / or polyether ester (IC) having a carboxyl group at one or both ends.

6. The thermosetting resin composition according to claim 3 or 4, wherein, The terminated polyether ester oligomer is a reaction product of a monofunctional alcohol (IA) containing monofunctional polypropylene glycol and a monofunctional or polyfunctional carboxylic acid and / or its anhydride (IB).

7. The thermosetting resin composition according to claim 3 or 4, wherein, The terminated polyether ester oligomer is a reaction product of a monofunctional or polyfunctional alcohol (II-A) having one or more ether groups and a monofunctional carboxylic acid (II-B).

8. The thermosetting resin composition according to claim 3 or 4, wherein, End-capped polyether oligomers and / or end-capped polyether ester oligomers are reaction products of monofunctional or polyfunctional alcohols (III-A) having one or more ether groups and monofunctional isocyanates (III-B).

9. The thermosetting resin composition according to claim 1, wherein, The number average molecular weight of the modified resin (C) is 500 to 50,000.

10. The thermosetting resin composition according to claim 1, wherein, The content of the modified resin (C) is 5% to 45% by mass.

11. A cured product, which is a cured product of the thermosetting resin composition of claim 1.

12. A semiconductor sealing material comprising the thermosetting resin composition of claim 1.

13. A semiconductor device comprising the semiconductor sealing material of claim 12.

14. An insulating material for printed wiring boards comprising the thermosetting resin composition of claim 1.

15. A printed wiring board comprising the insulating material for a printed wiring board as described in claim 14.

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