Active ester, curable resin composition and cured product

Abstract

Provided are active esters capable of making their cured products exhibit excellent flexibility and low dielectric properties, curable resin compositions containing the active esters, and cured products obtained using the curable resin compositions, and further provided are semiconductor sealing materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, laminated films, laminated boards, fiber-reinforced composite materials, and fiber-reinforced resin molded products using the curable resin compositions. The present invention relates to an active ester characterized in that it has a structure in which a residue (A) of a polyol compound and a residue (Q) of an aromatic polycarboxylic acid are bonded via an ester bond, and the active ester is capped with a residue (C) of a terminal monovalent compound containing an aromatic hydroxyl group.

Description

Technical Field

[0001] The present invention relates to an active ester, a curable resin composition containing the active ester, and a cured product obtained from the curable resin composition. Background Art

[0002] Epoxy resin compositions containing epoxy resin and its curing agent as essential components have excellent heat resistance and insulation properties, and are therefore widely used in electronic components such as semiconductors and multilayer printed circuit boards. However, with the increase in signal speed and frequency, it has become increasingly difficult to obtain a low dielectric loss tangent while maintaining a sufficiently low dielectric constant.

[0003] Patent Document 1 discloses an epoxy resin composition using polyphenols as a curing agent in order to satisfy low dielectric properties. However, printed circuit boards and the like obtained using a cured product formed from an epoxy resin composition using polyphenols as a curing agent have a problem of lacking flexibility, and therefore, it is desired to develop a resin composition that can obtain a cured product having flexibility while maintaining low dielectric properties.

[0004] Patent Document 2 discloses a resin composition that can achieve low dielectric properties by using an active ester compound as a curing agent for epoxy resin as a material that can achieve low dielectric constant / low dielectric loss tangent. However, even when this resin composition is used, although low dielectric properties are exhibited, flexibility cannot be satisfied at the same time.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2004-169021

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 7-82348 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] Therefore, the problem to be solved by the present invention is to provide an active ester capable of making the obtained cured product exhibit excellent flexibility and low dielectric properties, a curable resin composition containing the above-mentioned active ester, and a cured product obtained using the above-mentioned curable resin composition, and further provide a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a laminated film, etc. using the above-mentioned curable resin composition.

[0011] Solutions for solving problems

[0012] The present inventors have conducted intensive studies to solve the above problems and have found that the use of a specific active ester in a curable resin composition can provide a cured product with excellent flexibility and low dielectric properties, thereby completing the present invention.

[0013] That is, the present invention is an active ester characterized in that it has a structure in which a residue (A) of a polyol compound and a residue (Q) of an aromatic polycarboxylic acid are bonded via an ester bond, and the active ester is capped with a residue (C) of a terminal monovalent aromatic hydroxyl group-containing compound.

[0014] The active ester of the present invention is preferably obtained by reacting an ester compound (iii) with a polyol compound (iv), wherein the ester compound (iii) is obtained by reacting an aromatic compound having at least two carboxyl groups and / or an acid halide or ester thereof (i) with an aromatic compound having one aromatic hydroxyl group (ii).

[0015] The active ester of the present invention is preferably represented by the following general formula (1).

[0016]

[0017] [In the above formula (1), A is a linear or branched alkylene chain, or a linear or branched alkylene ether chain, Q is an aromatic ring, x is an average repetition number of 0.01 or more, and Ar is a structure represented by the following general formula (2) or (3),

[0018]

[0019]

[0020] In the above formulae (2) and (3), * represents a site bonded to the oxygen atom bonded to Ar in the above formula (1), Ra is independently any one of a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a naphthyl group, y is an integer of 0 to 7, and z is an integer of 0 to 5.]

[0021] In the active ester of the present invention, the hydroxyl equivalent of the polyol compound is preferably less than 270 g / eq.

[0022] In the active ester of the present invention, the hydroxyl equivalent of the polyol compound is preferably 270 g / eq or more.

[0023] In the active ester of the present invention, the polyol compound is preferably a polyol having an aliphatic hydroxyl group.

[0024] In the active ester of the present invention, the hydroxyl equivalent of the polyol having an aliphatic hydroxyl group is preferably 270 g / eq or more.

[0025] In the active ester of the present invention, the aforementioned A is preferably a residue of the aforementioned polyol having an aliphatic hydroxyl group.

[0026] In the active ester of the present invention, the residue of the polyol having an aliphatic hydroxyl group is preferably at least one structural unit selected from the group consisting of a structural unit derived from a hydrocarbon polyol, a structural unit derived from a polycarbonate polyol, a structural unit derived from a polyester polyol, a structural unit derived from a polyether polyol, a structural unit derived from a polyurethane polyol, and a structural unit derived from a polysiloxane polyol.

[0027] The present invention relates to a curable resin composition comprising the above-mentioned active ester and an epoxy resin.

[0028] The present invention relates to a cured product obtained by subjecting the above-mentioned curable resin composition to a curing reaction.

[0029] The present invention relates to a prepreg comprising a reinforcing substrate and a semi-cured product of the curable resin composition impregnated into the reinforcing substrate.

[0030] The present invention relates to a circuit board obtained by laminating the above-mentioned prepreg and copper foil and then heat-compressing and molding them.

[0031] The present invention relates to a laminated film comprising the above-mentioned curable resin composition.

[0032] The present invention relates to a semiconductor sealing material comprising the above-mentioned curable resin composition.

[0033] The present invention relates to a semiconductor device comprising a cured product obtained by heating and curing the semiconductor sealing material.

[0034] Effects of the Invention

[0035] According to the present invention, an active ester capable of causing the obtained cured product to exhibit excellent flexibility and low dielectric properties, a curable resin composition containing the active ester, and a cured product obtained using the curable resin composition can be provided. Furthermore, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a laminated film, etc. using the curable resin composition can be provided, which is useful. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the GPC spectrum of the diphenyl isophthalate derivative (A) obtained in Synthesis Example 1.

[0037] Figure 2 This is the GPC spectrum of the diphenyl isophthalate derivative (B) obtained in Synthesis Example 2.

[0038] Figure 3This is the GPC spectrum of the diphenyl isophthalate derivative (C) obtained in Synthesis Example 3.

[0039] Figure 4 is the active ester (A-1) obtained in Example 1 13 C-NMR spectrum.

[0040] Figure 5 This is the FD-MS spectrum of the active ester (A-1) obtained in Example 1.

[0041] Figure 6 This is the GPC spectrum of the active ester (A-1) obtained in Example 1.

[0042] Figure 7 This is the GPC spectrum of the active ester (B-1) obtained in Example 2.

[0043] Figure 8 This is the GPC spectrum of the active ester (C-1) obtained in Example 3.

[0044] Fig. 9 This is the GPC spectrum of the active ester (A-2) obtained in Example 4.

[0045] Fig.10 This is the GPC spectrum of the active ester (A-3) obtained in Example 5.

[0046] Fig.11 This is the GPC spectrum of the active ester (D-1) obtained in Comparative Example 1.

[0047] Fig.12 This is the GPC spectrum of the active ester (E-1) obtained in Example 11.

[0048] Fig.13 This is the infrared spectrum of the active ester (E-1) obtained in Example 11.

[0049] Fig.14 This is the GPC spectrum of the active ester (E-2) obtained in Example 12.

[0050] Fig.15 This is the GPC spectrum of the active ester (E-3) obtained in Example 13. DETAILED DESCRIPTION

[0051] <Active ester (I)>

[0052] The active ester of the present invention is characterized in that it has a structure in which a residue (A) of a polyol compound and a residue (Q) of an aromatic polycarboxylic acid are bonded via an ester bond, and the active ester is capped with a residue (C) of a terminal monovalent aromatic hydroxyl group-containing compound.

[0053] The active ester has an ester bond and a low polar structure. By including the residue (A) of the polyol compound that can form a soft segment, a cured product obtained by using the active ester has excellent flexibility and low dielectric properties, which is useful.

[0054] The active ester of the present invention comprises the residue (A) of the aforementioned polyol compound, and as its valence, it is preferably 2 to 6, and more preferably 2. If the aforementioned valence is 2 or more, the number of functional groups of the generated active ester becomes 2 or more, which is excellent from the viewpoint of curability. In addition, as the residue (A) of the aforementioned polyol compound, it is more preferred to include a hydrocarbon chain or an ether chain, among which, from the viewpoint of heat resistance, it is further preferred to include a hydrocarbon chain. In addition, as a hydrocarbon chain, the number of carbon atoms is preferably 3 to 17, and more preferably 4 to 17. If the number of carbon atoms is within the aforementioned range, an active ester with excellent compatibility and heat resistance is formed, which becomes a preferred embodiment.

[0055] The active ester of the present invention comprises the residue (Q) of the aforementioned aromatic polycarboxylic acid, and its valence is preferably 2 to 4, and more preferably 2. If the valence is 2 or more, the number of functional groups of the generated active ester becomes 2 or more, which is excellent from the viewpoint of curability. In addition, the aforementioned aromatic is not particularly limited as long as it is a compound containing an aromatic ring having a carboxyl group.

[0056] The active ester of the present invention is an active ester blocked with the residue (C) of the aforementioned terminal monovalent aromatic hydroxyl-containing compound, and the aforementioned monovalent aromatic hydroxyl-containing compound is not particularly limited as long as it has an aromatic ring and one (monovalent) hydroxyl group on the aromatic ring.

[0057] It should be noted that the aforementioned "residue of a polyol compound (A)" in the present invention means a group obtained by removing a hydroxyl group from an alcohol, the aforementioned "residue of an aromatic polycarboxylic acid (Q)" means a group obtained by removing a carboxyl group from an aromatic polycarboxylic acid, and the "residue of a terminal monovalent aromatic hydroxyl-containing compound (C)" means a group obtained by removing a hydroxyl group from an aromatic hydroxyl-containing compound. In addition, the aforementioned alcohol includes not only aliphatic alcohols but also alcohols containing an aromatic ring.

[0058] <Active ester (II)>

[0059] The active ester of the present invention is preferably obtained by reacting an ester compound (iii) with a polyol compound (iv), wherein the ester compound (iii) is obtained by reacting an aromatic compound having at least two carboxyl groups and / or an acid halide or ester thereof (i) with an aromatic compound having one aromatic hydroxyl group (ii).

[0060] By reacting the above (i) and (ii), an ester compound (iii) having an ester bond is obtained, and further, by reacting the ester compound (iii) with the above (iv) to undergo an ester exchange reaction, an active ester containing an aryloxycarbonyl structure at the terminal can be obtained. The above active ester exhibits flexibility derived from the polyol compound (iv) and epoxy curing properties and low dielectric properties derived from the terminal aryloxycarbonyl group, and therefore, the cured product obtained using the active ester is excellent in flexibility and low dielectric properties and is useful.

[0061] The active ester of the present invention preferably uses the aromatic compound having at least two carboxyl groups and / or its acid halide or ester (i), and the number of the carboxyl groups is more preferably 2 to 4, and even more preferably 2. By setting the number of the carboxyl groups to at least 2 (2 or more), the number of functional groups of the generated active ester reaches 2 or more, which is excellent from the viewpoint of curability.

[0062] The active ester of the present invention preferably uses the aromatic compound (ii) having one aromatic hydroxyl group. When the aromatic compound has one aromatic hydroxyl group, the obtained active ester has an aryloxycarbonyl terminal, which is excellent in terms of dielectric properties.

[0063] The active ester of the present invention preferably uses an ester compound (iii), which is obtained by reacting the aforementioned aromatic compound having at least two carboxyl groups and / or its acyl halide or ester (i) with an aromatic compound having one aromatic hydroxyl group (ii). Since the aforementioned ester compound is a compound having an aryloxycarbonyl terminal, it has excellent dielectric properties and is therefore preferred.

[0064] The active ester of the present invention preferably uses the polyol compound (iv), and its valence is preferably 2 to 6, more preferably 2. When the valence is 2 or more, the number of functional groups of the generated active ester reaches 2 or more, which is excellent in terms of curability.

[0065] <Active ester (III)>

[0066] The active ester of the present invention is preferably represented by the following general formula (1).

[0067]

[0068] In the above formula (1), it is preferred that: A is a linear or branched alkylene chain, or a linear or branched alkylene ether chain, Q is an aromatic ring, x is an average repetition number of 0.01 or more, and Ar is a structure represented by the following general formula (2) or (3).

[0069]

[0070] Preferably, in the above formulae (2) and (3), * represents a site bonded to the oxygen atom bonded to Ar in the above formula (1), Ra is independently any one of a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a naphthyl group, y is an integer from 0 to 7, and z is an integer from 0 to 5.

[0071] The active ester has multiple ester bonds and contains a linear or branched alkylene chain or a linear or branched alkylene ether chain. Therefore, the chain structure has low polarity and constitutes a soft segment. Therefore, it is useful to obtain a cured product with excellent flexibility and low dielectric properties.

[0072] A in the above formula (1) is preferably a linear or branched alkylene chain or a linear or branched alkylene ether chain, more preferably a linear alkylene chain or a linear alkylene ether chain, wherein, from the viewpoint of thermal decomposition resistance, it is further preferred to include a linear alkylene ether chain. In addition, as a linear or branched chain, the number of carbon atoms is preferably 2 to 20, the number of carbon atoms is more preferably 4 to 18, and the number of carbon atoms is further preferably 6 to 16. If the number of carbon atoms is within the above range, an active ester with excellent compatibility is formed, which is a preferred embodiment.

[0073] Q in the above formula (1) is preferably an aromatic ring, more preferably any of a benzene ring, a naphthalene ring or an anthracene ring. Among them, a benzene ring is more preferred from the viewpoint of industrial availability and solubility of the raw material.

[0074] In the above formula (1), x is preferably an average repetition number of 0.01 or more, more preferably an average repetition number of 0.1 to 5, and even more preferably an average repetition number of 0.2 to 5 from the viewpoint of workability and flexibility of the obtained cured product.

[0075] Ra in the above formula (2) or (3) is preferably independently any one of a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group or a naphthyl group, among which, from the viewpoint of dielectric properties, workability and flexibility of the obtained cured product, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aralkyl group or a naphthyl group is more preferred.

[0076] It is preferred that y in the above formula (2) or (3) is an integer of 0 to 7 and z is an integer of 0 to 5, more preferably y and z are each independently an integer of 0 to 5, and from the viewpoint of reactivity and flexibility of the obtained cured product, it is further preferred that y and z are each independently an integer of 0 to 4.

[0077] The active ester of the present invention (e.g., the above-mentioned (I) to (III)) has a function as a curing agent for epoxy resins, etc., and has a soft segment in its structure, which can impart softness to the cured product obtained by using the above-mentioned active ester, and is a preferred embodiment. In addition, when the above-mentioned active ester reacts with the epoxy resin, the generation of hydroxyl groups can be prevented or suppressed, and low dielectric properties are excellent, which is useful.

[0078] The active ester of the present invention is not particularly limited as long as it is an ester compound having a structure shown in any one of the above-mentioned active esters (I) to (III). It is preferably a reaction product (equivalent to the above-mentioned active ester) obtained by reacting a reaction product (c) with a compound (d), wherein the reaction product (c) is an aromatic compound having two or more carboxyl groups and / or its acyl halide or ester (a) and an aromatic monohydroxy compound (b), and the compound (d) has two or more hydroxyl groups and has a straight or branched alkylene chain or a straight or branched alkylene ether chain. By using the above-mentioned active ester, a cured product with low dielectric loss tangent and better heat resistance can be obtained, which is a preferred embodiment. The reason may not be clear, but the obtained active ester contains an aryloxycarbonyl group at the end, and therefore, it shows high reactivity with the epoxy group of the epoxy resin described later. The generation of hydroxyl groups generated by the ring opening of the epoxy group can be prevented or suppressed by the high reactivity, which is a preferred embodiment. In addition, the aforementioned active ester has no hydroxyl group or almost no hydroxyl group in the molecule, and therefore, in the cured product obtained by the reaction of the aforementioned active ester, there is no or almost no hydroxyl group derived from the active ester. According to this active ester, the generation of hydroxyl groups during curing can be prevented or suppressed. In general, it is known that hydroxyl groups with high polarity will increase the dielectric loss tangent, but by using the aforementioned active ester, a low dielectric loss tangent of the cured product can be achieved, which is useful.

[0079] Furthermore, since the active ester has two or more ester bonds reactive with epoxy groups of the epoxy resin described below, the crosslinking density of the cured product is increased, and heat resistance can be improved.

[0080] The active ester of the present invention has a soft segment such as an alkylene chain or an alkylene ether chain, has no or almost no hydroxyl group, and therefore has a structure with low polarity. The obtained cured product can obtain excellent flexibility, and a curable resin composition (for example, an epoxy resin composition containing an epoxy resin) that can exhibit adhesion to copper foil and the like and low dielectric properties resulting from the flexibility can be provided. Furthermore, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a laminated film, etc. using the above-mentioned curable resin composition can be provided, which is a preferred embodiment.

[0081] The active ester preferably has a softening point of 200° C. or lower, more preferably 180° C. or lower, from the viewpoint of achieving better balance between handleability when preparing a curable resin composition described below and heat resistance and dielectric properties of the cured product.

[0082] [Aromatic compound having two or more carboxyl groups and / or its acid halide or ester (a)]

[0083] The aromatic compound having two or more carboxyl groups and / or its acyl halide or ester (a) (compound derived from the residue (Q) of the aromatic polycarboxylic acid) is a carboxylic acid having two or more carboxyl groups or its derivative, specifically, an acyl halide or ester (hereinafter sometimes referred to as "aromatic compound (a)"). The aromatic compound (a) has two or more carboxyl groups, etc., and thus reacts with the aromatic monohydroxy compound (b) described later, and further reacts with a compound (d) having two or more hydroxyl groups and having a linear or branched alkylene chain (aliphatic hydrocarbon group) or a linear or branched alkylene ether chain (alkyleneoxy group) (hereinafter sometimes referred to as "compound (d)") (compound derived from the residue (A) of the polyol compound), thereby forming a structure including both a flexible structural part derived from the compound (d) and an aryloxycarbonyl structure having epoxy curability at the terminal in the structure of the active ester, and forming an ester structure having high reactivity in the structure of the active ester.

[0084] The aromatic compound (a) is not particularly limited, and compounds having two or more carboxyl groups on a substituted or unsubstituted aromatic ring can be cited. It should be noted that "carboxyl groups, etc." can include: carboxyl groups; halogenated acyl groups such as fluorinated acyl groups, chlorinated acyl groups, and brominated acyl groups; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl and naphthoxycarbonyl groups. It should be noted that in the case of having a halogenated acyl group, the aromatic compound is an acyl halide, and in the case of having an alkoxycarbonyl or aryloxycarbonyl group, the aromatic compound can form an ester. Among these, the aromatic compound preferably has a carboxyl group, a halogenated acyl group, and an aryloxycarbonyl group, more preferably a carboxyl group, a halogenated acyl group, and further preferably a carboxyl group, a chlorinated acyl group, and a brominated acyl group.

[0085] The aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, a condensed aromatic ring, and an aromatic ring connected via an alkylene chain.

[0086] The aromatic compound (a) is not particularly limited, and examples thereof include benzene dicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid; benzene tricarboxylic acids such as trimellitic acid and 5-allyl trimellitic acid; naphthalene dicarboxylic acids such as naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allyl naphthalene-1,4-dicarboxylic acid, and 3,7-diallyl naphthalene-1,4-dicarboxylic acid; pyridine tricarboxylic acids such as 2,4,5-pyridine tricarboxylic acid; triazine carboxylic acids such as 1,3,5-triazine-2,4,6-tricarboxylic acid; and acid halides and esters thereof. Among these, benzene dicarboxylic acid and benzene trimeric acid are preferred, isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acid trichloride are more preferred, and isophthaloyl chloride, terephthaloyl chloride and 1,3,5-benzenetricarboxylic acid trichloride are still more preferred.

[0087] Among the above, from the viewpoint of the flexibility of the obtained cured product, the industrial availability of raw materials, and the workability, aromatic compounds whose aromatic rings are monocyclic aromatic rings, aromatic compounds whose aromatic rings are condensed aromatic rings, etc. are preferred, and benzene dicarboxylic acid, benzene tricarboxylic acid, naphthalene dicarboxylic acid, and their acyl halides are preferred, and benzene dicarboxylic acid, naphthalene dicarboxylic acid, and their acyl halides are more preferred, and isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 1,3,5-benzene tricarboxylic acid, and their acyl halides are further preferred. The above aromatic compound (a) may be used alone or in combination of two or more.

[0088] [Aromatic monohydroxy compound (b)]

[0089] The aromatic monohydroxy compound (b) used in the present invention (a compound derived from the residue (C) of the above-mentioned terminal monovalent aromatic hydroxyl-containing compound) can be listed, for example, alkylphenols such as phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, and tert-butylphenol; aralkylphenols such as o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrenated phenol, and 4-(α-cumyl)phenol; naphthol compounds such as 1-naphthol and 2-naphthol. They can be used alone or in combination of two or more. Among them, from the aspect of obtaining a cured product with excellent dielectric properties, o-cresol and naphthol are preferred.

[0090] The reaction of the aromatic compound (a) with the aromatic monohydroxy compound (b) is not particularly limited. For example, it can be carried out in the presence of an alkali catalyst at a temperature of 60°C or less with a reaction time of 1 to 24 hours. Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, and the like. They can be used alone or in combination of two or more. Among these, sodium hydroxide or potassium hydroxide is preferred from the perspective of high reaction efficiency. In addition, these catalysts can be used in the form of a 3 to 30% aqueous solution. In addition, at this time, in order to improve the reaction efficiency, a phase transfer catalyst can be used. Examples include alkyl ammonium salts, crown ethers, and the like. They can be used alone or in combination of two or more.

[0091] From the aspect of easy control of the reaction, the above reaction is preferably carried out in an organic solvent. The organic solvent used here can be listed as hydrocarbon solvents such as pentane and hexane; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. These can be used alone or as a mixed solvent of two or more.

[0092] The reaction ratio of the aromatic compound (a) to the aromatic monohydroxy compound (b) can be appropriately changed according to the desired molecular design. From the viewpoint of reducing unreacted ends and reducing excess reaction raw materials, the aromatic monohydroxy compound (b) is preferably in the range of 2.0 to 5.0 mol, more preferably 2.0 to 4.0 mol, and even more preferably 2.0 to 3.0 mol, relative to 1 mol of the aromatic compound (a).

[0093] After the reaction is completed, when an aqueous solution is used in the presence of an alkali catalyst, the aqueous layer is removed by allowing the reaction solution to stand for separation, and the remaining organic layer is washed with water, and the washing is repeated until the aqueous layer becomes almost neutral (pH is about 7), thereby obtaining a reaction product of the aromatic compound (a) and the aromatic monohydroxy compound (b) in which the content of inorganic salts that have an adverse effect on insulation properties is reduced, i.e., a reaction product (c).

[0094] [Compound (d) having two or more hydroxyl groups and having a linear or branched alkylene chain or a linear or branched oxyalkylene chain]

[0095] The active ester of the present invention can be produced by reacting the reaction product (c) with the compound (d) having two or more hydroxyl groups and having a linear or branched alkylene chain (aliphatic hydrocarbon group) or a linear or branched alkylene ether chain (oxyalkylene group). By using the compound (d), the alkylene chain (aliphatic hydrocarbon group) and alkylene ether chain (oxyalkylene group) derived from the compound (d) can be introduced into the structure of the obtained active ester to form a soft segment, and the cured product obtained using the active ester can be given flexibility, and further, a structure with low polarity can be introduced, so that the low dielectric properties are excellent, which becomes a preferred mode. In addition, when synthesizing the active ester, the generation of hydroxyl groups can be prevented or suppressed, and the low dielectric properties are excellent, which is useful. It should be noted that the compound (d) is not particularly limited, and examples thereof include aliphatic polyol compounds (d-1), polyol compounds containing oxyalkylene groups (d-2), and the like.

[0096] [Aliphatic polyol compound (d-1)]

[0097] As the aforementioned aliphatic polyol compound (d-1), from the viewpoints that the softness, fracture toughness and tensile strength of the cured product are high and a cured product (curable resin composition) with excellent impregnation properties into a substrate and reinforcing fibers can be obtained, and from the viewpoint of the ease of controlling the molecular weight distribution of the reactant, the aforementioned aliphatic polyol compound (d-1) is preferably a diol compound containing two alcoholic hydroxyl groups, and further preferably a linear aliphatic diol compound having 2 to 20 carbon atoms, more preferably a linear aliphatic diol compound having 4 to 18 carbon atoms, and still more preferably a linear aliphatic diol compound having 6 to 16 carbon atoms.

[0098] Examples of the aliphatic polyol compound (d-1) include linear aliphatic diol compounds such as ethylene glycol (number average molecular weight: 62), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; propylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-ethylbutane-1,4-butanediol, 2,3-dimethyl-1, Aliphatic diol compounds having a branched chain, such as 4-butanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 3,3-dimethylpentane-1,5-diol, 2,2-diethyl-1,3-propanediol, 3-propylpentane-1,5-diol, 2,2-diethyl-1,4-butanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dipropyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, and 2,5-diethyl-1,6-hexanediol; and aliphatic polyol compounds having three or more functions, such as trimethylolethane, trimethylolpropane, glycerol, hexanetriol, and pentaerythritol. These aliphatic polyol compounds may be used alone or in combination of two or more.

[0099] [Polyol compound containing oxyalkylene group (d-2)]

[0100] As the polyol compound (d-2) containing an oxyalkylene group, a diol compound containing two alcoholic hydroxyl groups is preferred, from the viewpoint that the softness, fracture toughness and tensile strength of the cured product are high and a cured product (curable resin composition) having excellent impregnation into a substrate or reinforcing fiber is obtained. It should be noted that, when the hydroxyl equivalent of the polyol compound is less than 270 g / eq as described later, a diol compound having a hydroxyl equivalent of 50 to 269 g / eq of the polyol compound (d-2) containing an oxyalkylene group is more preferred, and a diol compound having a hydroxyl equivalent of 100 to 250 g / eq is further preferred.

[0101] Examples of the aforementioned oxyalkylene group-containing diol compound (d-2) include ethylene oxide and propylene oxide adducts of diols represented by diethylene glycol and dipropylene glycol, and ethylene oxide and propylene oxide adducts of polyphenol compounds represented by ethylene oxide adducts of bisphenol A. These diol compounds may be used alone or in combination of two or more.

[0102] As the number average molecular weight (Mn) of the compound (d), it is preferred to use a compound in the range of 62 to 1000, and more preferably a compound in the range of 62 to 500. If the number average molecular weight is within the above range, the workability becomes good, which is preferred. The number average molecular weight (Mn) of the compound (d) is the nominal value of the manufacturer or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described below.

[0103] As the compound (d), a commercially available product may be used. Examples of the commercially available product include diethylene glycol manufactured by Mitsubishi Chemical Corporation and BPA-2 diol manufactured by Nippon Emulsifier Co., Ltd.

[0104] By reacting the reaction product (c) with the compound (d), an ester exchange reaction occurs, and the active ester of the present invention can be obtained. As the reaction conditions, for example, the active ester can be obtained by stirring / reacting at a temperature of 50 to 250° C. for 1 to 24 hours. In addition, the reaction can be promoted by adding a base catalyst, wherein an amine catalyst (alkylamines such as triethylamine, arylamines such as triphenylamine, cyclopentane amines such as DBU and DBN, heterocyclic amines such as imidazole and pyridine). It should be noted that after the reaction, in order to remove the excess aromatic monohydroxy compound (b), a high-purity active ester can be obtained by distilling under normal pressure or reduced pressure (e.g., 0.9 to 0.01 atmospheres).

[0105] In the above reaction, the same solvent as that used in the reaction of the aromatic compound (a) and the aromatic monohydroxy compound (b) can be used.

[0106] The reaction ratio of the reaction product (c) and the compound (d) can be appropriately changed according to the desired molecular design. However, from the perspective of forming an active ester having better workability and flexibility, the hydroxyl group equivalent of the compound (d) relative to 1 equivalent of the active ester group of the reaction product (c) is preferably in the range of 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol, and even more preferably 0.3 to 0.7 mol.

[0107] In the active ester of the present invention, the hydroxyl equivalent of the polyol compound is preferably less than 270 g / eq, more preferably 31 g / eq or more and less than 270 g / eq, and further preferably 38 g / eq or more and less than 250 g / eq. When the hydroxyl equivalent is less than 270 g / eq, the cured product is excellent in terms of heat resistance.

[0108] When the total number of aromatic ester groups in the active ester structure is defined as the number of functional groups of the active ester, from the perspective of obtaining a cured product having excellent curability and low dielectric constant and dielectric loss tangent (low dielectric properties), when the hydroxyl equivalent of the polyol compound is less than 270 g / eq, the functional group equivalent of the active ester of the present invention is preferably in the range of 160 to 1500 g / eq, more preferably in the range of 180 to 1200 g / eq, and even more preferably in the range of 200 to 660 g / eq.

[0109] When the hydroxyl equivalent of the polyol compound is less than 270 g / eq, the number average molecular weight (Mn) of the active ester of the present invention is preferably 320 to 3000, more preferably 360 to 2400. When the number average molecular weight (Mn) is 320 or more, it is preferred from the perspective of excellent dielectric loss tangent. On the other hand, when the number average molecular weight (Mn) is 3000 or less, it is preferred from the perspective of excellent moldability.

[0110] In the active ester of the present invention, the hydroxyl equivalent of the polyol compound is preferably 270 g / eq or more, more preferably 280 g / eq or more, and further preferably 300 to 10000 g / eq. When the hydroxyl equivalent is 270 g / eq or more, the properties derived from the polyol compound are easily expressed, and therefore, the cured product is excellent in flexibility.

[0111] When the total number of aromatic ester groups in the active ester structure is defined as the number of functional groups of the active ester, from the perspective of obtaining a cured product having excellent curability and low dielectric constant and dielectric loss tangent (low dielectric properties), when the hydroxyl equivalent of the polyol compound is 270 g / eq or more, the functional group equivalent of the active ester of the present invention is preferably in the range of 160 to 3000 g / eq, more preferably in the range of 180 to 2800 g / eq, and even more preferably in the range of 200 to 2600 g / eq.

[0112] When the hydroxyl equivalent of the polyol compound is 270 g / eq or more, the number average molecular weight (Mn) of the active ester of the present invention is preferably 320 to 6000, more preferably 360 to 5600, and particularly preferably 400 to 5200. When the number average molecular weight (Mn) is 320 or more, it is preferred from the perspective of excellent dielectric loss tangent. On the other hand, when the number average molecular weight (Mn) is 6000 or less, it is preferred from the perspective of excellent moldability.

[0113] It should be noted that the hydroxyl equivalent of the polyol compound can satisfy low dielectric properties, whether it is less than 270 g / eq or more than 270 g / eq. For example, when it is particularly desired to improve the heat resistance of the cured product obtained using the active ester of the present invention, the hydroxyl equivalent is preferably less than 270 g / eq.

[0114] In the active ester of the present invention, the polyol compound is preferably a polyol having an aliphatic hydroxyl group. The active ester has a plurality of ester bonds and includes a structure derived from the polyol having an aliphatic hydroxyl group, and the structure has low polarity and constitutes a soft segment, so that a cured product having excellent softness and low dielectric properties can be obtained, which is useful.

[0115] When the polyol compound is a polyol having an aliphatic hydroxyl group, and the residue (A) of the polyol compound is a residue of the polyol having an aliphatic hydroxyl group (when A in the above formula (1) is a residue of a polyol having an aliphatic hydroxyl group), it is more preferred that the residue contains at least one structure selected from the group consisting of a hydrocarbon bond, a (carbonic acid) ester bond, an ether bond, a urethane bond and a siloxane bond, and from the viewpoint of flexibility and heat resistance, it is further preferred that the residue contains at least one structure selected from the group consisting of a hydrocarbon bond, a (carbonic acid) ester bond and an ether bond.

[0116] <Active ester (IV)>

[0117] In the active ester of the present invention, the residue of the polyol having an aliphatic hydroxyl group is preferably at least one structural unit selected from the group consisting of a structural unit derived from a hydrocarbon polyol, a structural unit derived from a polycarbonate polyol, a structural unit derived from a polyester polyol, a structural unit derived from a polyether polyol, a structural unit derived from a polyurethane polyol, and a structural unit derived from a polysiloxane polyol.

[0118] The active ester includes a structural unit derived from a compound including a specific structure having a hydroxyl group. These structures have low polarity and constitute a soft segment. Therefore, a cured product having excellent flexibility and low dielectric properties can be obtained, which is useful.

[0119] As the structural unit derived from the hydrocarbon polyol, it is preferable to use an olefin polymer or dimer alcohol having a terminal diol obtained by polymerizing one or more olefin monomers such as ethylene, propylene, butadiene, and styrene.

[0120] The structural unit derived from the polycarbonate polyol is preferably obtained by using a polycarbonate polyol having a terminal diol obtained by polymerizing one or more divalent diols such as pentanediol, 1,6-hexanediol, and methylpentanediol via a carbonate bond.

[0121] As the structural unit derived from the polyester polyol, it is preferred to use a polyester polyol having a terminal diol obtained by polycondensing a diol monomer such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, pentanediol, 1,6-hexanediol, and methylpentanediol with one or more of a dicarboxylic acid monomers such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.

[0122] As the structural unit derived from the polyether polyol, it is preferable to use a polyether polyol having a terminal diol obtained by adding an epoxy compound such as ethylene oxide or propylene oxide to a diol compound such as ethylene glycol, propylene glycol, or bisphenol A.

[0123] As the structural unit derived from the polyurethane polyol, it is preferred to use a polyurethane polyol having a terminal diol obtained by polymerizing the various polyols described above with one or more of polyisocyanates such as diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI).

[0124] As the structural unit derived from the polysiloxane polyol, it is preferably obtained by using a polysiloxane polyol having a structural unit such as dimethylsiloxane or methylphenylsiloxane.

[0125] The active ester (IV) of the present invention, when used together with epoxy resin, has the function of a curing agent, has a soft segment in its structure, and can impart flexibility to the cured product obtained by using the active ester, which is a preferred embodiment. In addition, when the active ester reacts with the epoxy resin, the generation of hydroxyl groups can be prevented or suppressed, and the low dielectric properties are excellent, which is useful.

[0126] The active ester of the present invention is not particularly limited as long as it is an ester compound having the structure shown in the above active ester (IV). For example, it is preferably a reaction product (equivalent to the above active ester) obtained by reacting the reaction product (c-1) with any compound having at least two hydroxyl groups among hydrocarbon polyol (e-1), polycarbonate polyol (e-2), polyester polyol (e-3), polyether polyol (e-4), polyurethane polyol (e-5) and polysiloxane polyol (e-6), wherein the reaction product (c-1) is a reaction product of an aromatic compound having two or more carboxyl groups and / or its acyl halide or ester (a-1) and an aromatic monohydroxy compound (b-1). By using the above active ester, a cured product having a low dielectric loss tangent and better heat resistance is obtained. The aforementioned active ester contains an aryloxycarbonyl group at the end, therefore, it shows high reactivity with the epoxy group reaction possessed by the epoxy resin described later, and utilizing this high reactivity, it is possible to prevent or suppress the generation of hydroxyl groups produced by the ring-opening of the epoxy group, becoming a preferred mode. In addition, the aforementioned active ester does not have or hardly has a hydroxyl group in the molecule, therefore, in the cured product obtained by the reaction of the aforementioned active ester, there is also no or hardly any hydroxyl group derived from the active ester. Like this, according to the aforementioned active ester, it is possible to prevent or suppress the generation of hydroxyl groups during curing. In general, it is known that hydroxyl groups with high polarity can increase the dielectric loss tangent, but by using the aforementioned active ester, it is useful to achieve the low dielectric loss tangent of the cured product.

[0127] Furthermore, since the active ester has two or more ester bonds reactive with epoxy groups of the epoxy resin described below, the crosslinking density of the cured product is increased, and heat resistance can be improved.

[0128] The active ester of the present invention has a soft segment and has or almost no hydroxyl group, and therefore has a structure with low polarity. The obtained cured product can obtain excellent flexibility, and a curable resin composition (e.g., an epoxy resin composition containing an epoxy resin) that can show adhesion to copper foil, etc. due to this flexibility can be provided. Furthermore, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit substrate, a laminated film, etc. using the above-mentioned curable resin composition can be provided, which is a preferred embodiment.

[0129] The active ester preferably has a softening point of 200° C. or lower, more preferably 180° C. or lower, from the viewpoint of achieving better balance between handling properties when preparing a curable resin composition described below and heat resistance and dielectric properties of the cured product.

[0130] [Aromatic compound having two or more carboxyl groups and / or its acid halide or ester (a-1)]

[0131] The aromatic compound having two or more carboxyl groups and / or its acid halide or ester (a-1) (compound derived from the residue (Q) of the aromatic polycarboxylic acid) is a carboxylic acid having two or more carboxyl groups or its derivative, specifically, an acid halide or an ester (hereinafter sometimes referred to as "aromatic compound (a-1)"). The aromatic compound (a-1) has two or more carboxyl groups, etc., and thus reacts with the aromatic monohydroxy compound (b-1) described later, and further reacts with any compound having at least two or more hydroxyl groups among hydrocarbon polyol (e-1), polycarbonate polyol (e-2), polyester polyol (e-3), polyether polyol (e-4), polyurethane polyol (e-5) or polysiloxane polyol (e-6), thereby forming a structure including both a flexible structural portion derived from the compound having at least two or more hydroxyl groups and an aryloxycarbonyl structure having epoxy curability at the terminal in the structure of the active ester.

[0132] As the aforementioned aromatic compound, etc. (a-1), there is no particular limitation, and compounds having two or more carboxyl groups, etc. on a substituted or unsubstituted aromatic ring can be cited. It should be noted that "carboxyl groups, etc." can be cited as: carboxyl groups; halogenated acyl groups such as fluorinated acyl groups, chlorinated acyl groups, and brominated acyl groups; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl and naphthoxycarbonyl groups, etc. It should be noted that in the case of having halogenated acyl groups, the aforementioned aromatic compounds can form acyl halides, and in the case of having alkoxycarbonyl and aryloxycarbonyl groups, the aforementioned aromatic compounds can form esters. Among these, the aforementioned aromatic compound preferably has a carboxyl group, a halogenated acyl group, and an aryloxycarbonyl group, more preferably a carboxyl group and a halogenated acyl group, and particularly preferably a carboxyl group, a chlorinated acyl group, and a brominated acyl group.

[0133] The aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, a condensed aromatic ring, and an aromatic ring connected via an alkylene group.

[0134] The aromatic compounds (a-1) are not particularly limited, and examples thereof include benzene dicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid; benzene tricarboxylic acids such as trimellitic acid and 5-allyl trimellitic acid; naphthalene dicarboxylic acids such as naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allyl naphthalene-1,4-dicarboxylic acid, and 3,7-diallyl naphthalene-1,4-dicarboxylic acid; pyridine tricarboxylic acids such as 2,4,5-pyridine tricarboxylic acid; triazine carboxylic acids such as 1,3,5-triazine-2,4,6-tricarboxylic acid; and acid halides and esters thereof. Among these, benzene dicarboxylic acid and benzene trimeric acid are preferred, isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acid trichloride are more preferred, and isophthaloyl chloride, terephthaloyl chloride and 1,3,5-benzenetricarboxylic acid trichloride are still more preferred.

[0135] Among the above, from the viewpoint of the softness of the obtained cured product, the industrial availability of raw materials, and the workability, aromatic compounds whose aromatic rings are monocyclic aromatic rings, aromatic compounds whose aromatic rings are condensed aromatic rings, etc. are preferred, and benzene dicarboxylic acid, benzene tricarboxylic acid, naphthalene dicarboxylic acid, and their acyl halides are preferred, and benzene dicarboxylic acid, naphthalene dicarboxylic acid, and their acyl halides are more preferred, and isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and their acyl halides are further preferred. The above aromatic compounds (a-1) can be used alone or in combination of two or more.

[0136] [Aromatic monohydroxy compound (b-1)]

[0137] The aromatic monohydroxy compound (b-1) used in the present invention (a compound derived from the residue (C) of the above-mentioned terminal monovalent aromatic hydroxyl-containing compound) can be listed, for example, alkylphenols such as phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, and tert-butylphenol; aralkylphenols such as o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrenated phenol, and 4-(α-cumyl)phenol; naphthol compounds such as 1-naphthol and 2-naphthol. They can be used alone or in combination of two or more. Among them, from the aspect of obtaining a cured product with excellent dielectric properties, o-cresol and naphthol are preferred.

[0138] The reaction of the aromatic compound (a-1) and the aromatic monohydroxy compound (b-1) is not particularly limited. For example, it can be carried out in the presence of an alkali catalyst at a temperature of 60°C or less with a reaction time of 1 to 24 hours. Examples of alkali catalysts that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, and the like. They can be used alone or in combination of two or more. Among these, sodium hydroxide or potassium hydroxide is preferred from the perspective of high reaction efficiency. In addition, these catalysts can be used in the form of a 3 to 30% aqueous solution. In addition, at this time, in order to improve the reaction efficiency, a phase transfer catalyst can be used. Examples include alkyl ammonium salts, crown ethers, and the like. They can be used alone or in combination of two or more.

[0139] From the perspective of easy reaction control, the above reaction is preferably carried out in an organic solvent. The organic solvent used here includes, for example, hydrocarbon solvents such as pentane and hexane; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. They can be used alone or as a mixed solvent of two or more.

[0140] The reaction ratio of the aforementioned aromatic compound (a-1) and the aforementioned aromatic monohydroxy compound (b-1) can be appropriately changed according to the desired molecular design. In particular, from the perspective of forming an active ester with better solvent solubility and high curability, the aforementioned aromatic monohydroxy compound (b-1) is preferably in the range of 2.0 to 5.0 mol, more preferably 2.0 to 4.0 mol, and even more preferably 2.0 to 3.0 mol, relative to 1 mol of the aforementioned aromatic compound (a-1).

[0141] After the reaction is completed, when an aqueous solution is used in the presence of an alkali catalyst, the aqueous layer is removed by allowing the reaction solution to stand for separation, and the remaining organic layer is washed with water, and washed repeatedly with water until the aqueous layer is almost neutral (pH is about 7), thereby obtaining the reaction product of the aforementioned aromatic compound (a-1) and the aforementioned aromatic monohydroxy compound (b-1), in which the content of inorganic salts that have an adverse effect on insulation is reduced, i.e., the reaction product (c-1).

[0142] [Compound having at least two hydroxyl groups]

[0143] The active ester of the present invention can be produced by reacting the aforementioned reaction product (c-1) with any compound having at least two or more hydroxyl groups (compounds derived from the residue of the polyol having aliphatic hydroxyl groups) in hydrocarbon polyol (e-1), polycarbonate polyol (e-2), polyester polyol (e-3), polyether polyol (e-4), polyurethane polyol (e-5) or polysiloxane polyol (e-6) (ester exchange reaction). By using any one of the aforementioned compounds having at least two or more hydroxyl groups, a soft segment can be introduced into the structure of the obtained active ester, and the cured product obtained using the aforementioned active ester can be given flexibility and adhesion to copper foil, etc. derived from the flexibility, which is a preferred mode. In addition, it is useful to help improve the adhesion of ester bonds to metals such as copper foil. Furthermore, when synthesizing the aforementioned active ester, the generation of hydroxyl groups can be prevented or suppressed, and the low dielectric properties are excellent, which is useful.

[0144] Regarding the active ester obtained using the aforementioned compound having at least two or more hydroxyl groups, such as the hydrocarbon polyol (e-1), due to its low polarity, it has excellent dielectric properties such as dielectric constant and dielectric loss tangent. Therefore, a curable resin composition can be obtained that can maintain a sufficiently low dielectric constant and exhibit a sufficiently low dielectric loss tangent in the high frequency band (high frequency region) of the MHz band to the GHz band. Therefore, it can be used as a high-frequency molding material and is useful.

[0145] [Hydrocarbon polyol (e-1)]

[0146] The hydrocarbon polyol (e-1) is not particularly limited, and specifically refers to an olefin polyol having an olefin monomer compound such as ethylene, propylene, butadiene, styrene, etc. as an essential monomer, or a diol compound synthesized from a dimer acid. Among them, an olefin polyol is preferred, and from the viewpoint of flexibility, a polybutadiene polymer having a butadiene monomer as an essential monomer is more preferred.

[0147] The olefin polyol may be a product obtained by copolymerizing other polymerizable monomers. Examples of the other polymerizable monomers include aliphatic monoolefin compounds such as butene, pentene, 2-methyl-1-pentene, hexene, 3-methyl-1-hexene, and 3-methyl-2-hexene; alicyclic monoolefin compounds such as cyclohexene; styrene compounds such as 4-methylstyrene and α-methylstyrene; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and 2-(dimethylamino)ethyl (meth)acrylate. Acrylate compounds; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl ether compounds such as vinyl methyl ether and vinyl ethyl ether; vinyl ketone compounds such as vinyl methyl ketone and methyl isopropenyl ketone; ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride; compounds containing nitrogen atoms such as (meth)acrylonitrile, (meth)acrylamide, vinylpyridine, and vinylpyrrolidone; compounds containing halogen atoms such as vinyl chloride, vinylidene chloride, and vinyl fluoride, etc. These may be used alone or in combination of two or more.

[0148] The number average molecular weight (Mn) of the olefin polyol is preferably 500 to 10,000, more preferably 700 to 6,000, and even more preferably 900 to 4,000. If the number average molecular weight is within the above range, an active ester having excellent dielectric properties and workability is formed, which is preferred. The number average molecular weight (Mn) of the olefin polyol is the nominal value of the manufacturer or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described below.

[0149] The aforementioned olefin polyol can be a commercial product. As a commercial product, for example, the G series manufactured by Nippon Soda Co., Ltd. ("G-1000" number average molecular weight (Mn) is 1400, hydroxyl value is 68 to 78 mgKOH / g; "G-2000" number average molecular weight (Mn) is 1900, hydroxyl value is 35 to 55 mgKOH / g; "G-3000" number average molecular weight (Mn) is 3000, hydroxyl value is 27 mgKOH / g or more, etc., all are terminal hydroxyl polybutadiene) etc. As the aforementioned dimer alcohol, a commercial product can be used. As a commercial product, for example, PRIPOL 2033 (hydroxyl value is 202 to 212 mgKOH / g) manufactured by CRODA JAPAN Co., Ltd. can be listed.

[0150] [Polycarbonate polyol (e-2)]

[0151] The polycarbonate polyol (e-2) is not particularly limited, and for example, a polycarbonate polyol having a hydroxyl group at a terminal obtained by reacting a carbonate and / or phosgene with a low molecular weight polyol can be used.

[0152] As the carbonate ester, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, diphenyl carbonate, etc. can be used.

[0153] As the low molecular weight polyol, from the viewpoint of imparting flexibility, a low molecular weight polyol having 2 to 20 carbon atoms is preferably used, and a low molecular weight polyol having 4 to 18 carbon atoms is more preferably used.

[0154] As the low molecular weight polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-biphenol, etc.

[0155] As the polycarbonate polyol, aliphatic polycarbonate polyol and alicyclic polycarbonate polyol are preferably used, and in particular, aliphatic polycarbonate polyol is more preferably used from the viewpoint of flexibility.

[0156] The aliphatic polycarbonate polyol is not particularly limited, and for example, one obtained by reacting 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, or the like is preferably used.

[0157] The alicyclic polycarbonate polyol is not particularly limited, and for example, alicyclic polycarbonate polyols obtained by reacting cyclohexanedimethanol and derivatives thereof are preferably used.

[0158] The number average molecular weight (Mn) of the polycarbonate polyol (e-2) is preferably in the range of 500 to 5000, and more preferably in the range of 800 to 3000. If the number average molecular weight is in the above range, the workability becomes good, which is preferred. The number average molecular weight (Mn) of the polycarbonate polyol (e-2) is the nominal value of the manufacturer or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described below.

[0159] The polycarbonate polyol (e-2) may be a commercially available product. Examples of commercially available products include Kuraray Polyol series ("C-2090" manufactured by Kuraray Co., Ltd., Kuraray Polyol series "PHC" manufactured by Kuraray Co., Ltd., and polycarbonate diol "DURANOL" manufactured by Asahi Kasei Corporation.

[0160] [Polyester polyol (e-3)]

[0161] The polyester polyol (e-3) is not particularly limited and includes, for example, polyester polyols obtained by reacting dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or dialkyl esters thereof, or mixtures thereof, with diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, or mixtures thereof; or polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, poly(β-methyl-γ-valerolactone).

[0162] The polyester polyol (e-3) preferably has a number average molecular weight (Mn) in the range of 500 to 5000, and more preferably has a number average molecular weight in the range of 800 to 3000. If the number average molecular weight is within the above range, an active ester having excellent dielectric properties and workability is formed, which is preferred. The number average molecular weight (Mn) of the polyester polyol (e-3) is the nominal value of the manufacturer or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described below.

[0163] A commercial item can be used as the polyester polyol (e-3), and examples of the commercial item include POLYLITE series manufactured by DIC Corporation.

[0164] [Polyether polyol (e-4)]

[0165] The polyether polyol (e-4) is not particularly limited and examples thereof include polyether polyols obtained by polymerizing ethylene oxide compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as an initiator.

[0166] The number average molecular weight (Mn) of the polyether polyol (e-4) is preferably in the range of 500 to 5000, and more preferably in the range of 800 to 3000. When the number average molecular weight is within the above range, an active ester having excellent dielectric properties and workability is formed, which is preferred. The number average molecular weight (Mn) of the polyether polyol (e-4) is the nominal value of the manufacturer or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described below.

[0167] As the polyether polyol (e-4), a commercially available product can be used. Commercially available products include, for example, SANNIX GP-400, GP-600, GP-1000, GP-1500, GP-3000, GP-4000V, GA-5000S, FA-908, FA-961, FA-921, FA-703, and FA-757 manufactured by Sanyo Chemical; ACTCOL G-28, MN-5000, MN-4000, P-31, and MN-1500 manufactured by Mitsui Chemicals; EXCENOL 1030, 4030, 5030, 230, 828, and 837 manufactured by AGC; PREMINOL 3005, 3010, 3015, 3020, 7001, 7006, and 7012; PREMINOL S3006, 3011, and PREMINOL 7021 (tetrafunctional).

[0168] [Polyurethane polyol (e-5)]

[0169] The aforementioned polyurethane polyol (e-5) is not particularly limited, and examples thereof include polyols having a carbamate bond in one molecule. For example, among the reactants of the various polyols and polyisocyanates mentioned above, preferably, polyurethane polyols obtained by reacting with an NCO / OH ratio of less than 1 can be listed, and more preferably, substances having an NCO / OH ratio of less than 0.9 can be listed.

[0170] Examples of the polyisocyanate include aromatic polyisocyanates such as toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and triphenylmethane triisocyanate; aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(isocyanatocyclohexyl), lysine diisocyanate, trimethylhexamethylene diisocyanate, and 1,3-(isocyanatomethyl)cyclohexane; derivatives (modified products) of polyisocyanates such as biuret forms of these aromatic or aliphatic polyisocyanates or isocyanurate forms of these aromatic or aliphatic polyisocyanates, and adducts obtained by modifying these aromatic or aliphatic polyisocyanates with trimethylolpropane.

[0171] It is preferred to use a polyurethane polyol (e-5) having a number average molecular weight (Mn) in the range of 500 to 5000, and more preferably in the range of 800 to 3000. If the number average molecular weight is within the above range, an active ester having excellent dielectric properties and workability is formed, which is preferred. The number average molecular weight (Mn) of the polyurethane polyol (e-5) is the nominal value of the manufacturer, or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described below.

[0172] As the polyurethane polyol (e-5), a commercially available product can be used.

[0173] [Polysilicone polyol (e-6)]

[0174] The polysiloxane polyol (e-6) is not particularly limited, and examples thereof include polyols having a siloxane bond in one molecule, such as dimethyl polysiloxane and methylphenyl polysiloxane having a hydroxyl group terminal.

[0175] The number average molecular weight (Mn) of the polysiloxane polyol (e-6) is preferably in the range of 500 to 5000, and preferably in the range of 800 to 3000. When the number average molecular weight is within the above range, an active ester having excellent dielectric properties and workability is formed, which is preferred. The number average molecular weight (Mn) of the polysiloxane polyol (e-6) is the nominal value of the manufacturer or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described below.

[0176] Commercially available products may be used as the polysiloxane polyol (e-6), and examples of the commercially available products include KF-6000, KF-6001, KF-6002, KF-6003, X-22-176DX, X-22-176F, and X-22-176-GX-A manufactured by Shin-Etsu Chemical Co., Ltd.

[0177] The active ester of the present invention can be obtained by reacting the reaction product (c-1) with any of the polyols (e-1) to (e-6) having at least two or more hydroxyl groups to cause an ester exchange reaction. The reaction conditions are not particularly limited, and the active ester can be obtained by stirring / reacting for 1 to 24 hours at a temperature of 50 to 250° C., for example. In addition, the reaction can be promoted by adding a base catalyst, especially an amine catalyst (alkylamines such as triethylamine; arylamines such as triphenylamine; ring-contracting amines such as DBU and DBN; heterocyclic amines such as imidazole and pyridine). It should be noted that after the reaction, in order to remove the excess aromatic monohydroxy compound (b-1), a high-purity active ester can be obtained by distilling under normal pressure or under reduced pressure (e.g., 0.9 to 0.01 atmospheres). During the reaction, an antioxidant can be used in combination to prevent deterioration caused by the mixing of trace amounts of oxygen. Specific examples include "4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-1,6-di-tert-butylphenol (manufactured by BASF Japan, trade name: IRGANOX 565) (hindered phenol-based antioxidant)" and the like.

[0178] In the above reaction, the same solvent as that used in the reaction of the aromatic compound (a-1) and the aromatic monohydroxy compound (b-1) can be used.

[0179] The reaction ratio of the reaction product (c-1) and any of the compound polyols (e-1) to (e-6) having at least two hydroxyl groups can be appropriately changed according to the desired molecular design. From the perspective of forming an active ester with better workability and flexibility, the hydroxyl group equivalent of any of the compound polyols (e-1) to (e-6) having at least two hydroxyl groups is preferably in the range of 0.01 to 0.9 mol, more preferably 0.05 to 0.9 mol, and even more preferably 0.1 to 0.8 mol, relative to 1 equivalent of the active ester group of the reaction product (c-1).

[0180] When the total number of aromatic active ester groups in the active ester structure is defined as the number of functional groups of the active ester, from the perspective of obtaining a cured product having excellent curability and low dielectric constant and dielectric loss tangent (low dielectric properties), when the hydroxyl equivalent of the polyol having an aliphatic hydroxyl group is 270 g / eq or more, the functional group equivalent of the active ester of the present invention is preferably in the range of 160 to 3000 g / eq, more preferably in the range of 180 to 2800 g / eq, and even more preferably in the range of 200 to 2600 g / eq.

[0181] When the hydroxyl equivalent of the polyol having aliphatic hydroxyl groups is 270 g / eq or more, the number average molecular weight (Mn) of the active ester of the present invention is preferably 320 to 6000, more preferably 360 to 5600, and particularly preferably 400 to 5200. When the number average molecular weight (Mn) is 320 or more, it is preferred from the perspective of excellent dielectric loss tangent. On the other hand, when the number average molecular weight (Mn) is 6000 or less, it is preferred from the perspective of excellent moldability.

[0182] <Curable Resin Composition>

[0183] The curable resin composition of the present invention preferably contains the above-mentioned active ester and an epoxy resin.

[0184] [Epoxy resin]

[0185] The epoxy resin is not particularly limited, but is preferably a curable resin that contains two or more epoxy groups in a molecule and can be cured by forming a crosslinked network via the epoxy groups.

[0186] The epoxy resin is not particularly limited, and examples thereof include novolac epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, α-naphthol novolac epoxy resins, β-naphthol novolac epoxy resins, bisphenol A novolac epoxy resins, and biphenyl novolac epoxy resins;

[0187] Aralkyl epoxy resins such as phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, phenol biphenyl aralkyl epoxy resin, etc.;

[0188] Bisphenol-A epoxy resin, bisphenol-AP epoxy resin, bisphenol-AF epoxy resin, bisphenol-B epoxy resin, bisphenol-BP epoxy resin, bisphenol-C epoxy resin, bisphenol-E epoxy resin, bisphenol-F epoxy resin, bisphenol-S epoxy resin, tetrabromobisphenol-A epoxy resin and other bisphenol-type epoxy resins;

[0189] Biphenyl type epoxy resins such as biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton;

[0190] Naphthalene type epoxy resin;

[0191] Binaphthol type epoxy resin; Binaphthol type epoxy resin;

[0192] Dicyclopentadiene phenol type epoxy resin and other dicyclopentadiene type epoxy resins;

[0193] Glycidylamine epoxy resins such as tetraglycidyldiaminodiphenylmethane epoxy resin, triglycidyl-p-aminophenol epoxy resin, and glycidylamine epoxy resin of diaminodiphenylsulfone;

[0194] Diglycidyl ester type epoxy resins such as 2,6-naphthalene diglycidyl ester type epoxy resin and glycidyl ester type epoxy resin of hexahydrophthalic anhydride;

[0195] Benzopyran type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran.

[0196] Among these epoxy resins, so-called glycidyl ether epoxy resins obtained by epoxidizing a phenol compound are preferred, and among them, novolac epoxy resins, aralkyl epoxy resins, and dicyclopentadiene epoxy resins are more preferred from the viewpoint of dielectric properties.

[0197] In addition, the above-mentioned epoxy resins may be used alone or in combination of two or more kinds.

[0198] The epoxy equivalent of the epoxy resin is preferably 120 to 400 g / eq, more preferably 150 to 300 g / eq. If the epoxy equivalent of the epoxy resin is 120 g / eq or more, the dielectric properties of the obtained cured product are more excellent, so it is preferred. On the other hand, if the epoxy equivalent of the epoxy resin is 400 g / eq or less, it is preferred from the perspective of excellent balance between heat resistance and dielectric loss tangent of the obtained cured product.

[0199] The softening point of the epoxy resin is preferably 20 to 200° C., more preferably 40 to 150° C. If the softening point of the epoxy resin is 20° C. or higher, rapid curing can be achieved, which is preferred. On the other hand, if the softening point of the epoxy resin is 200° C. or lower, it is preferred from the perspective of excellent moldability.

[0200] The functional group equivalent ratio (active ester / epoxy resin) of the amount of the active ester used relative to the amount of the epoxy resin used is more preferably 0.2 to 2, and more preferably 0.4 to 1.5. If the functional group equivalent ratio is 0.2 or more, the dielectric loss tangent of the obtained cured product can be lower and the flexibility is higher, so it is preferred. If the functional group equivalent ratio exceeds 2, the heat resistance and curing properties will decrease, so it is preferably used within the above range.

[0201] The curable resin composition of the present invention may contain, in addition to the above-mentioned active ester and epoxy resin, other curing agents, other resins, solvents, additives and the like within a range not impairing the effects of the present invention.

[0202] [Other curing agents]

[0203] In the curable resin composition of the present invention, other curing agents may be used in combination with the above-mentioned active ester.

[0204] The other curing agent is not particularly limited, and examples thereof include amine curing agents, acid anhydride curing agents, and phenol resin curing agents.

[0205] The amine curing agent is not particularly limited, and examples thereof include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, menthanediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N'-dimethylpiperazine, and triethylenediamine; and aromatic amines such as meta-phenylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0206] Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol ditrimellitate, glycerol trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endo-methylenetetrahydrophthalic anhydride, methyl-endo-methylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexene dicarboxylic anhydride.

[0207] Examples of the phenolic resin curing agent include phenol novolac resins, cresol novolac resins, naphthol novolac resins, bisphenol novolac resins, biphenyl novolac resins, dicyclopentadiene-phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, trisphenol methane type resins, tetraphenol ethane type resins, and aminotriazine-modified phenolic resins.

[0208] The above-mentioned other curing agents may be used alone or in combination of two or more.

[0209] [Other resins]

[0210] The curable resin composition of the present invention may contain other resins in addition to the epoxy resin. It should be noted that in the present specification, "other resins" refer to resins other than epoxy resins.

[0211] Specific examples of the aforementioned other resins are not particularly limited, and include maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene oxide resins, polyimide resins, cyanate ester resins, benzoxazine resins, cresol novolac resins containing triazine, cyanate ester resins, styrene-maleic anhydride resins, diallyl bisphenol, allyl isocyanurate and other allyl-containing resins, polyphosphates, phosphate-carbonate copolymers, etc. These other resins may be used alone or in combination of two or more.

[0212] [Solvent]

[0213] The curable resin composition of the present invention may be prepared without a solvent, or may contain a solvent. The solvent has a function of adjusting the viscosity of the curable resin composition, etc.

[0214] Specific examples of the above-mentioned solvents are not particularly limited, and include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc. These solvents may be used alone or in combination of two or more.

[0215] The amount of the solvent used is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, relative to the total mass of the curable resin composition. If the amount of the solvent is 10% by mass or more, it is preferred from the perspective of excellent handling properties. On the other hand, if the amount of the solvent is 90% by mass or less, it is preferred from the perspective of economic efficiency.

[0216] [additive]

[0217] The curable resin composition of the present invention may contain additives. Examples of the additives include a curing accelerator, a flame retardant, and a filler.

[0218] (Curing accelerator)

[0219] The curing accelerator is not particularly limited, and examples thereof include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators.

[0220] Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethyl phosphite and triethyl phosphite; phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, and tetrabutylphosphonium decanoate.

[0221] Examples of the amine-based curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU), and 1,5-diazabicyclo[4.3.0]-nonene-5 (DBN).

[0222] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-methylimidazole. 1-Cyanoethyl-2-undecylimidazolium trimellitate, 1-Cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, etc.

[0223] Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-butylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, and 1-phenylbiguanidine.

[0224] Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

[0225] Among the above-mentioned curing accelerators, 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP) are preferably used.

[0226] In addition, the above-mentioned curing accelerators may be used alone or in combination of two or more.

[0227] The amount of the curing accelerator used can be appropriately adjusted to obtain the desired curability, and is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of the mixture of the epoxy resin and the active ester. If the amount of the curing accelerator used is 0.01 parts by mass or more, it is preferred from the perspective of excellent curability. On the other hand, if the amount of the curing accelerator used is 5 parts by mass or less, it is preferred from the perspective of excellent insulation reliability.

[0228] (Flame Retardant)

[0229] The flame retardant is not particularly limited, and examples thereof include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, and halogen-based flame retardants.

[0230] The inorganic phosphorus-based flame retardant is not particularly limited, and examples thereof include red phosphorus; ammonium phosphates such as ammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.

[0231] The organophosphorus flame retardant is not particularly limited, and examples thereof include phosphate esters such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetradecyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl)methacrylate acid phosphate; diphenylphosphines such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. , 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylanthraquinonephosphine oxide, diphenylphenylphosphino-1,4-dioxynaphthalene, 1,4-cyclooctylphosphinyl-1,4-benzenediol, 1,5-cyclooctylphosphinyl-1,4-benzenediol and other phosphorus-containing phenols; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydrooxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic phosphorus compounds; compounds obtained by reacting the above-mentioned phosphate esters, the above-mentioned diphenylphosphine, the above-mentioned phosphorus-containing phenols with epoxy resins, aldehyde compounds, phenol compounds, etc.

[0232] The halogen flame retardant is not particularly limited, and examples thereof include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, and tetrabromophthalic acid.

[0233] The above flame retardants may be used alone or in combination of two or more.

[0234] The amount of the flame retardant is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin. If the amount of the flame retardant is 0.1 parts by mass or more, it is preferred because it can impart flame retardancy. On the other hand, if the amount of the flame retardant is 50 parts by mass or less, it is preferred because it can both maintain dielectric properties and impart flame retardancy.

[0235] (Bulking Agent)

[0236] Examples of fillers include organic fillers and inorganic fillers. Organic fillers have the function of increasing elongation and mechanical strength, while inorganic fillers have the function of reducing thermal expansion coefficient and imparting flame retardancy.

[0237] The organic filler is not particularly limited, and examples thereof include polyamide particles.

[0238] As the aforementioned inorganic filler, there is no particular limitation, and silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. can be listed. Among these, silicon dioxide is preferably used. At this time, as silicon dioxide, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used.

[0239] In addition, the aforementioned filler can be surface treated as required. At this time, as an available surface treatment agent, it is not particularly limited, and aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organic silicon azane compounds, titanate coupling agents, etc. can be used. As a specific example of the surface treatment agent, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc. can be listed.

[0240] In addition, the above-mentioned fillers may be used alone or in combination of two or more.

[0241] The amount of the filler is preferably 0.5 to 95 parts by mass, more preferably 5 to 80 parts by mass, relative to 100 parts by mass of the epoxy resin. If the amount of the filler is 0.5 parts by mass or more, the effect of the filler can be fully imparted, so it is preferred. On the other hand, in order not to increase the viscosity of the compound and damage the moldability, the amount of the filler is preferably 95 parts by mass or less.

[0242] <Cured product>

[0243] The present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction. The active ester itself has a low dielectric loss tangent, so the dielectric loss tangent of the cured product obtained from the curable resin composition containing the active ester is also low. In addition, the obtained cured product can exhibit flexibility, adhesion to metals such as copper foil and low dielectric properties derived from the flexibility, which is a preferred embodiment.

[0244] As a method for obtaining a cured product by subjecting the curable resin composition to a curing reaction, for example, the heating temperature during heat curing is not particularly limited but is 100 to 300° C., and the heating time is preferably 1 to 24 hours.

[0245] <Application of curable resin composition>

[0246] As the purposes of using the above-mentioned curable resin composition, circuit substrate insulating materials such as printed circuit board materials, resin compositions for flexible wiring substrates, interlayer insulating materials for laminated substrates, adhesive films for laminated substrates, resin injection molding materials, adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, laminated films, laminated substrates, fiber-reinforced composite materials, and molded products formed by curing the above-mentioned composite materials can be listed. Among these various purposes, in printed circuit board materials, circuit substrate insulating materials, and laminated adhesive films, passive components such as capacitors and active components such as IC chips can be embedded in the substrate. Insulating materials for so-called electronic component built-in substrates. And then, among the above, the flexible application of cured products has excellent flexibility, adhesion, low dielectric properties and heat resistance, and the curable resin composition of the present invention is preferably used for semiconductor sealing materials, semiconductor devices, prepregs, flexible wiring substrates, circuit substrates, laminated films, laminated substrates, multilayer printed circuit boards, fiber-reinforced composite materials and molded products formed by curing the above-mentioned composite materials. Hereinafter, a method for producing the semiconductor sealing material and the like from the curable resin composition will be described.

[0247] 1. Semiconductor sealing materials

[0248] The present invention relates to a semiconductor sealing material containing the above-mentioned curable resin composition. As a method for obtaining a semiconductor sealing material from the above-mentioned curable resin composition, there can be cited a method of fully melt-mixing the above-mentioned curable resin composition, a curing accelerator, and a compounding agent such as an inorganic filler until uniform using an extruder, a kneader, a roller, etc. as needed. At this time, as an inorganic filler, fused silica is usually used, but when used as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, high-filling or fused silica, crystalline silica, alumina, silicon nitride, etc. having a thermal conductivity higher than that of fused silica can be used. Regarding its filling rate, it is preferred to use an inorganic filler in the range of 30 to 95 parts by mass relative to 100 parts by mass of the curable resin composition, wherein, in order to achieve the improvement of flame retardancy, moisture resistance, resistance to solder cracking, and the reduction of the linear expansion coefficient, it is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more.

[0249] 2. Semiconductor devices

[0250] The present invention relates to a semiconductor device, comprising a cured product obtained by heating and curing the semiconductor sealing material. As a method for obtaining a semiconductor device from the curable resin composition, there can be cited a method in which the semiconductor sealing material is injection molded or molded using a transfer molding machine, an injection molding machine, etc., and then heated at 50 to 200° C. for 2 to 10 hours.

[0251] 3. Prepreg

[0252] The present invention relates to a prepreg, which has a reinforcing substrate and a semi-cured product of the curable resin composition impregnated into the reinforcing substrate. As a method for obtaining a prepreg from the curable resin composition, the following method can be cited: after the curable resin composition prepared as a varnish by mixing the following organic solvent is impregnated into a reinforcing substrate (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.), it is preferably heated at 50 to 170° C. according to the heating temperature corresponding to the type of solvent used. The mass ratio of the resin composition to the reinforcing substrate used at this time is not particularly limited, and it is generally preferred to prepare in a manner that the resin component in the prepreg is 20 to 60% by mass.

[0253] Examples of the organic solvent used herein include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like. The selection and appropriate amount thereof can be appropriately selected depending on the intended use. For example, when a printed circuit board is further manufactured from the prepreg as described below, it is preferred to use a polar solvent having a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, and dimethylformamide. In addition, it is preferred to use the solvent in a ratio of 40 to 80% by mass of the non-volatile component.

[0254] 4. Circuit board

[0255] The present invention relates to a circuit board, which is obtained by laminating the above-mentioned prepreg and copper foil, and heating and pressing them. As a method for obtaining a printed circuit board from the above-mentioned curable resin composition, there can be cited a method of laminating the above-mentioned prepreg by a conventional method, appropriately overlapping copper foil, and heating and pressing them at 170 to 300° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[0256] 5. Flexible wiring substrate

[0257] As a method for manufacturing a flexible wiring substrate from the above-mentioned curable resin composition, there can be cited a method comprising the following three steps. The first step is a step of applying a curable resin composition mixed with an active ester, an epoxy resin and an organic solvent to an electrically insulating film using a coater such as a reverse roll coater or a comma coater, the second step is a step of heating the electrically insulating film coated with the curable resin composition at 60 to 170° C. for 1 to 15 minutes using a heater to volatilize the solvent from the electrically insulating film and to B-stage the curable resin composition, and the third step is a step of thermally pressing a metal foil to an adhesive on the electrically insulating film in which the curable resin composition has been B-staged using a heating roller or the like (the pressing pressure is preferably 2 to 200 N / cm and the pressing temperature is preferably 40 to 200° C.). It should be noted that if sufficient adhesive performance can be obtained by going through the above three steps, the process may be terminated here. If complete adhesive performance is required, it is preferred to further perform post-curing at 100 to 200° C. for 1 to 24 hours. The thickness of the curable resin composition film after final curing is preferably in the range of 5 to 100 μm.

[0258] 6.Laminated substrate

[0259] As a method for manufacturing a laminated substrate from the above-mentioned curable resin composition, a method including the following three steps can be cited. The first step is to use a spraying method, a curtain coating method, etc., to apply the above-mentioned curable resin composition appropriately mixed with rubber, filler, etc. to a circuit substrate formed with a circuit, and then solidify it. The second step is to treat it with a roughening agent after opening a predetermined through-hole portion as required, and wash its surface with hot water to form unevenness, and plate metals such as copper. The third step is to repeat this operation in sequence as desired, and alternately laminate resin insulation layers and conductor layers of predetermined circuit patterns to form a process. It should be noted that the opening of the through-hole portion is preferably performed after the outermost resin insulation layer is formed. In addition to the above-mentioned solution coating, the first step can also be performed by a lamination method based on a laminated film that has been pre-coated to a desired thickness and dried. The laminated substrate of the present invention can also be manufactured by heat-pressing the resin-coated copper foil obtained by semi-curing the resin composition on the copper foil at 170 to 250° C. onto a wiring substrate having a circuit formed thereon, thereby forming a rough surface and omitting the plating process.

[0260] 7. Laminated film

[0261] The present invention relates to a laminated film comprising the aforementioned curable resin composition. As a method for producing the laminated film of the present invention, there can be cited a method of producing the laminated film by coating the aforementioned curable resin composition on a support film to form a curable resin composition layer to prepare an adhesive film for a multilayer printed circuit board.

[0262] When manufacturing a laminated film from a curable resin composition, it is important that the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that enables the resin to be filled into the via holes or through holes present in the circuit substrate while laminating the circuit substrate. It is preferred to mix the above-mentioned components in a manner that exhibits this characteristic.

[0263] Here, the through hole of the multilayer printed circuit board usually has a diameter of 0.1 to 0.5 mm and a depth of 0.1 to 1.2 mm, and it is usually preferable to fill the resin within this range. It should be noted that when laminating both sides of the circuit board, it is desirable that about 1 / 2 of the through hole is filled.

[0264] Specifically, in the method for producing the adhesive film, after preparing the above-mentioned curable resin composition in the form of a varnish, the varnish-like composition is applied to the surface of a supporting film (Y), and then the organic solvent is dried by heating or hot air blowing, thereby forming a composition layer (X) composed of the curable resin composition.

[0265] The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of 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.

[0266] The composition layer (X) in the present invention may be protected by a protective film as described below. Protection by a protective film can prevent the surface of the resin composition layer from being attached with dirt or damaged.

[0267] Examples of the supporting film and protective film 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 release paper, copper foil, aluminum foil, and other metal foils. It should be noted that the supporting film and protective film may be subjected to release treatment in addition to matte treatment and corona treatment.

[0268] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0269] The support film (Y) is peeled off after being laminated on the circuit board or after being heat-cured to form an insulating layer. If the support film (Y) is peeled off after the adhesive film is heat-cured, it is possible to prevent the adhesion of dirt and the like during the curing process. When peeling off after curing, the support film is usually subjected to a demolding treatment in advance.

[0270] 8. Multilayer printed circuit board

[0271] It should be noted that the film obtained by the above operation can also be used to manufacture a multilayer printed circuit board. In the manufacturing method of such a multilayer printed circuit board, when, for example, the composition layer (X) is protected by a protective film, after peeling them off, the composition layer (X) is directly laminated to one or both sides of the circuit substrate by, for example, a vacuum lamination method. The lamination method can be intermittent or continuous using a roller. In addition, before lamination, the adhesive film and the circuit substrate can be heated (preheated) in advance as needed.

[0272] Regarding the lamination conditions, the pressing temperature (lamination temperature) is preferably 70 to 140° C., and the pressing pressure is preferably 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), preferably lamination is carried out under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0273] 9. Fiber-reinforced composite materials

[0274] As a method for producing a fiber-reinforced composite material from the curable resin composition, each component constituting the curable resin composition is uniformly mixed to prepare a varnish, and then the varnish is impregnated into a reinforcing substrate composed of reinforcing fibers and then polymerized.

[0275] Specifically, the curing temperature during the polymerization reaction is preferably in the range of 50 to 250°C, and particularly preferably cured at 50 to 100°C to obtain a tack-free cured product, which is then treated at 120 to 200°C.

[0276] Here, the reinforcing fiber can be any one of twisted yarn, untwisted yarn or untwisted yarn, and untwisted yarn and untwisted yarn are preferred from the perspective of both the formability and mechanical strength of the fiber-reinforced plastic component. Furthermore, regarding the form of the reinforcing fiber, a form in which the fiber direction is aligned in one direction and a fabric can be used. The fabric can be freely selected from plain weave, satin weave, etc. according to the use site and purpose. Specifically, from the perspective of excellent mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc. can be listed, and two or more of them can also be used in combination. Among these, carbon fiber is preferred from the perspective of good strength of the molded product, and various carbon fibers such as polyacrylonitrile, asphalt, and rayon can be used for the carbon fiber. Among them, polyacrylonitrile carbon fiber, which can easily obtain high-strength carbon fiber, is preferred. Here, the amount of reinforcing fiber used when the varnish is impregnated into the reinforcing substrate formed by the reinforcing fiber to make a fiber-reinforced composite material is preferably an amount in which the volume content of the reinforcing fiber in the fiber-reinforced composite material becomes 40 to 85%.

[0277] 10. Fiber-reinforced resin molded products

[0278] As a method for producing a fiber-reinforced resin molded product from the curable resin composition, the following methods can be cited: a hand lay-up method or a spray method in which a fiber skeleton is laid in a mold and the varnish is gradually laminated in multiple layers; a vacuum bag method in which a base material formed of reinforcing fibers is impregnated with the varnish while being laminated and molded using either a male mold or a female mold, and the product obtained is covered with a flexible mold capable of exerting pressure on the molded product, airtightly sealed, and vacuum (decompressed) molded; an SMC press method in which a varnish containing reinforcing fibers is formed into a sheet in advance and the product obtained is compression molded using a mold; an RTM method in which the varnish is injected into a mating mold filled with fibers, and a prepreg in which the varnish is impregnated in the reinforcing fibers is produced and sintered using a large autoclave, etc. It should be noted that the fiber-reinforced resin molded product obtained above is a molded product having reinforcing fibers and a cured product of a curable resin composition. Specifically, the amount of reinforcing fibers in the fiber-reinforced resin molded product is preferably in the range of 40 to 70% by mass, and from the viewpoint of strength, it is particularly preferably in the range of 50 to 70% by mass.

[0279] 11. Others

[0280] The method for manufacturing semiconductor sealing materials etc. has been described above, but other cured products can also be manufactured from curable resin compositions. As the manufacturing method of other cured products, they can be manufactured by the curing method according to the general curable resin composition. For example, the heating temperature condition can be appropriately selected according to the type, purpose, etc. of the combined curing agent.

[0281] Example

[0282] Next, the present invention will be described in more detail based on Examples and Comparative Examples. Hereinafter, "parts" and "%" are based on mass unless otherwise specified. It should be noted that for GPC measurement, 13 C-NMR measurement, FD-MS spectral measurement, and infrared spectral measurement, the measurements were carried out under the following conditions and the like.

[0283] <GPC Measurement>

[0284] The measurement was carried out using the following measurement apparatus and measurement conditions to obtain the GPC spectra of diphenyl isophthalate derivatives, resins containing phenolic hydroxyl groups, and active esters obtained in the following Synthesis Examples / Examples, etc. Based on the results of the aforementioned GPC spectra, the formation of the target products (diphenyl isophthalate derivatives, resins containing phenolic hydroxyl groups, and active esters) was confirmed based on the decrease and disappearance of the raw material peaks.

[0285] Measurement apparatus: "HLC-8320GPC" manufactured by Tosoh Corporation

[0286] Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GELG4000HXL" manufactured by Tosoh Corporation

[0287] Detector: RI (differential refractometer)

[0288] Data processing: "GPC Workstation Eco SEC-Work Station" manufactured by Tosoh Corporation

[0289] Measurement conditions: Column temperature is 40 °C

[0290] Eluent is tetrahydrofuran

[0291] Flow rate is 1.0 ml / minute

[0292] Standard: According to the measurement manual of the aforementioned "GPC Workstation Eco SEC Work Station", the following monodisperse polystyrene with known molecular weight was used.

[0293] (Using polystyrene)

[0294] "A-500" manufactured by Tosoh Corporation

[0295] "A-1000" manufactured by Tosoh Corporation

[0296] "A-2500" manufactured by Tosoh Corporation

[0297] "A-5000" manufactured by Tosoh Corporation

[0298] "F-1" manufactured by Tosoh Corporation

[0299] "F-2" manufactured by Tosoh Corporation

[0300] "F-4" manufactured by Tosoh Corporation

[0301] "F-10" manufactured by Tosoh Corporation

[0302] "F-20" manufactured by Tosoh Corporation

[0303] "F-40" manufactured by Tosoh Corporation

[0304] "F-80" manufactured by Tosoh Corporation

[0305] "F-128" manufactured by Tosoh Corporation

[0306] Sample: A 1.0 mass% tetrahydrofuran solution of the diphenyl isophthalate derivative, resin containing phenolic hydroxyl groups, and active ester obtained in the following synthesis examples / Examples, etc. was filtered through a microfilter, and the resulting product (50 μl) was used.

[0307] <FD-MS Spectrum Measurement>

[0308] The FD-MS spectrum was measured using the following measuring apparatus and measurement conditions. Based on the results, a mass spectrometry peak corresponding to the compound with the repeat number x = 1 of the target product (active ester) was confirmed.

[0309] Measuring apparatus: JMS-T100GC AccuTOF

[0310] Measurement conditions

[0311] Measurement range: m / z = 4.00 - 2000.00

[0312] Rate of change: 51.2 mA / min

[0313] Final current value: 45 mA

[0314] Cathode voltage: -10 kV

[0315] Recording interval: 0.07 sec

[0316] < 13 <C-NMR Measurement>

[0317] Regarding 13The measurement conditions of C-NMR were as follows. From this result, it was confirmed that a structure derived from an aliphatic diol was introduced into the active ester.

[0318] Device: AL-400 manufactured by NEC Corporation

[0319] Measurement mode: SGNNE (1H complete decoupling method to eliminate NOE)

[0320] Solvent: dimethyl sulfoxide

[0321] Pulse angle: 45° pulse

[0322] Sample concentration: 30% by mass

[0323] Cumulative times: 1000 times

[0324] <Infrared spectroscopy>

[0325] Measuring equipment: FT / IR-4100 Fourier transform infrared spectrophotometer manufactured by JASCO Corporation. Sample preparation conditions: The solution was coated on a KBr plate to prepare a measuring sample.

[0326] (I) Group: Examples and Comparative Examples thereof in the case of using a polyol compound having a hydroxyl equivalent of less than 270 g / eq are shown below.

[0327] (Synthesis Example 1): Synthesis of diphenyl isophthalate derivative (A)

[0328] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 808.0 g of isophthaloyl chloride (the number of moles of acyl chloride groups: 4.0 moles) and 4140.0 g of toluene were added, and the system was replaced with nitrogen under reduced pressure to dissolve. Next, 864.0 g (8.0 moles) of o-cresol was added, and the system was replaced with nitrogen under reduced pressure to dissolve. Thereafter, 2.07 g of tetrabutylammonium bromide was dissolved, and the system was controlled to below 60°C while nitrogen purging was performed, and 1648.0 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Then, stirring was continued for 1 hour under the same conditions. After the reaction was completed, the liquid was allowed to stand for separation, and the water layer was removed. Furthermore, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the liquid was allowed to stand for separation to remove the water layer. This operation was repeated until the pH of the water layer reached 7. Thereafter, water and toluene were removed by dehydration by decantation to obtain a diphenyl isophthalate derivative (A) as a crystalline compound. Figure 1 The GPC spectrum of the obtained diphenyl isophthalate derivative (A) is shown in FIG.

[0329] (Synthesis Example 2): Synthesis of diphenyl isophthalate derivative (B)

[0330] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 142.1 g of isophthaloyl chloride (the number of moles of acyl chloride groups: 0.7 moles) and 954.0 g of toluene were added, and the system was replaced with nitrogen under reduced pressure to dissolve. Next, 188.0 g of phenol (1.4 moles) was added, and the system was replaced with nitrogen under reduced pressure to dissolve. Thereafter, 0.33 g of tetrabutylammonium bromide was dissolved, and while nitrogen was purged, the system was controlled to below 60°C, and 288.4 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Then, stirring was continued under the same conditions for 1 hour. After the reaction was completed, the liquid was allowed to stand and separated, and the water layer was removed. Furthermore, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the liquid was allowed to stand and separated to remove the water layer. This operation was repeated until the pH of the water layer reached 7. Thereafter, water and toluene were removed by dehydration by decantation to obtain a diphenyl isophthalate derivative (B) as a crystalline compound. Figure 2 The GPC spectrum of the obtained diphenyl isophthalate derivative (B) is shown in FIG.

[0331] (Synthesis Example 3): Synthesis of diphenyl isophthalate derivative (C)

[0332] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 142.1 g of isophthaloyl chloride (the number of moles of acyl chloride group: 0.7 mole) and 903.0 g of toluene were added, and the system was replaced with nitrogen under reduced pressure to dissolve. Next, 210.0 g (1.4 moles) of p-tert-butylphenol (hereinafter abbreviated as "PTBP") was added, and the system was replaced with nitrogen under reduced pressure to dissolve. Thereafter, 0.45 g of tetrabutylammonium bromide was dissolved, and the system was controlled to below 60°C while nitrogen purging was performed, and 288.4 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Then, stirring was continued for 1 hour under the same conditions. After the reaction was completed, the liquid was allowed to stand for separation, and the water layer was removed. Furthermore, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the liquid was allowed to stand for separation to remove the water layer. This operation was repeated until the pH of the water layer reached 7. Thereafter, water and toluene were removed by dehydration by decantation to obtain a diphenyl isophthalate derivative (C) as a crystalline compound. Figure 3 The GPC spectrum of the obtained diphenyl isophthalate derivative (C) is shown in FIG.

[0333] (Comparative Synthesis Example 1): Synthesis of a Phenolic Hydroxyl Group-Containing Resin (D) (See Japanese Patent No. 6403027)

[0334] 127 g (0.5 mol) of diglycidyl ether of 1,6-hexanediol (manufactured by DIC Corporation: trade name: SR-16HL, epoxy equivalent: 127 g / eq) and 228 g (1.0 mol) of bisphenol A (hydroxy equivalent: 114 g / eq) were added to a flask equipped with a thermometer and a stirrer. After heating to 140°C over 30 minutes, 1.8 g of a 4% aqueous sodium hydroxide solution was added to the flask. Thereafter, the temperature in the flask was raised to 150°C over 30 minutes, and then reacted at 150°C for 5 hours. Thereafter, a neutralizing amount of sodium phosphate was added to the flask to obtain a resin (D) containing phenolic hydroxyl groups. The formation thereof and the hydroxyl equivalent of the obtained resin (D) containing phenolic hydroxyl groups were confirmed to be 300 g / eq based on the GPC spectrum.

[0335] (Example 1): Synthesis of active ester (A-1)

[0336] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 30.0 g of 1,9-nonanediol (hydroxyl equivalent: 80 g / eq), 129.68 g of the diphenyl isophthalate derivative (A) obtained in Synthesis Example 1, and 0.80 g of 1,8-diazabicyclo[5.4.0]-undecene-7 (hereinafter abbreviated as "DBU") were added, the temperature was raised to 190°C, and the mixture was stirred until the reaction was completed. The end time of the reaction was confirmed by GPC. Thereafter, o-cresol was removed by vacuum distillation to obtain an active ester (A-1). According to the feed ratio, the functional group equivalent and average repetition number x (refer to the above general formula (1)) of the obtained active ester (A-1) were 319 g / eq and x=1, respectively. Regarding the obtained active ester (A-1), Figure 4 Shown in 13 C-NMR spectrum, in Figure 5 The FD-MS spectrum is shown in Figure 6 The GPC spectrum is shown in . In addition, from the results of the NMR spectrum and the FD-MS spectrum, the residues (A), (Q) and (C) constituting the active ester (A-1) can be confirmed.

[0337] It should be noted that the average number of repetitions x in the active ester (A-1) of the following structural formula is calculated from the charge ratio based on the following general formula (4) (also refer to the above general formula (1)). In addition, the same method is used to calculate the active esters (B-1), (C-1), (A-2) and (A-3).

[0338] (Average number of repetitions x in the obtained active ester) = (number of moles of hydroxyl groups in the polyol compound) / [(number of moles of active ester groups in the active ester group-containing compound used as a raw material) - (number of moles of hydroxyl groups in the polyol compound)] (4)

[0339] The aforementioned active ester group-containing compound is a diphenyl isophthalate derivative (A) in Example 1 and is a raw material used in the synthesis of the active ester (A-1).

[0340]

[0341] (Example 2): Synthesis of active ester (B-1)

[0342] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 30.0 g of 1,9-nonanediol (hydroxyl equivalent: 80 g / eq), 119.18 g of the diphenyl isophthalate derivative (B) obtained in Synthesis Example 2, and 0.75 g of DBU were added. After the system was replaced with nitrogen under reduced pressure, the temperature was raised to 190°C and stirred until the reaction was completed. The end time of the reaction was confirmed by GPC. Thereafter, phenol was removed by reduced pressure distillation to obtain an active ester (B-1). According to the feed ratio, the functional group equivalent and average repetition number x of the obtained active ester (B-1) were 306 g / eq and x=1, respectively. Figure 7 The GPC spectrum of the obtained active ester (B-1) is shown in FIG.

[0343] (Example 3): Synthesis of active ester (C-1)

[0344] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 8.5 g of 1,9-nonanediol (hydroxyl equivalent: 80 g / eq), 45.67 g of the diphenyl isophthalate derivative (C) obtained in Synthesis Example 3, and 0.27 g of DBU were added. After the system was replaced with nitrogen under reduced pressure, the temperature was raised to 190°C and stirred until the reaction was completed. The end time of the reaction was confirmed by GPC. Thereafter, PTBP was removed by reduced pressure distillation to obtain an active ester (C-1). According to the feed ratio, the functional group equivalent and average repetition number x of the obtained active ester (C-1) were 363 g / eq and x=1, respectively. Figure 8 The GPC spectrum of the obtained active ester (C-1) is shown in FIG.

[0345] (Example 4): Synthesis of active ester (A-2)

[0346] In Example 1, 30.0 g of 1,6-hexanediol (hydroxyl equivalent: 59 g / eq) was used instead of 1,9-nonanediol, the amount of diphenyl isophthalate derivative (A) was changed from 129.68 g to 175.86 g, and DBU was changed from 0.80 g to 1.03 g. The same operation as in Example 1 was performed to obtain an active ester (A-2). Based on the feed ratio, the functional group equivalent and the average repeating number x of the obtained active ester (A-2) were 299 g / eq and x=1, respectively. Fig. 9The GPC spectrum of the obtained active ester (A-2) is shown in FIG.

[0347] (Example 5): Synthesis of active ester (A-3)

[0348] In Example 1, 40.0 g of 1,12-dodecanediol (hydroxyl equivalent: 101 g / eq) was used instead of 1,9-nonanediol, the amount of diphenyl isophthalate derivative (A) was changed from 129.68 g to 136.95 g, and DBU was changed from 0.80 g to 0.88 g. The same operation as in Example 1 was performed to obtain an active ester (A-3). Based on the feed ratio, the functional group equivalent and the average repeating number x of the obtained active ester (A-3) were 342 g / eq and x=1, respectively. Fig.10 The GPC spectrum of the obtained active ester (A-3) is shown in FIG.

[0349] (Comparative Example 1): Synthesis of active ester (D-1)

[0350] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 300 g of the resin (D) containing phenolic hydroxyl groups obtained in Comparative Synthesis Example 1 (hydroxyl equivalent: 300 g / eq) and 1212 g of methyl isobutyl ketone (hereinafter abbreviated as "MIBK") were added, and the system was replaced with nitrogen under reduced pressure to dissolve the resin (D) containing phenolic hydroxyl groups. Next, 140.5 g (1.0 mol) of benzoyl chloride was added to the flask, and then, while nitrogen was purged, the system was controlled to below 60°C, and 216 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and stirring was continued for 1 hour under the above conditions. After the reaction was completed, the liquid was allowed to stand for separation, and the water layer was removed. Thereafter, water was added to the MIBK phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 10 minutes, and the liquid was allowed to stand for separation to remove the water layer. This operation was repeated until the pH of the water layer reached 7. Thereafter, water was removed by decantation dehydration, and then MIBK was removed by dehydration under reduced pressure to obtain active ester (D-1). Based on the feed ratio, the functional group equivalent of the obtained active ester (D-1) was 404 g / eq. Fig.11 The GPC spectrum of the obtained active ester (D-1) is shown in FIG.

[0351] (Examples 6 to 10 and Comparative Example 2)

[0352] Preparation of test pieces 1 (for measuring glass transition temperature and dielectric properties)

[0353] As shown in Table 1, a cresol novolac epoxy resin (manufactured by DIC Corporation, EPICLONN-655-EXP-S, epoxy equivalent of 201 g / eq, softening point of 59°C) and separately synthesized active esters and a curing accelerator (catalyst) (N,N-dimethyl-4-aminopyridine, hereinafter abbreviated as DMAP) were mixed in a prescribed ratio to obtain a curable resin composition (epoxy resin composition).

[0354] The obtained curable resin composition (epoxy resin composition) was heated and mixed, and then cooled to a solid state, and then pressed at 180° C. for 20 minutes to cure / form a cured product, which was then further heated at 175° C. for 6 hours to prepare a test piece.

[0355] <Glass transition temperature>

[0356] The test piece was evaluated using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3°C / min) and the temperature at which the ratio of elastic modulus change to viscoelastic modulus change reached the maximum (tanδ maximum) was taken as the glass transition temperature (°C). The results are shown in Table 2.

[0357] <Dielectric properties>

[0358] According to JIS-C-6481, the dielectric constant and dielectric loss tangent of the test piece at 1 GHz and 10 GHz were measured after the test piece was absolutely dried and stored in a room at 23°C and 50% humidity for 24 hours using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies. The results are shown in Table 2.

[0359] Preparation of test pieces 2 (for measuring elongation, tensile modulus, and tensile strength)

[0360] As shown in Table 1, cresol novolac epoxy resin (DIC Corporation, EPICLONN-655-EXP-S, epoxy equivalent of 201 g / eq) and synthesized active ester, DMAP as a curing accelerator (catalyst) were heated and mixed in a predetermined ratio, and the resulting curable resin composition (epoxy resin composition) was poured into a mold frame processed to a thickness of 2 mm, and then heated and cured at 180° C. for 5 hours to obtain a cured product. This was used as a test piece.

[0361] <Determination of elongation, tensile strength, and tensile modulus>

[0362] The elongation, tensile strength and tensile modulus of the test piece of the cured product obtained above were measured in accordance with JIS K7181 (2 mm / min).

[0363] [Table 1]

[0364]

[0365] [Table 2]

[0366]

[0367] From the results in Table 2, it can be confirmed that in all examples, the use of the desired active ester resulted in excellent heat resistance, dielectric properties (especially low dielectric loss tangent) and flexibility. On the other hand, it can be confirmed that in Comparative Example 2, since the desired active ester was not used, the dielectric properties were poor and both flexibility and dielectric properties could not be satisfied.

[0368] (II) Group: Examples and Comparative Examples thereof in the case of using a polyol compound having a hydroxyl equivalent of 270 g / eq or more are shown below.

[0369] In addition, in group (II), the active ester common to group (I), the curable resin composition containing the active ester, the cured product obtained from the curable resin composition, the synthesis conditions, the evaluation results, etc. are common.

[0370] (Example 11): Synthesis of active ester (E-1)

[0371] Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 200 g of polybutadiene having hydroxyl groups at both ends (manufactured by Nippon Soda Co., Ltd.: trade name: G-1000, hydroxyl value: 74.2 mgKOH / g, hydroxyl equivalent: 756 g / eq), 91.5 g of the diphenyl isophthalate derivative (A) obtained in Synthesis Example 1, 0.29 g of DBU, and 0.29 g of 4-[[4,6-bis(octylthio)-1,3,5-triazine-2-yl]amino]-1,6-di-tert-butylphenol (manufactured by BASF JAPAN Co., Ltd., trade name: IRGANOX565) were added, and the system was replaced with nitrogen under reduced pressure, and then the temperature was raised to 180° C. and stirred until the reaction was completed. The completion time of the reaction was confirmed by GPC. Thereafter, o-cresol was removed by reduced pressure distillation to obtain an active ester (E-1). Based on the feed ratio, the functional group equivalent and average repeating number x (refer to the above general formula (1)) of the obtained active ester (E-1) were 995 g / eq and x=1, respectively. Fig.12 and Fig.13 The GPC spectrum of the obtained active ester (E-1) is shown in ( Fig.12 ) and infrared spectroscopy ( Fig.13 ). The presence of a butadiene skeleton, an active ester bond, and an ester bond was confirmed, and the disappearance of the hydroxyl group confirmed the formation of the target product.

[0372] It should be noted that the average repeating number x in the above active ester (E-1) is calculated from the charging ratio based on the following general formula (4) (refer to the above general formula (1)). In addition, the same method is used to calculate the active ester (E-2) and the active ester (E-3).

[0373] (Average number of repetitions x in the obtained active ester) = (the number of moles of hydroxyl groups in the compound having at least two hydroxyl groups) / [(the number of moles of active ester groups in the active ester group-containing compound used as a raw material) - (the number of moles of hydroxyl groups in the compound having at least two hydroxyl groups)]... (4)

[0374] The aforementioned active ester group-containing compound is a diphenyl isophthalate derivative (A) in Example 11 and is a raw material used in the synthesis of the active ester (E-1).

[0375] (Example 12): Synthesis of active ester (E-2)

[0376] In Example 11, IRGANOX 565 was removed, 200.0 g of polycarbonate polyol (Kuraray Co., Ltd., trade name: C-2090, hydroxyl value: 56.8 mgKOH / g, hydroxyl equivalent: 988 g / eq) was used instead of G-1000, the amount of the diphenyl isophthalate derivative (A) obtained in Synthesis Example 1 was changed from 91.5 g to 70.0 g, and DBU was changed from 0.29 g to 0.27 g. The same operation as in Example 11 was performed to obtain an active ester (E-2). Based on the charging ratio, the functional group equivalent and the average repeating number x of the active ester (E-2) were 1194 g / eq and x=1, respectively. Fig.14 The GPC spectrum of the obtained active ester (E-2) is shown in FIG.

[0377] (Example 13): Synthesis of active ester (E-3)

[0378] In Example 11, IRGANOX 565 was removed, 50.0 g of polyester polyol (manufactured by CRODA JAPAN, trade name: PRIPLAST 1837LQGD, hydroxyl value: 110 mgKOH / g, hydroxyl equivalent: 510 g / eq) was used instead of G-1000, the amount of the diphenyl isophthalate derivative (A) obtained in Synthesis Example 1 was changed from 91.5 g to 34.0 g, and DBU was changed from 0.29 g to 0.084 g, and the same operation as in Example 1 was performed to obtain an active ester (E-3). Based on the charging ratio, the functional group equivalent and the average repeating number x of the active ester (E-3) were 748 g / eq and x=1, respectively. Fig.15 The GPC spectrum of the obtained active ester (E-3) is shown in . In addition, regarding Example 13, synthesis confirmation was performed, but evaluation was not performed.

[0379] (Example 14, Example 15 and Comparative Example 2)

[0380] Preparation of test piece 1 (for measuring dielectric properties)

[0381] As shown in Table 3, a cresol novolac epoxy resin (manufactured by DIC Corporation, EPICLONN-655-EXP-S, epoxy equivalent of 201 g / eq, softening point of 59°C) and separately synthesized active esters and a curing accelerator (catalyst) (N,N-dimethyl-4-aminopyridine, hereinafter abbreviated as DMAP) were mixed in a prescribed ratio to obtain a curable resin composition (epoxy resin composition).

[0382] The obtained curable resin composition (epoxy resin composition) was heated and mixed, and then cooled to a solid state, and then pressed at 180° C. for 20 minutes to cure / form a cured product, which was then further heated at 175° C. for 5 hours to prepare a test piece.

[0383] <Dielectric properties>

[0384] According to JIS-C-6481, the dielectric constant and dielectric loss tangent of the test piece at 10 GHz were measured after absolute drying and storage in a room at 23°C and 50% humidity for 24 hours using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies. The results are shown in Table 4.

[0385] Preparation of test pieces 2 (for measuring elongation, tensile modulus, and tensile strength)

[0386] As shown in Table 3, cresol novolac epoxy resin (DIC Corporation, EPICLONN-655-EXP-S, epoxy equivalent of 201 g / eq) and synthesized active ester, DMAP as a curing accelerator (catalyst) were heated and mixed in a predetermined ratio, and the resulting curable resin composition (epoxy resin composition) was poured into a mold frame processed to a thickness of 2 mm, and then heated and cured at 180° C. for 5 hours to obtain a cured product. This was used as a test piece.

[0387] <Determination of elongation, tensile modulus, and tensile strength>

[0388] The elongation, tensile strength and tensile modulus of the test piece of the cured product obtained above were measured in accordance with JIS K7181 (2 mm / min).

[0389] [Table 3]

[0390]

[0391] [Table 4]

[0392]

[0393] The results in Table 4 show that the dielectric properties (especially low dielectric loss tangent) and flexibility are excellent in all examples by using the desired active ester. On the other hand, in Comparative Example 2, since the desired active ester is not used, the dielectric properties and flexibility are inferior to those in the examples.

[0394] The curable resin composition containing the active ester of the present invention has excellent flexibility and low dielectric properties in its cured product, and therefore can be suitably used in electronic components, etc., and can be particularly suitably used in semiconductor sealing materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, build-up films, build-up boards, fiber-reinforced composite materials, and molded products.

Claims

1. A curable resin composition, characterized in that It contains an active ester and an epoxy resin, wherein the active ester has a structure in which a residue (A) of a polyol compound and a residue (Q) of an aromatic polycarboxylic acid are bonded via an ester bond, and the active ester is capped with a residue (C) of a terminal monovalent aromatic hydroxyl-containing compound. The active ester is represented by the following general formula (1): In the above formula (1), A is a linear or branched alkylene chain, or a linear or branched alkylene ether chain, Q is an aromatic ring, x is an average repeating number of 0.01 or more, and Ar is a structure represented by the following general formula (2) or (3), In the above formulae (2) and (3), * represents a site bonded to the oxygen atom bonded to Ar in the above formula (1), Ra is independently any one of a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an aralkyl group, y is an integer of 0 to 7, and z is an integer of 0 to 5.

2. The curable resin composition according to claim 1, characterized in that The active ester is obtained by reacting an ester compound (iii) with a polyol compound (iv), wherein the ester compound (iii) is obtained by reacting an aromatic compound having at least two carboxyl groups and / or an acid halide or ester thereof (i) with an aromatic compound having one aromatic hydroxyl group (ii).

3. The curable resin composition according to claim 1 or 2, characterized in that The hydroxyl equivalent of the polyol compound is less than 270 g / eq.

4. The curable resin composition according to claim 1 or 2, characterized in that The polyol compound has a hydroxyl equivalent of 270 g / eq or more.

5. The curable resin composition according to claim 1 or 2, characterized in that The polyol compound is a polyol having an aliphatic hydroxyl group.

6. The curable resin composition according to claim 5, characterized in that The polyol having an aliphatic hydroxyl group has a hydroxyl group equivalent of 270 g / eq or more.

7. The curable resin composition according to claim 1, characterized in that The A is a residue of a polyol having an aliphatic hydroxyl group.

8. The curable resin composition according to claim 7, characterized in that The residue of the polyol having an aliphatic hydroxyl group is at least one structural unit selected from the group consisting of a structural unit derived from a hydrocarbon polyol, a structural unit derived from a polycarbonate polyol, a structural unit derived from a polyester polyol, a structural unit derived from a polyether polyol, a structural unit derived from a polyurethane polyol, and a structural unit derived from a polysiloxane polyol.

9. The curable resin composition according to claim 1 or 2, characterized in that The aryl group is naphthyl.

10. A solidified product, characterized in that: The curable resin composition according to any one of claims 1 to 9 is subjected to a curing reaction.

11. A prepreg, characterized in that: The semi-cured product comprises a reinforcing substrate and the curable resin composition according to any one of claims 1 to 9 impregnated into the reinforcing substrate.

12. A circuit substrate, characterized in that: The prepreg according to claim 11 and copper foil are laminated and heat-pressed to form the laminate.

13. A laminated film, characterized in that: The present invention contains the curable resin composition according to any one of claims 1 to 9.

14. A semiconductor sealing material, characterized in that: The present invention contains the curable resin composition according to any one of claims 1 to 9.

15. A semiconductor device, characterized in that: The semiconductor sealing material according to claim 14 is cured by heating.

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