阅读说明：本技术 活性酯化合物 (Active ester compound ) 是由 冈本竜也 佐藤泰 于 2018-04-10 设计创作，主要内容包括：提供：固化物的介电特性和铜箔密合性优异的活性酯化合物、含有其的固化性组合物和其固化物、使用前述固化性组合物而成的半导体密封材料、印刷电路板和积层薄膜。具体而言,为如下活性酯化合物、含有其的固化性组合物和其固化物、使用前述固化性组合物而成的半导体密封材料、印刷电路板和积层薄膜,所述活性酯化合物在分子结构中具有氟化烃结构部位(F)和多个芳香族酯结构部位(E),且在分子末端具有芳基氧基羰基结构(P)或芳基羰基氧基结构(A)。(Providing: an active ester compound having excellent dielectric properties of a cured product and copper foil adhesion, a curable composition containing the same, a cured product thereof, and a semiconductor sealing material, a printed wiring board, and a multilayer film each using the curable composition. Specifically, the present invention relates to an active ester compound having a fluorinated hydrocarbon structural site (F) and a plurality of aromatic ester structural sites (E) in a molecular structure and having an aryloxycarbonyl structure (P) or an arylcarbonyloxy structure (a) at a molecular end, a curable composition containing the same, a cured product thereof, and a semiconductor sealing material, a printed wiring board, and a build-up film each using the curable composition.)

1. An active ester compound having a fluorinated hydrocarbon structural site (F) and a plurality of aromatic ester structural sites (E) in a molecular structure and having an aryloxycarbonyl structure (P) or an arylcarbonyloxy structure (A) at a molecular end.

2. The active ester compound according to claim 1, wherein the aryloxycarbonyl structure (P) is a structural site derived from an aromatic monohydroxy compound (a1), and the arylcarbonyloxy structure (a) is a structural site derived from an aromatic monocarboxylic acid or an acid halide thereof (a 4).

3. The active ester compound according to claim 1, which is an ester of an aromatic monohydroxy compound (a1), an aromatic polycarboxylic acid or an acid halide thereof (a2), and a compound (a3) having 2 or more phenolic hydroxyl groups in the molecular structure, wherein any one or more of the compounds (a1), (a2) and (a3) has a fluorinated hydrocarbon structural site (F) in the molecular structure.

4. The active ester compound according to claim 1, which is an esterified product of a compound (a3) having 2 or more phenolic hydroxyl groups in a molecular structure and an aromatic monocarboxylic acid or an acid halide thereof (a4), and either one or both of the compound (a3) or (a4) has a fluorinated hydrocarbon structural site (F) in a molecular structure.

5. The active ester compound according to claim 1, which is an esterified product of an aromatic polycarboxylic acid or an acid halide thereof (a2), a compound having 2 or more phenolic hydroxyl groups in the molecular structure (a3), and an aromatic monocarboxylic acid or an acid halide thereof (a4), and any one or more of the compounds (a2), (a3), and (a4) has a fluorinated hydrocarbon structural site (F) in the molecular structure.

6. The active ester compound according to claim 1, wherein the fluorinated hydrocarbon moiety (F) is a perfluoroalkyl group having 1 to 6 carbon atoms.

7. A curable composition comprising: the reactive ester compound according to any one of claims 1 to 6 and a curing agent.

8. The curable composition according to claim 7, further comprising a poly (fluoroalkylene) resin.

9. A cured product of the curable composition according to claim 7 or 8.

10. A semiconductor sealing material comprising the curable composition according to claim 7 or 8.

11. A printed wiring board comprising the curable composition according to claim 7 or 8.

12. A multilayer film comprising the curable composition according to claim 7 or 8.

Technical Field

The present invention relates to: an active ester compound having excellent dielectric properties of a cured product and copper foil adhesion, a curable composition containing the same, a cured product thereof, and a semiconductor sealing material, a printed wiring board, and a multilayer film each using the curable composition.

Background

In the technical field of insulating materials used for semiconductors, multilayer printed wiring boards, and the like, development of new resin materials meeting the market trend of various electronic components has been demanded along with the reduction in thickness and size of the electronic components. As specific required properties, heat resistance, moisture absorption resistance, and copper foil adhesion of a cured product are not necessarily all important, and it is also important that a cured product as a measure for speeding up a signal and increasing a frequency has a low dielectric constant and a low dielectric loss tangent, that physical properties such as a glass transition temperature (Tg) as reliability under high temperature conditions do not change, that warpage as a measure accompanied by thinning, and that a cure shrinkage ratio and a linear expansion coefficient as a measure for strain are low.

As a resin material having excellent dielectric characteristics of a cured product, the following resin compositions are known: the epoxy resin composition is composed of a main agent containing a polytetrafluoroethylene dispersion and an epoxy resin, and an acid anhydride curing agent (see patent document 1 below). The epoxy resin composition described in patent document 1 contains a polytetrafluoroethylene dispersion to reduce the values of dielectric constant and dielectric loss tangent, but the adhesion to copper foil is insufficient, and it cannot be applied to fine wiring accompanied with miniaturization of electronic components.

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object to be solved by the present invention is to provide: an active ester compound having excellent dielectric properties of a cured product and copper foil adhesion, a curable composition containing the same, a cured product thereof, and a semiconductor sealing material, a printed wiring board, and a multilayer film each using the curable composition.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have found that an active ester compound having a fluorinated hydrocarbon structural site and a plurality of aromatic ester structural sites in a molecular structure and having an aryloxycarbonyl structure or an arylcarbonyloxy structure at a molecular terminal has excellent dielectric properties of a cured product, has high adhesion to a copper foil, and has high utility value as a curing agent for an epoxy resin for electronic parts, and the like, and thus have completed the present invention.

That is, the present invention relates to an active ester compound having a fluorinated hydrocarbon structural site (F) and a plurality of aromatic ester structural sites (E) in a molecular structure, and having an aryloxycarbonyl structure (P) or an aryloxycarbonyl structure (a) at a molecular end.

The present invention further relates to a curable composition containing: the aforementioned active ester compound, and a curing agent.

The present invention further relates to a curable composition containing: the aforementioned active ester compound, a curing agent, and a poly (fluoroalkylene) resin.

The present invention further relates to a cured product of the curable composition.

The present invention further relates to a semiconductor sealing material which is obtained by using the curable composition.

The present invention further relates to a printed wiring board using the curable composition.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: an active ester compound having excellent dielectric properties of a cured product and copper foil adhesion, a curable composition containing the same, a cured product thereof, and a semiconductor sealing material, a printed wiring board, and a multilayer film each using the curable composition.

Drawings

FIG. 1 is a GPC chart of the active ester compound (1) obtained in example 1.

FIG. 2 is a GPC chart of the active ester compound (2) obtained in example 2.

FIG. 3 is a GPC chart of the active ester compound (3) obtained in example 3.

FIG. 4 is a GPC chart of the active ester compound (4) obtained in example 4.

Detailed Description

The present invention will be described in detail below.

The active ester compound of the present invention is characterized by having a fluorinated hydrocarbon structural site (F) and a plurality of aromatic ester structural sites (E) in a molecular structure, and having an aryloxycarbonyl structure (P) or an arylcarbonyloxy structure (a) at a molecular end.

The fluorinated hydrocarbon structural moiety (F) is a structure in which some or all of the hydrogen atoms in a hydrocarbon group such as an aliphatic hydrocarbon group, an alicyclic ring structure-containing hydrocarbon group, or an aromatic ring-containing hydrocarbon group are substituted with fluorine atoms. The aliphatic hydrocarbon group may be linear or branched, and may have one or more unsaturated bonds. The hydrocarbon group may be a 1-valent hydrocarbon group such as an alkyl group, or a 2-valent hydrocarbon group such as an alkylene group. The alkylene group may be present as a structural site in which a plurality of alkylene groups such as a (poly) oxyalkylene structure are linked by an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, an ester bond, or the like.

Examples of the alicyclic structure included in the alicyclic structure-containing hydrocarbon group include a cyclopentane structure, a cyclohexane structure, a norbornane structure, a norbornene structure, a tricyclodecane structure, a dicyclopentadiene structure, and an adamantane structure. The alicyclic structure-containing hydrocarbon group may have a structural site such as an alkyl group or an alkylene group in addition to the alicyclic structure. The alicyclic structure-containing hydrocarbon group may be a 1-valent hydrocarbon group such as a cycloalkyl group, or a 2-valent hydrocarbon group such as a cycloalkylene group.

Examples of the aromatic ring structure of the aromatic ring-containing hydrocarbon group include a benzene ring, a naphthalene ring, and an anthracene ring. The aromatic ring-containing hydrocarbon group may have a structural site such as an alkyl group or an alkylene group in addition to the aromatic ring structure. The aromatic ring-containing hydrocarbon group may be a 1-valent hydrocarbon group such as an aryl group or an aralkyl group, or a 2-valent hydrocarbon group such as an arylene group or a dialkylene aromatic hydrocarbon.

The active ester compound of the present invention has one or more of the aforementioned fluorinated hydrocarbon structural sites (F). When a plurality of fluorinated hydrocarbon structural sites (F) are present, the structural sites may be the same or different. Among them, the hydrocarbon structure in the fluorinated hydrocarbon structural portion (F) is preferably an aliphatic hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of providing an active ester compound having more excellent adhesion to a copper foil. Further preferably a perfluoroalkyl group having 1 to 6 carbon atoms.

The aromatic ester structural moiety (E) is an ester bond moiety formed by a hydroxyl group bonded to an aromatic ring and a carboxyl group bonded to an aromatic ring. Such an aromatic ester structural moiety (E) has high reactivity with a curing agent such as an epoxy resin.

Specific examples of the aryloxycarbonyl structure (P) include a structural site represented by the following structural formula (1). Specific examples of the arylcarbonyloxy structure (a) include a structural site represented by the following structural formula (2).

[ wherein Ar is an aromatic ring optionally having a substituent. ]

Ar in the structural formulae (1) and (2) represents an aromatic ring. Specifically, a benzene ring, a naphthalene ring, an anthracene ring, and the like can be mentioned. Among them, naphthalene rings are preferable because they are active ester compounds which are excellent not only in the physical properties of cured products but also in the miscibility with curing agents and other resin components.

The substituent on the aromatic nucleus may include, in addition to the fluorinated hydrocarbon structural moiety (F), an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group, and the like. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Specific examples thereof include: methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and the like. Examples of the alkoxy group include methoxy, ethoxy, propyloxy, butoxy, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a structural site obtained by substituting the aromatic nucleus thereof with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, an anthracyloxy group, and a structural site obtained by substituting the aromatic nucleus thereof with the alkyl group, the alkoxy group, the halogen atom, and the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site obtained by substituting the aforementioned alkyl group, alkoxy group, halogen atom, and the like for the aromatic nucleus thereof.

The active ester compound of the present invention is not particularly limited in specific structure as long as it has the fluorinated hydrocarbon structural site (F) and the plurality of aromatic ester structural sites (E) in the molecular structure and has the aryloxycarbonyl structure (P) or the arylcarbonyloxy structure (a) at the molecular end, and various structures can be adopted. The molecular weight is also not particularly limited, and may be a single molecular weight compound or an oligomer or polymer having a molecular weight distribution. Specific examples of the active ester compound include the following compounds (a1) to (a 4). These are merely examples of the active ester compound, and the active ester compound of the present invention is not limited thereto. In addition, the active ester compounds can be used alone, can also be combined with more than 2.

Active ester compound (a 1): is an active ester compound as follows: an ester of an aromatic monohydroxy compound (a1) and an aromatic polycarboxylic acid or an acid halide thereof (a2), wherein either or both of the compound (a1) or (a2) has a fluorinated hydrocarbon structural moiety (F) in the molecular structure

Active ester compound (a 2): is an active ester compound as follows: an ester of a compound (a3) having 2 or more phenolic hydroxyl groups in its molecular structure with an aromatic monocarboxylic acid or its acid halide (a4), wherein either one or both of the compound (a3) or (a4) has a fluorinated hydrocarbon moiety (F) in its molecular structure

Active ester compound (a 3): is an active ester compound as follows: an esterified product of an aromatic monohydroxy compound (a1), an aromatic polycarboxylic acid or an acid halide thereof (a2), and a compound (a3) having 2 or more phenolic hydroxyl groups in the molecular structure, wherein at least one of the compounds (a1), (a2) and (a3) has a fluorinated hydrocarbon structural site (F) in the molecular structure

Active ester compound (a 4): is an active ester compound as follows: an esterified product of an aromatic polycarboxylic acid or an acid halide thereof (a2), a compound having 2 or more phenolic hydroxyl groups in the molecular structure (a3), and an aromatic monocarboxylic acid or an acid halide thereof (a4), wherein at least one of the compounds (a2), (a3) and (a4) has a fluorinated hydrocarbon structural site (F) in the molecular structure

Specific examples of the aromatic monohydroxy compound (a1) include phenol, a phenol compound having one or more substituents on the aromatic nucleus of phenol, naphthol, a naphthol compound having one or more substituents on the aromatic nucleus of naphthol, anthraphenol, an anthraphenol compound having one or more substituents on the aromatic nucleus of anthraphenol, and the like. Examples of the substituent on the aromatic nucleus include the fluorinated hydrocarbon moiety (F), an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group and the like, and specific examples thereof are as described above. The aromatic monohydroxy compound (a1) may be used singly or in combination of 2 or more.

Among them, phenol compounds or naphthol compounds are preferable, and phenol, naphthol, or compounds having 1 or 2 substituents on the aromatic nucleus thereof are more preferable, because they are active ester compounds having not only excellent dielectric properties and copper foil adhesion of cured products but also excellent various performances such as heat resistance. The substituent on the aromatic nucleus is preferably the fluorinated hydrocarbon moiety (F), an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an aralkyl group.

Examples of the aromatic polycarboxylic acid or acid halide thereof (a2) include: benzene dicarboxylic acids such as isophthalic acid and terephthalic acid; benzene tricarboxylic acids such as trimellitic acid; naphthalenedicarboxylic acids such as naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid and naphthalene-2, 7-dicarboxylic acid; acid halides thereof; compounds having one or more substituents on their aromatic nucleus, and the like. Examples of the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. Examples of the substituent on the aromatic nucleus include the fluorinated hydrocarbon structural moiety (F), an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group, and the like, and specific examples thereof are as described above. The aromatic polycarboxylic acids or acid halides thereof (a2) may be used alone or in combination of 2 or more. Among them, from the viewpoint of being an active ester compound which is excellent not only in dielectric characteristics and copper foil adhesion of a cured product but also in various performances such as heat resistance, a benzenedicarboxylic acid such as isophthalic acid and terephthalic acid or an acid halide thereof is preferable.

Examples of the compound (a3) having 2 or more phenolic hydroxyl groups in the molecular structure include: various aromatic polyhydroxy compounds, novolak type resins using one or more of the aromatic monohydroxy compounds (a1) as a reaction raw material, reaction products using one or more of the aromatic monohydroxy compounds (a1) and a compound (x) represented by any one of the following structural formulae (x-1) to (x-5) as an essential reaction raw material, and the like,

[ wherein h is 0 or 1. R¹Each independently is any of the fluorinated hydrocarbon structural site (F), an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group and an aralkyl group, i is 0 or an integer of 1 to 4. Z is any of a vinyl group, a halogenated methyl group, a hydroxymethyl group, and an alkoxymethyl group. Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4.]。

Examples of the various aromatic polyhydroxy compounds include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, polyhydroxy biphenyl, poly (hydroxyphenyl) alkane, and other bisphenol compounds, and also include compounds having one or more substituents on carbon atoms of these compounds. Examples of the substituent on the carbon atom include the fluorinated hydrocarbon moiety (F), an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group and the like, and specific examples thereof are as described above.

With respect to R in the aforementioned structural formulae (x-1) to (x-5)¹Specific examples of the fluorinated hydrocarbon moiety (F), the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, the aryl group, the aryloxy group and the aralkyl group are as described above. The reaction between the aromatic monohydroxy compound (a1) and the compound (x) can be carried out by heating and stirring under acid catalysis at a temperature of about 80 to 180 ℃.

The compounds (a3) having 2 or more phenolic hydroxyl groups in the molecular structure may be used alone or in combination of 2 or more. Among them, bis (hydroxyphenyl) fluoroalkanes represented by the following structural formula (3) are preferable because they are active ester compounds which are excellent not only in dielectric characteristics of cured products and adhesion to copper foils but also in various performances such as heat resistance.

[ in the formula, R²Each independently a fluorinated aliphatic hydrocarbon group. R³Is any one of the fluorinated hydrocarbon structural part (F), an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group and an aralkyl group, and n is 0 or an integer of 1 to 4.]

In connection with the foregoingR in the formula (1)²The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Among them, an alkyl group having 1 to 6 carbon atoms is preferable.

Examples of the aromatic monocarboxylic acid or the acid halide thereof (a4) include: benzoic acid, benzoyl halide, compounds having one or more substituents on the carbon atoms of these compounds, and the like. Examples of the substituent on the carbon atom include the fluorinated hydrocarbon moiety (F), an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group and the like, and specific examples thereof are as described above. These may be used alone or in combination of 2 or more.

These active ester compounds can be produced, for example, by mixing and stirring the reaction raw materials in the presence of an alkali catalyst under a temperature condition of about 40 to 65 ℃. The reaction may be carried out in an organic solvent as required. After the reaction, the reaction product can be purified by washing with water, reprecipitation, or the like.

Examples of the base catalyst include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These may be used alone or in combination of 2 or more. The aqueous solution may be used in the form of an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide having high catalytic activity is preferable.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, 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 and N-methylpyrrolidone. These solvents may be used alone or in the form of a mixture of 2 or more solvents.

The reaction ratio of each reaction raw material can be appropriately adjusted according to desired physical properties of the obtained active ester compound, and the following is particularly preferable.

In the production of the active ester compound (a1), the reaction ratio of the aromatic monohydroxy compound (a1) and the aromatic polycarboxylic acid or its acid halide (a2) is preferably 0.95 to 1.05 mol based on 1 mol of the total of the carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or its acid halide (a2) in order to obtain the desired active ester compound (a1) at a high yield.

In the production of the active ester compound (a2), the ratio of the reaction between the compound (A3) having 2 or more phenolic hydroxyl groups in the molecular structure and the esterified product of the aromatic monocarboxylic acid or its acid halide (a4) is preferably 0.95 to 1.05 mol of the aromatic monocarboxylic acid or its acid halide (a4) based on 1 mol of the total phenolic hydroxyl groups of the compound (A3) having 2 or more phenolic hydroxyl groups in the molecular structure, in view of obtaining the target active ester compound (a2) at a high yield.

In the production of the active ester compound (a3), the reaction ratio of the aromatic monohydroxy compound (a1), the aromatic polycarboxylic acid or acid halide thereof (a2), and the compound having 2 or more phenolic hydroxyl groups in the molecular structure (a3) is preferably such that the ratio of the number of moles of hydroxyl groups of the aromatic monohydroxy compound (a1) to the number of moles of hydroxyl groups of the compound having 2 or more phenolic hydroxyl groups in the molecular structure (a3) is 10/90 to 75/25, more preferably 20/80 to 60/40. Further, the total amount of the hydroxyl groups of the aromatic monohydroxy compound (a1) and the compound (a3) having 2 or more phenolic hydroxyl groups in the molecular structure is preferably in the range of 0.9 to 1.1 mol based on 1 mol of the total amount of the carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or the acid halide group thereof (a 2).

In the production of the active ester compound (a4), the reaction ratio of the aromatic polycarboxylic acid or its acid halide (a2), the compound having 2 or more phenolic hydroxyl groups in the molecular structure (a3), and the aromatic monocarboxylic acid or its acid halide (a4) is preferably 0.5 to 5 moles, more preferably 0.8 to 3 moles, of the total of the carboxyl groups or the acid halide groups of the aromatic polycarboxylic acid or its acid halide (a2) to 1 mole of the total of the carboxyl groups or the acid halide groups of the aromatic monocarboxylic acid or its acid halide (a 4). In addition, the total of the carboxyl group or acid halide group of the aromatic polycarboxylic acid or acid halide thereof (a2) and the aromatic monocarboxylic acid or acid halide thereof (a4) is preferably in the range of 0.9 to 1.1 to 1 mol of the hydroxyl group of the compound (a3) having 2 or more phenolic hydroxyl groups in the molecular structure.

The melt viscosities of the active ester compounds (A1) and (A2) at 150 ℃ are preferably in the range of 0.01 to 5 dPas. In the present invention, the melt viscosity at 150 ℃ is a value measured by an ICI viscometer according to ASTM D4287.

The softening points of the active ester compounds (A3) and (A4) measured according to JIS K7234 are preferably in the range of 40 to 200 ℃, and more preferably in the range of 50 to 180 ℃. The functional group equivalent is preferably in the range of 150 to 350 g/equivalent in view of excellent balance between curability and various properties of the cured product. In the present invention, the functional group in the active ester compound means an ester bond site and a phenolic hydroxyl group in the active ester compound. The equivalent of the functional group of the active ester compound is a value calculated from the amount of the reaction raw material charged.

The acid value and hydroxyl value of the active ester compound of the present invention are preferably 10mgKOH/g or less, more preferably 5mgKOH/g or less, from the viewpoint of providing an active ester compound which is excellent in the balance among dielectric characteristics, copper foil adhesiveness, and other properties of a cured product.

The acid value and hydroxyl value of the active ester compound of the present invention are preferably 10mgKOH/g or less, more preferably 5mgKOH/g or less, from the viewpoint of providing an active ester compound which is excellent in the balance among dielectric characteristics, copper foil adhesiveness, and other properties of a cured product.

The fluorine atom content in the active ester compound of the present invention is preferably in the range of 5 to 40% by mass, more preferably in the range of 10 to 30% by mass, from the viewpoint of obtaining an active ester compound excellent in balance among dielectric characteristics, copper foil adhesiveness, and other properties of a cured product. The fluorine atom content can be calculated from the type of raw material and the ratio thereof at the time of resin design, or can be actually measured by combustion ion chromatography. In the present invention, the above range is preferable among the measured values of the latter.

The active ester compound of the present invention may be used in combination with an active ester compound having no fluorinated hydrocarbon structural site (F). In the above case, the fluorine atom content in the total of the two is preferably in the range of 5 to 40 mass%, more preferably in the range of 10 to 30 mass%.

The curable composition of the present invention contains the active ester compound and a curing agent. The curing agent is not particularly limited as long as it is a compound capable of reacting with the active ester compound of the present invention, and various compounds can be used. An example of the curing agent is an epoxy resin. Examples of the epoxy resin include polyglycidyl ethers of the compound (a3) having 2 or more phenolic hydroxyl groups in the molecular structure.

In the curable composition of the present invention, the blending ratio of the active ester compound and the curing agent is not particularly limited, and can be appropriately adjusted according to the desired properties of the cured product and the like. In an example of a formulation when an epoxy resin is used as a curing agent, the total amount of functional groups in the active ester compound is preferably 0.7 to 1.5 mol based on 1 mol of the total amount of epoxy groups in the epoxy resin.

When an epoxy resin is used as the curing agent, a phenol resin, an amine compound, an acid anhydride, or the like, which is generally used as a curing agent for an epoxy resin, may be used in combination with the active ester compound of the present invention. The compounding ratio when using them is not particularly limited, and the fluorine atom content in the epoxy resin curing agent containing the active ester compound of the present invention is preferably in the range of 5 to 40 mass%, more preferably in the range of 10 to 30 mass%.

The curable composition of the present invention may further contain a curing accelerator. Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, lewis acids, and amine complex salts. Among these, triphenylphosphine is preferable as the phosphorus compound, 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable as the tertiary amine, 2-ethyl-4-methylimidazole is preferable as the imidazole compound, and 4-dimethylaminopyridine and 2-phenylimidazole are preferable as the pyridine compound, from the viewpoint of excellent curability, heat resistance, dielectric characteristics, moisture absorption resistance and the like. The amount of the curing accelerator added is preferably in the range of 0.01 to 15% by mass based on 100 parts by mass of the curable composition.

The curable composition of the present invention may further contain other resin components. Examples of the other resin components include: a phenolic hydroxyl group-containing compound such as the compound (a3) having 2 or more phenolic hydroxyl groups in the molecular structure; diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF₃Amine compounds such as amine complexes and guanidine derivatives; amide compounds such as polyamide resins synthesized from dicyandiamide, a dimer of linolenic acid, and ethylenediamine; a benzoxazine compound; cyanate ester resin; bismaleimide resin; styrene-maleic anhydride resin; allyl group-containing resins represented by diallyl bisphenol and triallyl isocyanurate; polyphosphate esters, phosphate-carbonate copolymers; poly (fluoroalkylene) resins which are polymers containing a fluoroalkylene compound such as tetrafluoroethylene, trifluoropropene or hexafluoropropylene as an essential monomer component, and the like. These may be used alone or in combination of 2 or more. Among these, the poly (fluoroalkylene) resin is preferred from the viewpoint of providing a curable composition having a cured product with more excellent dielectric properties and copper foil adhesion.

The blending ratio of these other resin components is not particularly limited, and may be appropriately adjusted according to the desired properties of the cured product and the like. As an example of the compounding ratio, it is preferable to use the range of 1 to 50 mass% with respect to the resin solid content of the curable composition of the present invention. The resin solid component of the curable composition means a component other than the solvent of the curable composition.

The curable composition of the present invention may contain various additives such as a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

Examples of the flame retardant include: inorganic phosphorus compounds such as ammonium phosphates and phosphoric acid amides, including red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate and ammonium polyphosphate; organic phosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting these compounds with compounds such as epoxy resins and phenol resins; nitrogen flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, and the like; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, the amount of the flame retardants is preferably in the range of 0.1 to 20% by mass in the curable composition.

For example: when the curable composition of the present invention is used for a semiconductor sealing material, the inorganic filler is added. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, the fused silica is preferable in that an inorganic filler can be added in a larger amount. The fused silica may be in a crushed form or a spherical form, and a spherical form is preferably mainly used in order to increase the amount of the fused silica to be blended and to suppress an increase in melt viscosity of the curable composition. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable composition.

When the curable composition of the present invention is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

The active ester compound of the present invention and the curable composition using the same have: high curing property, and excellent properties of the cured product such as dielectric properties, heat resistance, and moisture absorption resistance. In addition, general performance requirements required for resin materials, such as solubility in general-purpose organic solvents and storage stability, are sufficiently high. Therefore, the resin composition can be widely used for applications such as coating materials, adhesives, and molded articles, in addition to electronic materials such as semiconductor sealing materials, printed wiring boards, and resist materials.

When the curable composition of the present invention is used for a semiconductor sealing material, it is generally preferable to blend an inorganic filler. The semiconductor sealing material can be prepared by mixing the compounds using an extruder, kneader, roller, or the like, for example. Examples of a method for molding a semiconductor package using the obtained semiconductor sealing material include the following methods: the semiconductor sealing material is molded by casting or by a transfer molding machine, an injection molding machine or the like, and further heated at a temperature of 50 to 200 ℃ for 2 to 10 hours, whereby a semiconductor device as a molded article can be obtained.

When the curable composition of the present invention is used for printed wiring boards and build-up adhesive films, it is generally preferable to use the composition diluted with an organic solvent. Examples of the organic solvent include methyl Ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol Ethyl ether acetate (Ethyl diglycolate), and propylene glycol monomethyl ether acetate. The type and amount of the organic solvent can be suitably adjusted depending on the use environment of the curable composition, and for example, in the case of printed wiring board use, a polar solvent having a boiling point of 160 ℃ or less such as methyl ethyl ketone, acetone, or dimethylformamide is preferably used, and the nonvolatile content is preferably 40 to 80 mass%. For the use of the build-up adhesive film, it is preferable to use a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone, an acetate solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, a carbitol solvent such as cellosolve, butyl carbitol, an aromatic hydrocarbon solvent such as toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or the like, and it is preferable to use them in such a ratio that the nonvolatile content is 30 to 60 mass%.

Further, examples of the method for producing a printed wiring board using the curable composition of the present invention include the following methods: the reinforcing base material is impregnated with the curable composition and cured to obtain a prepreg, which is stacked on a copper foil and then thermally bonded. The reinforcing base material may be paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, or the like. The impregnation amount of the curable composition is not particularly limited, and it is usually preferably prepared so that the resin component in the prepreg is 20 to 60 mass%.