WO2021124938A1 - Curable composition - Google Patents

Abstract

Provided is a curable composition with which it is possible to form a flexible and heat-resistant cured article.　This curable composition contains a curable compound and a silicate.　The silicate is preferably a flaky silicate or a lipophilic silicate.　The curable compound is preferably a compound represented by formula (1). In the formula, R1 and R2 each indicate a curable functional group, and D1 and D2 each indicate a single bond or a linking group. L indicates a divalent group including the structures represented by formulas (I) and (II). Ar1 to Ar3 each indicate an arylene group, or a group in which two or more arylene groups are bonded by a single bond or a linking group. X indicates -CO-, -S-, or -SO2-, and Y may be the same as or different from each other and indicate -S-, -SO2-, -O-, -CO-, -COO-, or -CONH-.

Description

Curable composition

The present disclosure relates to a curable composition and a cured or semi-cured product thereof. The present application claims the priority of Japanese Patent Application No. 2019-229223 filed in Japan on December 19, 2019, the contents of which are incorporated herein by reference.

Engineering plastics are plastics with improved heat resistance and mechanical properties, and are heavily used as essential materials for miniaturization, weight reduction, high performance, and high reliability of various parts. However, engineering plastics have a problem of poor workability because they have a high melting temperature and low solvent solubility.

For example, the polyimide described in Patent Document 1 and the like has excellent heat resistance and strength characteristics, but is sparingly soluble and sparingly meltable, so that it cannot be melt-molded or used as a matrix resin for composite materials. It was difficult.

Polyetheretherketone (PEEK), also called super engineering plastic, is a thermoplastic resin having excellent heat resistance, flame retardancy, and electrical characteristics at a continuous use temperature of 260 ° C., but has a melting point of 343 ° C. Therefore, it is particularly difficult to melt and is difficult to dissolve in a solvent, so that it is inferior in processability (for example, Patent Document 2).

Therefore, there is a demand for a curable composition capable of forming a cured product having excellent processability and heat resistance.

Japanese Unexamined Patent Publication No. 2000-219741 Special Publication No. 60-322642

Therefore, an object of the present disclosure is to provide a curable composition capable of forming a cured product having heat resistance and flexibility.
Another object of the present disclosure is to provide a curable composition capable of forming a cured product having low CTE (coefficient of linear expansion), heat resistance, and flexibility.
Another object of the present disclosure is to provide a curable composition capable of forming a cured product having excellent processability, low CTE, heat resistance, and flexibility.
Another object of the present disclosure is to provide a semi-cured product capable of forming a cured product having heat resistance and flexibility.
Another object of the present disclosure is to provide a semi-cured product capable of forming a cured product having low CTE, heat resistance, and flexibility.
Another object of the present disclosure is to provide a cured product having heat resistance and flexibility.
Another object of the present disclosure is to provide a cured product having low CTE, heat resistance, and flexibility.
Another object of the present disclosure is to provide a laminate in which the cured product is laminated on a substrate.
Another object of the present disclosure is to provide an electronic device comprising the laminate.

As a result of diligent studies to solve the above problems, the present inventors have found that a composition obtained by adding a specific amount of silicate to a curable compound can solve the above problems. This disclosure has been completed based on these findings.

That is, the present disclosure provides a curable composition containing a curable compound and a silicate, wherein the content of the silicate is 0.01 to 95 parts by weight with respect to 100 parts by weight of the curable compound.

The present disclosure also provides the curable composition in which the silicate is a flaky silicate.

The present disclosure also provides the curable composition in which the silicate has the following properties 1 and 2.
Characteristic 1: A PVC ring for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface is filled with silicate until the height from the upper flat surface of the vinyl chloride ring reaches 5.0 mm, and the maximum pressurization is performed. Pressurize at 7 MPa for 3 minutes to smooth the PVC ring surface, and 5 minutes after decompression, the PVC ring surface rises. Characteristic 2: Salt for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface. The billing is filled with silicate until the height from the upper plane of the vinyl chloride ring reaches 3.0 mm, and the surface of the vinyl chloride ring is smoothed by pressurizing at a maximum pressurization of 5 MPa for 3 minutes. Does not cause swelling on the surface of

The present disclosure also _{provides the curable composition in which the maximum diameter L 1} of the silicate, the diameter L ₂ orthogonal to the maximum diameter L ₁ , and the thickness W satisfy the following formulas (a) and (b). To do.
0.2L ₁ ≤ L ₂ ≤ L ₁ (a)
0.001L ₁ ≤ W ≤ 0.08L ₁ (b)

The present disclosure also provides the curable composition in which the silicate is a lipophilic silicate.

The present disclosure also provides the curable composition in which the silicate comprises an alkali metal.

The present disclosure also provides the curable composition having a magnesium content of silicate of 10% by weight or more.

The present disclosure also provides the curable composition in which the silicate is flaky silicate and the sodium content is less than 3.0% by weight.

The present disclosure also provides the curable composition in which the silicate is a flaky silicate and the potassium content is 1.0% by weight or more.

The present disclosure also provides the curable composition in which the silicate is a flaky silicate and the aluminum content is 0.5% by weight or more.

The present disclosure also provides the curable composition in which the silicate contains a fluorine atom.

The present disclosure also provides the curable composition in which the silicate is mica.

In the present disclosure, the curable compound is also described in the following formula (1).

[In the formula, R ¹ and R ² indicate the same or different curable functional groups, and D ¹ and D ² indicate the same or different single bond or linking group. L represents a divalent group having a repeating unit including a structure represented by the following formula (I) and a structure represented by the following formula (II).

(In the formula, Ar ¹ to Ar ³ are the same or different, and represent an arylene group or a group in which two or more arylene groups are bonded via a single bond or a linking group. X indicates -CO-, -S-. , Or -SO _2- , Y indicates the same or different, -S-, -SO _2- , -O-, -CO-, -COO-, or -CONH-. N is 0 or more. Indicates an integer)]
The curable composition which is a compound represented by is provided.

^{The present disclosure also provides the curable composition in which R 1} and R ² in the formula (1) are the same or different curable functional groups having a cyclic imide structure.

In the present disclosure, R ¹ and R ² in the formula (1) are the same or different groups selected from the groups represented by the following formulas (r-1) to (r-6). A curable composition is provided.

(The bond extending from the nitrogen atom in the formula bonds with D ¹ or D ² )

The present disclosure also provides a cured product of the curable composition.

The present disclosure also provides a semi-cured product of the curable composition.

The present disclosure also provides a laminate having a structure in which the cured product is laminated on a substrate.

The present disclosure also provides the laminate in which the substrate is a copper substrate.

The present disclosure also provides an electronic device having a printed circuit board with conductor wiring on a substrate made of a cured product of the curable composition.

The curable composition of the present disclosure can be heated to obtain a cured product having heat resistance and flexibility. Further, the cured product preferably has a low CTE and has a heat ray expansion integer comparable to that of copper. Therefore, the laminated body in which the cured product is laminated on the copper substrate prevents the laminated body from being curled due to the shrinkage of the cured product even when exposed to a high temperature environment. Can be done.
Therefore, the curable composition can be suitably used, for example, as a raw material for an electronic circuit substrate to which copper wiring is applied.

It is a figure which shows ^{the 1} H-NMR spectrum (DMSO-d ₆ ) of the diamine (1) obtained in the preparation example. It is a figure which shows the FTIR spectrum of the diamine (1) obtained in the preparation example. It is a figure which shows ^{the 1} H-NMR spectrum (CDCl ₃ ) of the curable compound A obtained in the preparation example. It is a figure which shows the FTIR spectrum of the curable compound A obtained in the preparation example. It is a figure which shows the scanning electron microscope image (SEM image) of the mica (NK-8G) used in an Example. It is a figure which shows the scanning electron microscope image (SEM image) of the mica (MAE) used in an Example. It is a figure which shows the scanning electron microscope image (SEM image) of the mica (ME100) used in an Example. It is a figure which shows the scanning electron microscope image (SEM image) of the mica (MK200) used in an Example.

[Curable composition]
The curable composition of the present disclosure is a curable composition containing a curable compound and a silicate.

(Curable compound)
The curable compound is a compound capable of forming a cured product by subjecting it to heat treatment. As the curable compound, a compound represented by the following formula (1) is preferable in that the melting temperature is low, the solvent solubility is excellent, the usability is excellent, and the cured product has super heat resistance.

In formula (1), R ¹ and R ² represent the same or different curable functional group, and D ¹ and D ² represent the same or different single bond or linking group. L represents a divalent group having a repeating unit including a structure represented by the following formula (I) and a structure represented by the following formula (II).

(In the formula, Ar ¹ to Ar ³ are the same or different, and represent an arylene group or a group in which two or more arylene groups are bonded via a single bond or a linking group. X indicates -CO-, -S-. , Or -SO _2- , Y indicates the same or different, -S-, -SO _2- , -O-, -CO-, -COO-, or -CONH-. N is 0 or more. Indicates an integer)

In the formula, R ¹ and R ² represent curable functional groups. R ¹ and R ² may be the same or different from each other. As the ^{curable functional group in R 1} and R ² , for example, a curable functional group having a cyclic imide structure such as a group represented by the following formula (r) is preferable.

(The bond extending from the nitrogen atom in the formula bonds with D ¹ or D ² )

In the above formula (r), Q represents C or CH. The two Qs in the formula are bonded via a single bond or a double bond. n'is an integer of 0 or more (for example, an integer of 0 to 3, preferably 0 or 1). R ³ to R ⁶ are the same or different, and have a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group (preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2 to 10 carbon atoms). From 10 alkynyl groups), aromatic hydrocarbon groups (preferably aryl groups having 6 to 10 carbon atoms such as phenyl groups and naphthyl groups), or the saturated or unsaturated aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Indicates a group to which two or more selected groups are bonded. The ^{two groups selected from R 3} to R ⁶ may be bonded to each other to form a ring with adjacent carbon atoms.

Examples of the ring in which two groups selected from R ³ to R ⁶ may be bonded to each other to form together with adjacent carbon atoms include, for example, an alicyclic having 3 to 20 carbon atoms and 6 to 14 carbon atoms. Aromatic rings can be mentioned. The alicyclic having 3 to 20 carbon atoms has, for example, about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. Cycloalkane ring; cycloalkene ring having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as cyclopentene ring and cyclohexene ring; perhydronaphthalene ring, norbornane ring, norbornene ring, adamantane. Ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Cross-linked cyclic hydrocarbon groups such as dodecane rings are included. The aromatic ring having 6 to 14 carbon atoms includes a benzene ring, a naphthalene ring and the like.

As the curable functional group having a cyclic imide structure, a curable functional group having a cyclic unsaturated imide structure or a curable functional group having a cyclic imide structure having an arylethynyl group is preferable, and particularly preferably. It is a group selected from the groups represented by the following formulas (r-1) to (r-6), and particularly preferably a group represented by the following formula (r-1) or (r-5).

(The bond extending from the nitrogen atom in the formula binds to ^{D 1} or D ^{2 in the formula (1))}

One or more substituents may be bonded to the groups represented by the formulas (r-1) to (r-6). Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom and the like.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group and the like. Chain-like or branched chain-like alkyl groups can be mentioned.

Examples of the alkoxy group having 1 to 6 carbon atoms include a linear or branched alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, and a t-butyloxy group.

In formula (1), D ¹ and D ² represent a single bond or a linking group, which are the same or different. Examples of the linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a group in which a plurality of these are linked. Can be mentioned.

The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

Examples of the divalent aliphatic hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a linear or branched alkaneylene group having 2 to 18 carbon atoms. Can be mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group and a trimethylene group. Examples of the linear or branched alkenylene group having 2 to 18 carbon atoms include a vinylene group, a 1-methylvinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group and the like.

Examples of the divalent alicyclic hydrocarbon group include a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, for example, 1,2-cyclopentylene group and 1,3-cyclopenti. Cycloalkylene groups (including cycloalkylidene group) such as len group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, cyclohexylidene group Can be mentioned.

Examples of the divalent aromatic hydrocarbon group include an arylene group having 6 to 14 carbon atoms, for example, a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, and 3 , 3'-biphenylene group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,8-naphthalenediyl group, anthracendiyl group and the like.

The heterocycle constituting the divalent heterocyclic group includes an aromatic heterocycle and a non-aromatic heterocycle. Such a heterocycle includes a 3 to 10-membered ring (preferably 4 to 6-membered) having a carbon atom and at least one heteroatom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) in the atoms constituting the ring. Rings) and fused rings thereof. Specifically, a heterocycle containing an oxygen atom as a heteroatom (for example, a 3-membered ring such as an oxyran ring; a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isooxazole ring, a γ-butyrolactone ring). 5-membered rings such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholin ring and the like; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromen ring, chroman ring, isochroman ring and the like. Fused rings; 3- ^{oxatricyclo [4.3.1.1 4,8} ] undecane-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonane-2-one ring , Etc.), Heterocycles containing sulfur atoms as heteroatoms (eg, 5-membered rings such as thiophene ring, thiazole ring, isothiazole ring, thiazizole ring; 6-membered ring such as 4-oxo-4H-thiopyran ring) A 5-membered ring such as a fused ring such as a benzothiophene ring or a heterocycle containing a nitrogen atom as a heteroatom (for example, a pyrrol ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, etc.; isocyanul ring, a pyridine ring, a pyridazine). 6-membered rings such as a ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring; an indole ring, an indolin ring, a quinoline ring, an acridin ring, a naphthylidine ring, a quinazoline ring, a fused ring such as a purine ring, etc.) and the like. The divalent heterocyclic group is a group obtained by removing two hydrogen atoms from the structural formula of the heterocycle.

Among the D ¹ and D ² , it is preferable to contain a divalent aromatic hydrocarbon group in that a cured product having particularly excellent heat resistance can be obtained. As the divalent aromatic hydrocarbon group, a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, and a group represented by the following formulas (d-1) to (d-4) is more preferable. It is a group selected from, and particularly preferably a group represented by the following formula (d-1) (1,2-phenylene group, 1,3-phenylene group, or 1,4-phenylene group).

Further, D ¹ and D ² are at least one group selected from the group consisting of a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imide bond together with the divalent aromatic hydrocarbon group. Is preferable, and a group in which an ether bond is linked to the divalent aromatic hydrocarbon group is particularly preferable.

^{Therefore, the R 1-} D ¹ -group and the R ^2- D ^2- group in the formula (1) are the same or different and are represented by the following formula (rd-1) or (rd-2). A group containing the above is preferable, and a group represented by the following formula (rd-1-1) or (rd-2-1) is particularly preferable.

(A bond extending from a phenylene group or an oxygen atom in the formula binds to L in the formula (1))

L in the formula (1) represents a divalent group having a repeating unit including the structure represented by the above formula (I) and the structure represented by the above formula (II). ^{Ars 1} to Ar ³ in the formula (I) and the formula (II) represent the same or different arylene groups, or groups in which two or more arylene groups are bonded via a single bond or a linking group. X is -CO -, - S-, or -SO ₂ - indicates, Y are the same or _{different, -S -, - SO 2 -} , - O -, - CO -, - COO-, or -CONH -Indicates. n represents an integer of 0 or more, for example, an integer of 0 to 5, preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.

The arylene group is a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring (= aromatic hydrocarbon ring). Examples of the aromatic ring include aromatic rings having 6 to 14 carbon atoms such as benzene, naphthalene, anthracene, and phenanthrene. As the aromatic ring, an aromatic ring having 6 to 10 carbon atoms such as benzene and naphthalene is preferable, and as the allylene group, an arylene group having 6 to 10 carbon atoms is preferable.

Examples of the linking group include a divalent hydrocarbon group having 1 to 5 carbon atoms, a group in which one or more hydrogen atoms of a divalent hydrocarbon group having 1 to 5 carbon atoms are substituted with halogen atoms, and the like. Can be mentioned.

The divalent hydrocarbon group having 1 to 5 carbon atoms includes, for example, a linear or branched alkylene having 1 to 5 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group. Group: Linear or branched alkenylene group having 2 to 5 carbon atoms such as vinylene group, 1-methylvinylene group and propenylene group; 2 to 5 carbon atoms such as ethynylene group, propynylene group and 1-methylpropinylene group. A linear or branched alkynylene group or the like is included. As the hydrocarbon group, a linear or branched alkylene group having 1 to 5 carbon atoms is preferable, and a branched chain alkylene group having 1 to 5 carbon atoms is particularly preferable.

Therefore, the Ar ¹ to Ar ³ are the same or different, and two or more of the arylene groups having 6 to 14 carbon atoms or the arylene groups having 6 to 14 carbon atoms are single bonds and are directly linked to those having 1 to 5 carbon atoms. A chain or branched alkylene group, or a group in which one or more hydrogen atoms of a linear or branched alkylene group having 1 to 5 carbon atoms are bonded via a group substituted with a halogen atom. Preferably, in particular, two or more arylene groups having 6 to 14 carbon atoms or arylene groups having 6 to 14 carbon atoms are single bonds, branched chain alkylene groups having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. It is preferable that one or more of the hydrogen atoms of the branched alkylene group are bonded via a group substituted with a halogen atom.

As the Ars ¹ to Ar ³ , groups selected from the groups represented by the following formulas (a-1) to (a-5), which are the same or different from each other, are particularly preferable. The position of the joint in the following formula is not particularly limited.

^{As Ar 1} and Ar ² in the formula (I), an arylene group having 6 to 14 carbon atoms is preferable, and a group represented by the above formula (a-1) or (a-2) is particularly preferable. .. As the X in the formula (I), inter alia, -CO- or -SO ₂ - it is preferred. The structure represented by the formula (I) preferably includes a structure derived from benzophenone.

The proportion of the structure derived from the aromatic ring in the total amount of the compound represented by the formula (1) is 50% by weight or more, for example, 50 to 90% by weight, preferably 60 to 90% by weight, particularly preferably 65 to 80% by weight. Is.

The proportion of the structural unit derived from benzophenone in the total amount of the compound represented by the formula (1) is, for example, 5% by weight or more, preferably 10 to 62% by weight, and particularly preferably 15 to 60% by weight.

^{As Ar 3} in the formula (II), a group selected from the groups represented by the above formulas (a-1), (a-4), and (a-5) is preferable. Further, as Y, -S-, -O-, or -SO _2- is preferable. The structures represented by the formula (II) include, in particular, hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4, It preferably contains a structure derived from at least one compound selected from 4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulphon, and bisphenol A, in particular hydroquinone, resorcinol. , And structures derived from at least one compound selected from bisphenol A.

Hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'in the total amount of the compound represented by the formula (1). The proportion of structural units derived from −dihydroxybenzophenone, 4,4′-dihydroxydiphenylsulfide, 4,4′-dihydroxydiphenylsulphon, and bisphenol A is, for example, 5% by weight or more, preferably 10 to 55% by weight, particularly preferably. Is 15 to 53% by weight.

The proportion of the structural units derived from hydroquinone, resorcinol, and bisphenol A in the total amount of the compound represented by the formula (1) is, for example, 5% by weight or more, preferably 10 to 55% by weight, and particularly preferably 15 to 53. By weight%.

As L in the formula (1), a divalent group represented by the following formula (L-1) is preferable in that a cured product having particularly excellent heat resistance can be obtained.

M in the above formula (L-1) is the number of repeating units shown in parentheses contained in the molecular chain (= divalent group represented by the above formula (L-1)), that is, the average. The degree of polymerization is, for example, 2 to 50, preferably 3 to 40, more preferably 4 to 30, particularly preferably 5 to 20, and most preferably 5 to 10. When m is less than 2, the strength and heat resistance of the obtained cured product tend to be insufficient. On the other hand, when m is more than 50, the melting temperature tends to be high. There is also a tendency for solvent solubility to decrease. The value of m can be obtained by GPC measurement or NMR spectrum analysis. Further, n "in the above formula (L-1) indicates an integer of 0 or more, and Ar ¹ to Ar ³ , X, and Y are the same as above. In addition, a plurality of Ar ^{1 in the above formula (L-1).} Indicates the same group. The same applies to ^{Ar 2} and Ar ^3.

The L in the formula (1) is particularly preferably a divalent group represented by the following formula (L-1-1) or (L-1-2).

M1 and m2 in the above formula are repetitions shown in parentheses contained in the molecular chain (= divalent group represented by the above formula (L-1-1) or (L-1-2)). The number of units, that is, the average degree of polymerization, is, for example, 2 to 50, preferably 3 to 40, more preferably 4 to 30, particularly preferably 5 to 20, and most preferably 5 to 10. The values of m1 and m2 can be obtained by GPC measurement or NMR spectrum analysis.

Further, among the compounds represented by the formula (1), L in the formula (1) is a divalent group represented by the above formula (L-1-1) or (L-1-2). Since the compounds having m1 and m2 of 5 to 10 in the formula melt at 300 ° C. or lower (about 250 ° C.), they can be melt-molded at a lower temperature than PEEK or the like, and are particularly excellent in processability.

On the other hand, if the average degree of polymerization of the molecular chains is less than the above range, the obtained cured product tends to be brittle and the mechanical properties tend to deteriorate. Further, when the average degree of polymerization of the molecular chain exceeds the above range, the solubility in a solvent is lowered, the melt viscosity is increased, and the processability tends to be lowered.

The number average molecular weight (Mn) of the curable compound is, for example, 1000 to 15000, preferably 1000 to 14000, particularly preferably 1100 to 12000, and most preferably 1200 to 10000. The curable compound having a number average molecular weight has high solubility in a solvent, low melt viscosity, easy molding, and the obtained cured product (or molded product after curing) exhibits high toughness. To do. When the number average molecular weight is less than the above range, the toughness of the obtained cured product tends to decrease. On the other hand, when the number average molecular weight exceeds the above range, the solvent solubility of the curable compound tends to decrease, or the melt viscosity tends to become too high, resulting in a decrease in processability. Mn is obtained by subjecting it to gel permeation chromatography (GPC) measurement (solvent: chloroform, standard polystyrene conversion).

The curable compound has good solvent solubility. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide and the like. Amides; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, hexafluoro-2-propanol; dimethyl sulfoxide (DMSO), diethyl sulfoxide, benzylphenyl sulfoxide Sulfoxides such as: diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane, cyclopentylmethyl ether and the like; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; benzene, Aromatic hydrocarbons such as toluene and xylene; and a mixture of two or more of these can be mentioned. The curable compound is at least one solvent selected from ethers, ketones, amides, halogenated hydrocarbons, and sulfoxides (particularly, at least one selected from ethers, amides, halogenated hydrocarbons, and sulfoxides). It shows excellent solubility in one type of solvent).

The solubility of the curable compound in a solvent is, for example, 1 g or more, preferably 5 g or more, particularly preferably 10 g or more, with respect to 100 g of the solvent at 25 ° C.

The nitrogen atom content of the curable compound is, for example, 2.8 to 0.1% by weight, preferably 2.5 to 0.15% by weight, more preferably 2.0 to 0.20% by weight, and particularly preferably 2.0 to 0.20% by weight. It is 1.8 to 0.40% by weight, most preferably 1.5 to 0.70. The nitrogen atom content can be determined, for example, by CHN elemental analysis. A curable compound having a nitrogen atom content in the above range can form a cured product having excellent solvent solubility and excellent toughness and heat resistance. On the other hand, when the nitrogen atom content is less than the above range, it tends to be difficult to form a cured product having excellent toughness and heat resistance. Further, when the nitrogen atom content exceeds the above range, the solvent solubility tends to decrease.

The glass transition temperature (Tg) of the curable compound is, for example, 280 ° C. or lower (for example, 80 to 280 ° C.), preferably 80 to 250 ° C., and particularly preferably 100 to 200 ° C. When the curable compound has Tg in the above range, the melting temperature is low (that is, when the curable compound is melted, it can be melted by heating at a low temperature), so that the processability is excellent. On the other hand, when the Tg of the curable compound exceeds the above range, the melting temperature rises and the processability tends to decrease.

The compound represented by the above formula (1) can be produced, for example, by using the synthetic method described in Polymer 1989, p978. An example of a method for producing a compound represented by the above formula (1) is shown below, but the compound represented by the above formula (1) is not limited to that produced by this production method.

The compound represented by the following formula (1a) can be produced, for example, through the following steps [1] to [3]. In the following formula, Ar ¹ to Ar ³ , X, Y, n, R ³ to R ⁶ , Q, n'are the same as above. D represents a linking group and Z represents a halogen atom. m is the average degree of polymerization of the repeating unit, for example, 3 to 50, preferably 4 to 30, particularly preferably 5 to 20. Among the compounds represented by the above formula (1), compounds other than the compound represented by the following formula (1a) can also be produced according to the following method.
Step [1]: The reaction substrate is represented by the following formula (4) by reacting the compound represented by the following formula (2) with the compound represented by the following formula (3) in the presence of a base. Obtain the compound to be.
Step [2]: A diamine represented by the following formula (6) is obtained by reacting a compound represented by the following formula (4) with an amino alcohol (a compound represented by the following formula (5)).
Step [3]: A compound represented by the following formula (1a) is obtained by reacting a diamine represented by the following formula (6) with a cyclic acid anhydride (a compound represented by the following formula (7)).

(Step [1])
Examples of the compound represented by the above formula (2) include halides such as benzophenone, 2-naphthylphenyl ketone, and bis (2-naphthyl) ketone, and derivatives thereof.

Examples of the compound represented by the above formula (3) include hydroquinone, resorcinol, 2,6-naphthalene diol, 2,7-naphthalene diol, 1,5-naphthalene diol, 4,4'-dihydroxybiphenyl, 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl sulfone, bisphenol A, bisphenol F, bisphenol S, 2,5-dihydroxybiphenyl, and these. Derivatives of

Examples of the derivative include a compound represented by the above formula (2) and a compound in which a substituent is bonded to an aromatic hydrocarbon group of the compound represented by the formula (3). Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom and the like.

The amount of the compound represented by the formula (2) and the compound represented by the formula (3) is usually represented by the formula (2) with respect to 1 mol of the compound represented by the formula (3). It is desirable that the amount of the compound is 1 mol or more, and the amount of the compound represented by the formula (2) used is adjusted according to the average degree of polymerization of the molecular chains in the desired compound (1). For example, in the case of an average degree of polymerization of 5, about 1.2 mol of the compound represented by the formula (2) is about 1.2 mol (for example, 1.18 to 1.22 mol) with respect to 1 mol of the compound represented by the formula (3). When the average degree of polymerization is 10, the compound represented by the formula (2) is represented by about 1.1 mol (for example, 1.08 to 1.12 mol), and when the average degree of polymerization is 20, the compound represented by the formula (2) is represented. It is preferable to use about 1.05 mol (for example, 1.04 to 1.06 mol) of the compound to be used.

As the compound represented by the formula (2), it is preferable to use at least a halide of benzophenone, and the amount of the halide of benzophenone used in the total amount of the compound represented by the formula (2) (100 mol%). Is, for example, 10 mol% or more, preferably 30 mol% or more, particularly preferably 50 mol% or more, and most preferably 80 mol% or more. The upper limit is 100 mol%.

Examples of the compound represented by the formula (3) include hydroquinone, resorcinol, 2,6-naphthalene diol, 2,7-naphthalene diol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and 4,4'. At least one selected from −dihydroxybenzophenone, 4,4′-dihydroxydiphenylsulfide, 4,4′-dihydroxydiphenylsulphon, and bisphenol A (particularly at least one selected from hydroquinone, resorcinol, and bisphenol A). The compound is preferably used, and the total amount of the compounds used is, for example, 10 mol% or more, preferably 30 mol% or more, of the total amount of the compound represented by the formula (3) (100 mol%). , Particularly preferably 50 mol% or more, and most preferably 80 mol% or more. The upper limit is 100 mol%.

The reaction between the compound represented by the formula (2) and the compound represented by the formula (3) is a base (for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc.). Inorganic bases; at least one selected from organic bases such as pyridine and triethylamine). The amount of base used can be appropriately adjusted depending on the type of base. For example, the amount of the diacid base such as calcium hydroxide used is about 1.0 to 2.0 mol with respect to 1 mol of the compound represented by the formula (3).

Also, this reaction can be carried out in the presence of a solvent. As the solvent, for example, an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, or toluene, or a mixed solvent of two or more of these can be used.

The amount of the solvent used is, for example, about 5 to 20 times by weight with respect to the total (weight) of the reaction substrates. If the amount of the solvent used exceeds the above range, the concentration of the reaction substrate tends to decrease, and the reaction rate tends to decrease.

The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.

The reaction temperature is, for example, about 100 to 200 ° C. The reaction time is, for example, about 5 to 24 hours. Further, this reaction can be carried out by any method such as batch type, semi-batch type and continuous type.

After completion of this reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a separation means combining these. ..

(Step [2])
Examples of the compound represented by the above formula (5) include 4-aminophenol, 2-amino-6-hydroxynaphthalene, and positional isomers and derivatives thereof.

The amount of the compound represented by the above formula (5) can be appropriately adjusted according to the average degree of polymerization of the molecular chains in the desired curable compound. For example, in the case of an average degree of polymerization of 5, the amount is about 0.4 to 0.6 mol with respect to 1 mol of the compound represented by the formula (3), and in the case of an average degree of polymerization of 10, it is represented by the formula (3). In the case of an amount of about 0.2 to 0.4 mol with respect to 1 mol of the compound to be obtained and an average degree of polymerization of 20, 0.1 to 0. The amount is about 15 mol.

Since this reaction produces hydrogen halide as it progresses, it is preferable to carry out the reaction in the presence of a base that traps the generated hydrogen halide, because the effect of accelerating the progress of the reaction can be obtained. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate; and organic bases such as pyridine and triethylamine. These can be used alone or in combination of two or more.

The amount of the base used can be appropriately adjusted depending on the type of base. For example, the amount of a monoacid base such as sodium hydroxide used is about 1.0 to 3.0 mol with respect to 1 mol of the compound represented by the above formula (5).

Also, this reaction can be carried out in the presence of a solvent. As the solvent, the same solvent as that used in the step [1] can be used.

The reaction temperature is, for example, about 100 to 200 ° C. The reaction time is, for example, about 1 to 15 hours. Further, this reaction can be carried out by any method such as batch type, semi-batch type and continuous type.

After completion of this reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a separation means combining these. ..

(Step [3])
Examples of the cyclic acid anhydride (compound represented by the above formula (7)) include maleic anhydride, 2-phenylmaleic anhydride, 4-phenylethynyl-phthalic anhydride, and 4- (1-naphthylethaneyl). -Maleic anhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, derivatives thereof and the like can be mentioned.

The amount of the cyclic acid anhydride used can be appropriately adjusted according to the average degree of polymerization of the molecular chains in the desired curable compound. For example, when the average degree of polymerization is 5, the amount is about 0.4 to 0.8 mol with respect to 1 mol of the compound represented by the formula (3), and when the average degree of polymerization is 10, it is represented by the formula (3). In the case of an amount of about 0.2 to 0.4 mol with respect to 1 mol of the compound to be obtained and an average degree of polymerization of 20, 0.1 to 0. The amount is about 15 mol.

This reaction can be carried out in the presence of a solvent. As the solvent, the same solvent as that used in the step [1] can be used.

This reaction is preferably carried out at room temperature (1 to 30 ° C.). The reaction time is, for example, about 1 to 30 hours. Further, this reaction can be carried out by any method such as batch type, semi-batch type and continuous type.

Further, this reaction involves removing the by-produced water by azeotroping with a solvent that azeotropes with water (for example, toluene or the like) or by using a dehydrating agent (for example, acetic anhydride). It is preferable in that it promotes the progress of. Further, the removal of the produced water with a dehydrating agent is preferably performed in the presence of a basic catalyst (for example, triethylamine or the like).

After completion of this reaction, the obtained reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a separation means combining these. ..

The exothermic peak temperature of the compound represented by the formula (1) depends on the type of curable functional group, but is, for example, 170 to 450 ° C., preferably 200 to 430 ° C., particularly preferably 220 to 420 ° C. For example, in the case of the compound represented by the formula (1) and R ¹ and R ² are the groups represented by the above formula (r-5), the exothermic peak temperature is about 250 ° C. The exothermic peak temperature is determined by DSC measurement.

The curable composition may contain one of the curable compounds alone, or may contain two or more of the curable compounds in combination. The content of the curable compound in the total amount of the curable composition (or the total amount of the non-volatile content in the curable composition) (or the total amount when two or more kinds are contained) is, for example, 30% by weight or more, preferably 50. By weight or more, particularly preferably 70% by weight or more, most preferably 90% by weight or more. The upper limit is, for example, 95% by weight.

(Silicate)
The silicate, for example a plurality of anions consisting of SiO ₄ tetrahedron is a compound having less SiO tetrahedral sheet structure continuous to plane. Then, a part of Si forming the tetrahedral sheet structure may be replaced with cations such as ^{Al 3+} , Fe ³⁺ , B ³⁺ , and Ge ^4+. Further, the silicate may have an octahedral sheet structure in addition to the tetrahedral sheet structure, and the octahedral sheet structure is positive such as ^{Li +} , Mg ²⁺ , Fe ²⁺ , AL ³⁺ , Fe ^{3+ and the like.} It may contain ions. Furthermore, the silicate may have alkali metal ions between layers of a sheet structure such as a tetrahedral sheet structure or an octahedral sheet structure.

The silicate includes, for example, mica (mica), kaolin, talc, silica, montmorillonite and the like. Of these, mica is preferable because it has excellent dispersibility.

The shape of the silicate includes various shapes such as flaky, particulate, and needle-like, and among them, flaky silicate is preferable in terms of excellent dispersibility.

The thickness W of the flaky silicate is, for example, 0.5 μm or less, preferably 0.01 to 0.5 μm, and particularly preferably 0.05 to 0.5 μm.

The maximum diameter L ₁ of the flaky silicate is, for example, 5 to 40 μm, preferably 6 to 35 μm, and particularly preferably 7 to 30 μm.

The diameter L ₂ (hereinafter, may be referred to as “cross diameter L ₂ ”) orthogonal to the maximum diameter L ₁ of the flaky silicate is, for example, 3 to 30 μm, preferably 5 to 20 μm, and particularly preferably 8 to. It is 15 μm.

The maximum diameter L ₁ of the flaky silicate, the cross diameter L ₂ and the thickness W preferably satisfy the following formulas (a) and (b).
0.2L ₁ ≤ L ₂ ≤ L ₁ (a)
0.001L ₁ ≤ W ≤ 0.08L ₁ (b)

It is more preferable that the maximum diameter L ₁ of the flaky silicate, the cross diameter L ₂ and the thickness W satisfy the following formulas (a'), (b) and (c).
0.3L ₁ ≤ L ₂ ≤ 0.9L ₁ (a')
0.001L ₁ ≤ W ≤ 0.08L ₁ (b)
0.005L ₂ ≤ W ≤ 0.4L ₂ (c)

The diameters L ₁ , L ₂ and the thickness W of the flaky silicate are obtained by, for example, an image analysis method. That is, an electron microscope (SEM) is used to take an electron microscope image of a sufficient number (for example, 10 or more) of particulate matter, and the maximum diameter, cross diameter, and thickness of these particulate matter are measured. Is calculated by arithmetically averaging.

In addition, the silicate includes hydrophilic silicate and lipophilic silicate. The hydrophilic silicate in the form of flakes is superior in dispersibility as in the form of thick film, and has the effect of imparting low CTE property to the curable composition. Further, the lipophilic silicate has excellent dispersibility regardless of the particle size.

The lipophilic silicate is one in which at least a part of the alkali metal ions contained between the layers of the sheet structure is replaced with an organic ion exhibiting lipophilicity (for example, a quaternary ammonium ion).

The quaternary ammonium ion is represented by, for example, the following formula (d).

(In the formula, R ^a , R ^b , R ^c and R ^d represent alkyl groups having 1 to 20 carbon atoms which may have the same or different hydroxy groups).

The shape of the lipophilic silicate is in the form of flakes or particles. The maximum diameter L ₃ of the lipophilic silicate is, for example, 1 to 30 μm, preferably 2 to 25 μm, and particularly preferably 3 to 20 μm. The cross diameter _{L 4} perpendicular to the maximum diameter _{L 3} is from 0.1 to 0.9 times the maximum diameter _{L 3,} preferably 0.2 to 0.8 times. The thickness W ₁ is 0.05 to 1.0 times, preferably 0.1 to 0.9 times, the maximum diameter L _3.

Further, the silicates include swelling silicates and non-swelling silicates. Non-swelling silicate has excellent heat resistance. On the other hand, the swollen silicate ^{contains Na +} between layers and is excellent in heat resistance when it exhibits hydrophilicity, but when the Na ⁺ is replaced with an organic ion, it acquires lipophilicity and is heat resistant. The sex tends to decrease.

Furthermore, it is preferable that the silicate has an appropriate stress absorption property from the viewpoint of excellent dispersibility. As the silicate having appropriate stress absorption, a silicate having the following characteristics 1 and 2 is preferable.
Characteristic 1: A PVC ring for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface is filled with silicate until the height from the upper flat surface of the vinyl chloride ring reaches 5.0 mm, and the maximum pressurization is performed. Pressurize at 7 MPa for 3 minutes to smooth the PVC ring surface, and 5 minutes after decompression, the PVC ring surface rises. Characteristic 2: Salt for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface. The billing is filled with silicate until the height from the upper plane of the vinyl chloride ring reaches 3.0 mm, and the surface of the vinyl chloride ring is smoothed by pressurizing at a maximum pressurization of 5 MPa for 3 minutes. Does not cause swelling on the surface of

The silicate having both the above-mentioned characteristics 1 and the above-mentioned property 2 is a non-swelling type silicate (preferably a non-swelling type silicate having the above diameters L ₁ , L ₂ and the thickness W. A silicate that satisfies the formulas (a) and (b)).

Furthermore, as the silicate, a silicate containing an alkali metal (more specifically, a silicate containing an alkali metal between the layers of the sheet structure, that is, a non-swelling silicate) has dispersibility and heat resistance. It is preferable because it has excellent properties.

The alkali metal content (when two or more kinds are contained, the total amount thereof) is preferably, for example, 7.0% by weight or more, more preferably 8.0% by weight or more, and particularly preferably 9 of the total amount of silicate. It is 0.0% by weight or more, most preferably 9.5% by weight or more. The upper limit of the alkali metal content is, for example, 20% by weight, preferably 15% by weight, and particularly preferably 10% by weight.

Further, among the alkali metals, the content of potassium is preferably, for example, 1.0% by weight or more, more preferably 3.0% by weight or more, and particularly preferably 5.0% by weight, based on the total amount of silicate. As mentioned above, it is most preferably 7.0% by weight or more. The upper limit of the potassium content is, for example, 20% by weight, preferably 15% by weight, and particularly preferably 10% by weight.

Among the alkali metals, the content of sodium is preferably, for example, 5.0% by weight or less, more preferably 3.0% by weight or less, still more preferably less than 3.0% by weight, based on the total amount of silicate. It is particularly preferably 1.0% by weight or less, most preferably 0.5% by weight or less, and particularly preferably 0.1% by weight or less.

Silicates containing alkali metals (particularly potassium and sodium) in the above range include non-swelling silicates (particularly non-swelling mica).

Further, as the silicate, a silicate containing magnesium (more specifically, a silicate having an octahedral sheet structure containing magnesium) is preferable in that it has excellent dispersibility. The magnesium content is preferably 10% by weight or more (for example, 10 to 30% by weight) of the total amount of silicate, and more preferably 15% by weight or more (for example, 15 to 20% by weight).

Examples of the silicate containing magnesium in the above range include the above-mentioned flaky silicate and lipophilic silicate.

Further, as the silicate, a silicate containing aluminum (more specifically, a silicate having an octahedral sheet structure containing aluminum) is preferable in that it has excellent dispersibility. The aluminum content is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, particularly preferably 3.0% by weight or more, and most preferably 5.0% by weight of the total amount of silicate. % Or more. The upper limit of the aluminum content is, for example, 15% by weight, preferably 10% by weight, and particularly preferably 8% by weight.

Examples of the silicate containing aluminum in the above range include the above-mentioned flaky silicate and lipophilic silicate.

Furthermore, as the silicate, since the silicate containing a fluorine atom has excellent heat resistance and electrical properties (specifically, the dielectric constant and the dielectric loss tangent are low), the obtained cured product has excellent electrical properties. It is preferable in that it can exert. The fluorine atom content is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, particularly preferably 3.0% by weight or more, and most preferably 5.0% by weight of the total amount of silicate. Weight% or more. The upper limit of the content of fluorine atoms is, for example, 20% by weight, preferably 15% by weight, and particularly preferably 10% by weight.

Examples of the silicate containing a fluorine atom in the above range include synthetic mica.

The content of the silicate is 0.01 to 95 parts by weight, preferably 40 to 70 parts by weight, more preferably 45 to 65 parts by weight, and particularly preferably 50 to 60 parts by weight with respect to 100 parts by weight of the curable compound. Is. Since the curable composition contains a silicate in the above range, a cured product having heat resistance (for example, heat resistance of about 200 ° C.) and flexibility can be formed.

In particular, when a non-swelling silicate, a hydrophilic swelling silicate, or a flaky silicate is contained in the above range as the silicate, heat resistance (for example, heat resistance of 300 ° C. or higher) and possible A cured product having flexibility (in a mandrel test, for example, a diameter of 5 mm or less, preferably a diameter of 3 mm or less) can be formed.

Further, when the silicate contains a non-swelling silicate, a lipophilic swelling silicate, or a flaky silicate in the above range, low CTE and flexibility (in a mandrel test, for example, A cured product having a diameter of 5 mm or less, preferably 3 mm or less in diameter) can be formed.

Further, when flaky silicate (preferably non-swelling flaky silicate) is contained in the above range as the silicate, low CTE, heat resistance (for example, heat resistance of 300 ° C. or higher), and A cured product having flexibility (in a mandrel test, for example, a diameter of 5 mm or less, preferably a diameter of 3 mm or less) can be formed.

The CTE (coefficient of linear expansion) of the cured product is, for example, 10 × 10 ^-6 to 50 × 10 ^-6 / ° C, preferably 10 × 10 ^-6 to 30 × 10 ^-6 / ° C. The CTE of the cured product changes little even if the temperature range is different. For example, the difference between the coefficient of linear expansion (α1) in the region lower than Tg and the coefficient of linear expansion (α2) in the region higher than Tg is small, and α2 / α1 is, for example, 2.0 or less.

As described above, the silicate can be imparted to a curable composition or a cured product of the curable composition depending on the particle shape and properties (hydrophilic / lipophilic, swelling type / non-swelling type). Have a difference in. Therefore, it is preferable to select and use a silicate according to the application and required characteristics.

(Other ingredients)
The curable composition may contain other components, if necessary, in addition to the curable compound and the silicate. Other components include, for example, catalysts, radical polymerization initiators, organic resins (silicone resins, epoxy resins, fluororesins, etc.), solvents, stabilizers (antioxidants, UV absorbers, light retardant stabilizers, thermal stabilization). Agents, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardants, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes, plasticizers, mold release agents, Impact resistance improver, hue improver, fluidity improver, colorant (dye, pigment, etc.), dispersant, defoaming agent, defoaming agent, antibacterial agent, preservative, viscosity modifier, thickener, etc. Can be mentioned. These can be used alone or in combination of two or more.

The content of other components (particularly, other non-volatile components) (the total amount when two or more types are contained) is, for example, 50% by weight or less, preferably 40% by weight or less, more preferably 40% by weight or less, based on the total amount of the curable composition. Is 30% by weight or less, particularly preferably 20% by weight or less, most preferably 10% by weight or less, and particularly preferably 5% by weight or less.

The curable composition preferably contains at least the compound represented by the above formula (1) as a curable compound. Further, a curable compound other than the compound represented by the above formula (1) may be contained, but it is represented by the above formula (1) in the total amount (100% by weight) of the curable compound contained in the curable composition. The proportion of the compound is, for example, 70% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more. The upper limit is 100% by weight. Therefore, the content of the curable compound other than the compound represented by the above formula (1) is, for example, 30% by weight or less, preferably 20% by weight, based on the total amount (100% by weight) of the curable compound contained in the curable composition. % Or less, particularly preferably 10% by weight or less.

When the curable composition contains a compound represented by the above formula (1) as a curable compound, the compound represented by the above formula (1) is, for example, a ketone, an amide, a halogenated hydrocarbon, a sulfoxide, or the like. Since it has excellent solubility in ethers, esters, nitriles, aromatic hydrocarbons, and a mixture of two or more of these, these solvents can be contained.

By heating the curable composition, a cured product having heat resistance and flexibility can be formed. Further, when a specific silicate is contained, a cured product having low CTE, heat resistance, and flexibility can be formed. Further, the cured product of the curable composition has flame retardancy and good dielectric properties (low relative permittivity and dielectric loss tangent).

Further, the curable composition can form a semi-cured product (B stage) by adjusting the heating temperature and the heating time and stopping the curing reaction in the middle without completing the curing reaction.

Since the curable composition has the above characteristics, for example, harsh environmental temperatures in the fields of electronic information equipment, home appliances, automobiles, precision machinery, aircraft, space industry equipment, energy fields (oil drilling pipes / tubes, fuel containers), etc. Molding materials (eg, sizing agents) for composites (fiber reinforced plastics, prepregs, etc.) used under conditions, shielding materials, conductive materials (eg, heat conductive materials, etc.), insulating materials, adhesives (eg, heat resistant). It can be suitably used as a functional material such as a sex adhesive). In addition, sealants, paints, coating agents, inks, sealants, resists, molding materials, forming materials [automotive parts such as thrust washers, oil filters, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, pedals, etc.; Base material, electronic circuit board (especially electronic circuit board to which copper wiring is applied), electrical insulating material (insulating film, etc.), laminated board, electronic paper, touch panel, solar cell board, optical waveguide, light guide plate, holographic memory, silicon Semiconductor / liquid crystal manufacturing equipment parts such as wafer carriers, IC chip trays, electrolytic condenser trays, and insulating films; optical parts such as lenses; compressor parts such as pumps, valves, and seals; aircraft cabin interior parts; sterilization equipment, columns, and piping Medical equipment parts such as, food and beverage manufacturing equipment parts; housings used for personal computers, mobile phones, etc., and electricity represented by keyboard supports, which are members that support keyboards inside personal computers. -It can be preferably used as a forming material for electronic device members, etc.].

Since the curable composition can form a cured product having heat resistance and a low CTE comparable to that of copper, it is particularly preferably used as a raw material for an electronic circuit substrate to which copper wiring is applied. it can.

[Cured product, semi-cured product]
The cured product (or semi-cured product) of the present disclosure is a cured product (or semi-cured product) of the above-mentioned curable composition.

The cured product (or semi-cured product) is preferably represented by the formula (1), and R ¹ and R ² in the formula are cured functional groups having the same or different cyclic imide structure. A sex compound (particularly preferably, selected from the groups represented by the above formula (1), in which R ¹ and R ^{2 in} the formula are the same or different and are represented by the formulas (r-1) to (r-6). It is a cured product (or semi-cured product) of the curable compound which is the group to be formed.

The cured product (or semi-cured product) can be produced by subjecting the curable composition to heat treatment (heating temperature is, for example, 180 to 250 ° C.).

The heat treatment may be performed while the temperature is kept constant, or the temperature may be changed stepwise. The heat treatment temperature can be appropriately adjusted according to the heating time. For example, when it is desired to shorten the heating time, it is preferable to set the heating temperature higher.

The curable composition can be cured under normal pressure, reduced pressure or pressurized.

For example, when the curable composition contains a compound represented by the formula (1) as a curable compound, the compound represented by the formula (1) has a high proportion of a structure derived from an aromatic ring, and therefore, at a high temperature. A cured product (specifically, a cured product having heat resistance) can be formed without decomposition even when heated, and a cured product can be efficiently formed with excellent workability by heating at a high temperature for a short time. Can be done. Further, the heating means is not particularly limited, and known or commonly used means can be used.

Then, the semi-cured product (B stage) can be produced by adjusting the heating temperature and the heating time of the curable composition and stopping the curing reaction in the middle without completing the curing reaction. The degree of curing of the semi-cured product is, for example, 85% or less (for example, 10 to 85%, preferably 15 to 75%, and more preferably 20 to 70%).

The degree of curing of the semi-cured product can be calculated from the following formula by measuring the calorific value of the curable composition and the calorific value of the semi-cured product by DSC.
Curing degree (%) = [1- (calorific value of semi-cured product / calorific value of curable composition)] x 100

When the semi-cured product is a semi-cured product of a curable composition containing a compound represented by the formula (1) as a curable compound, the semi-cured product temporarily exhibits fluidity by heating. It can be made to follow a step. Further, by applying the heat treatment, a cured product having excellent heat resistance can be formed.

The cured product has a low CTE of the copper substrate and the same degree, the linear expansion coefficient, for example, ^{10 × 10 -6 ~ 50 × 10} -6 / ℃, preferably ^{10 × 10 -6 ~ 30 × 10} -6 / ℃. The coefficient of linear expansion does not change much even if the temperature range is different. For example, the difference between the coefficient of linear expansion (α1) in the region lower than Tg and the coefficient of linear expansion (α2) in the region higher than Tg is small, and α2 / α1 is, for example, 2.0 or less. Therefore, even if the laminated body of the cured product and the copper foil is exposed to a high temperature environment, curling of the laminated body can be suppressed.

Further, the cured product has, for example, a 5% weight loss temperature (T _d5 ) of 300 ° C. or higher, and a nitrogen atom content of 2.8 to 0.1 after being subjected to heat treatment at 320 ° C. for 30 minutes. By weight%.

_{The 5% weight loss temperature (T d5} ) of the cured product measured at a heating rate of 10 ° C./min (in nitrogen) is, for example, 300 ° C. or higher, preferably 400 ° C. or higher, particularly preferably 450 ° C. or higher, most preferably. It is preferably 500 ° C. or higher. The upper limit of the 5% weight loss temperature (T _d5 ) is, for example, 600 ° C., preferably 550 ° C., particularly preferably 530 ° C.

The nitrogen atom content after subjecting the cured product to heat treatment at 320 ° C. for 30 minutes is, for example, 2.8 to 0.1% by weight, preferably 2.5 to 0.15% by weight, more preferably. Is 2.0 to 0.20% by weight, particularly preferably 1.8 to 0.40% by weight, and most preferably 1.5 to 0.70% by weight. Therefore, the cured product is excellent in toughness and heat resistance. On the other hand, when the nitrogen atom content is lower than the above range, the toughness and heat resistance of the cured product tend to decrease.

The nitrogen atom content in the cured product after being subjected to the heat treatment can be determined, for example, by CHN elemental analysis.

The cured product may contain additives in addition to the polymer of the curable compound, but when the cured product is heat-treated at 320 ° C. for 30 minutes, it has a decomposition point and a boiling point of less than 320 ° C. Additives are decomposed and disappear, leaving only the polymer of the curable compound. Therefore, the nitrogen atom content in the cured product after the heat treatment can be estimated to be the nitrogen atom content contained in the polymer of the curable compound. The curing treatment can also be a heat treatment from the viewpoint of heat history.

In addition, the cured product has a peak in the region ^{of 1620 to 1750 cm -1 of the IR spectrum.} The peak is derived from the "-C (= O) -NC (= O)-" unit.

Furthermore, the cured product has excellent flame retardancy, and the flame resistance of the cured product having a thickness of 0.15 mm by a method conforming to UL94V is V-1 grade, that is, the following conditions 1 to 5 are satisfied.
(1) Burning duration is 30 seconds or less (2) Total burning time of 5 samples is 250 seconds or less (3) Red heat duration after the second flame contact is 60 seconds or less (4) Fixing clamp Does not burn to the part (5) Does not drop burning particles and burn the cotton laid underneath

Further, the cured product has excellent insulating properties, and the relative permittivity is, for example, 6 or less (for example, 1 to 6), preferably 5 or less (for example, 1 to 5), and particularly preferably 4 or less (for example, 1 to 4). .. The dielectric loss tangent is, for example, 0.05 or less (for example, 0.0001 to 0.05), preferably 0.0001 to 0.03, and particularly preferably 0.0001 to 0.015.

The "relative permittivity" and "dielectric loss tangent" are values measured at a measurement frequency of 1 MHz and a measurement temperature of 23 ° C. in accordance with JIS-C2138, or at frequencies of 1 GHz and 23 ° C. in accordance with ASTM D2520. It is a value to be measured.

[Laminate]
The laminate of the present disclosure has a structure in which a cured product or semi-cured product of the curable composition and a substrate are laminated. The laminate includes a cured product or semi-cured product / substrate of the curable composition and a cured product or semi-cured product / substrate of the substrate / curable composition.

The laminate can be produced, for example, by applying the curable composition onto a substrate and subjecting it to heat treatment.
In the laminated body, the curable composition is applied onto a support, and the semi-cured product obtained by heat-treating and semi-curing is peeled off from the support and placed on a substrate. It can also be produced by a method of further heat treatment.

Examples of the substrate material include semiconductor materials (for example, ceramics, SiC, gallium nitride, etc.), paper, coated paper, plastic films, wood, cloth, non-woven fabrics, metals (for example, stainless steel, aluminum alloys, copper). And so on.

Since the curable composition has a low CTE, curling can be suppressed even when laminated on a base material having a small coefficient of linear expansion (for example, a metal foil such as copper), resulting in shape stability. Excellent.

When the laminate has a cured product / substrate or substrate / cured product / substrate configuration, the adhesion between the cured product and the substrate is excellent. The tensile shear force between the substrate and the cured product (based on JIS K6850 (1999)) is, for example, 1 MPa or more, preferably 5 MPa or more, and particularly preferably 10 MPa or more. The tensile shear force can be measured at a tensile speed of 300 mm / min and a peeling angle of 180 ° using a tensile retesting machine (Tencilon UCT-5T manufactured by Orientec Co., Ltd.).

The laminated body also has a structure in which a substrate is laminated via a cured product having excellent heat resistance, flame retardancy, and insulating properties. Therefore, the laminated body can be suitably used as, for example, an electronic circuit board or the like.

[Printed circuit boards and electronic devices]
The printed circuit board of the present disclosure has a structure in which conductor wiring is applied on a substrate made of a cured product of the curable composition. Further, the electronic device has the printed circuit board.

The conductor wiring includes wiring using a conductor such as copper or aluminum. Of these, copper wiring is preferable because it has excellent conductivity.

The curable composition has excellent heat resistance and low CTE. Therefore, the surface of the substrate made of the cured product of the curable composition is exposed to thermal stress such as being subjected to a solder reflow process in which conductor wiring such as copper or aluminum having a small coefficient of linear expansion is applied. However, since the difference between the coefficient of thermal expansion of the substrate and the coefficient of thermal expansion of the conductor wiring is extremely small, it is possible to prevent the wiring from breaking.

And since the electronic device includes a printed circuit board having thermal stress resistance, it has high reliability.

As described above, each configuration of the present disclosure and combinations thereof are examples, and the configurations can be added, omitted, replaced, and changed as appropriate without departing from the gist of the present disclosure. In addition, the present disclosure is not limited by the embodiments, but is limited only by the description of the scope of claims.

Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited to these Examples.

The measurement was performed under the following conditions.
<NMR measurement>
Measuring device: BRUKER 400MHz / 54mm or BRUKER AVANCE 600MHz
Measuring solvent: Deuterated DMSO, deuterated chloroform, or deuterated chloroform / pentafluorophenol (PFP) = 2/1 (wt / wt) mixed solution Chemical shift: <GPC measurement based on TMS>
Equipment: Pump "LC-20AD" (manufactured by Shimadzu Corporation)
Detector: RID-10A (manufactured by Shimadzu Corporation) or TDA-301 and UV2501 (manufactured by Viscotek)
Solvent: THF or chloroform column: shodex GPC K-806L x 1 + shodex GPC K-803 x 1 + shodex GPC K-801 x 2 Flow velocity: 1.0 mL / min
Temperature: 40 ° C
Sample concentration: 0.1% (wt / vol)
Standard polystyrene conversion <DSC measurement>
Equipment: TA Q20
Temperature rise rate: 10 ° C / min
Atmosphere: Nitrogen atmosphere <TG / DTA measurement>
Equipment: NETZSCH TG209F3
Temperature rise rate: 10 ° C / min
Atmosphere: Nitrogen atmosphere <IR measurement>
Equipment: Perkin Elmer Spectram RX1 (ATR method)

Preparation Example 1
Preparation of Diamine (1) In a 500 mL (three-necked) flask equipped with a stirrer, a nitrogen introduction tube, and a Dean-Stark apparatus, 27.50 g of 4,4'-difluorobenzophenone, 23.98 g of bisphenol A, and anhydrous potassium carbonate (K ₂ CO). ₃ ) 21.77 g, 220 mL of N-methyl-2-pyrrolidone, and 110 mL of toluene were added and heated with stirring under a nitrogen atmosphere, and toluene was refluxed at 130 to 140 ° C. for 4 hours. Then, the mixture was further heated to distill off toluene at 170 to 180 ° C. Further, after continuing stirring at 170 to 180 ° C. for 10 hours, the temperature was returned to room temperature.

To the flask containing the obtained product, 5.04 g of 4-aminophenol, 6.39 g of anhydrous potassium carbonate, 30 mL of N-methyl-2-pyrrolidone, and 150 mL of toluene were added, and the mixture was stirred again in a nitrogen atmosphere. It was heated and the toluene was refluxed at 130-140 ° C. for 3 hours. Then, the mixture was heated to distill off toluene at 170 to 180 ° C., and stirring was continued for 4 hours while maintaining 170 to 180 ° C. Then, the mixture was cooled to room temperature, the reaction solution was added to 3000 mL of methanol, and the mixture was filtered to obtain a powdery solid. This powdery solid was repeatedly washed with methanol and water and then dried under reduced pressure at 100 ° C. for 8 hours to obtain a powdery solid (diamine (1), compound represented by the following formula, yield: 95%). .. The obtained powdery solid was subjected to GPC measurement (solvent: THF, standard polystyrene conversion) to obtain a number average molecular weight of 2920, a weight average molecular weight of 5100, and an average degree of polymerization (m-2) of 6.2. there were. ^{The 1} H-NMR spectrum of the obtained diamine (1) is shown in FIG. 1, and the FTIR spectrum is shown in FIG.

Preparation of curable compound A 5.88 g of maleic anhydride, 50 mL of N-methyl-2-pyrrolidone, and 200 mL of toluene were placed in a 1000 mL (three-necked) flask equipped with a stirrer, a nitrogen introduction tube and a drying tube, and nitrogen was substituted. did. A solution prepared by dissolving 48.57 g of the obtained diamine (1) in 330 mL of NMP was added thereto, and the mixture was stirred at room temperature for 24 hours under a nitrogen atmosphere. Then, 0.761 g of paratoluene sulphonic acid monohydrate was added, heated to 140 ° C., stirring was continued for 8 hours, and toluene was refluxed to remove water. After returning the reaction solution to room temperature, the reaction solution was added to 3000 mL of methanol and filtered to obtain a powdery solid. This powdery solid is repeatedly washed with methanol and water, and then dried under reduced pressure at 100 ° C. for 8 hours to obtain a powdery solid (curable compound A, a compound represented by the following formula (A), a structure derived from an aromatic ring). Ratio: 71% by weight, yield: 90%) was obtained. ^{The 1} H-NMR spectrum of the curable compound A is shown in FIG. 3, and the FTIR spectrum is shown in FIG.
^{1 1} H-NMR (CDCl ₃ ) δ: 1.71 (s), 6.87 (s), 7.02 (m), 7.09 (m), 7.17 (d, J = 8.8 Hz) , 7.26 (m), 7.37 (d, J = 8.8Hz), 7.80 (m)

Further, the viscosity of the curable compound A at 200 ° C. and a shear rate of 10 (1 / s) was measured by a rheometer and found to be 14 Pa · s.

Further, the number average molecular weight and the weight average molecular weight of the obtained curable compound A were determined by GPC measurement (solvent THF, standard polystyrene conversion). As a result, the number average molecular weight (Mn) was 3160 and the weight average molecular weight (Mw) was 5190.

Furthermore, the Tg of the obtained curable compound A was determined by DSC measurement. As a result, it was 131 ° C.

Example 1
As shown in Table 1 below, 45 parts by weight of the curable compound A and 55 parts by weight of toluene obtained in the preparation example and a radical polymerization initiator (t-butyl peroxybenzoate, trade name "Perbutyl Z", Nippon Oil & Fats Co., Ltd.) (Manufactured by) 0.45 parts by weight was blended and stirred with a rotation / revolution mixer (trade name "Awatori Rentaro ARE-310", manufactured by Shinky Co., Ltd.) for 4 hours.
Then, 24 parts by weight of mica was further added and stirred for 5 minutes, and then defoamed for 5 minutes to obtain a curable composition.

The obtained curable composition was placed on a copper foil (trade name "CF-T9DA-SV-18", manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., 10 cm x 10 cm) with a thickness of 100 μm in a wet state. It was applied using an applicator so as to obtain a coating film / copper foil laminate.
The obtained coating film / copper foil laminate is heated at 105 ° C. for 10 minutes and then at 150 ° C. for 10 minutes to volatilize toluene using a hot plate to obtain a dry coating film / copper foil laminate. It was.
Then, the obtained dry coating film / copper foil laminate was heated at 250 ° C. for 1 hour under vacuum conditions to cure the coating film to obtain a cured product / copper foil laminate.

The obtained cured product / copper foil laminate was immersed in an aqueous iron (III) chloride solution (40% by weight) overnight to remove the copper foil at room temperature to obtain a cured product. For the obtained cured product, α1 (coefficient of linear expansion in a region lower than Tg) and α2 (coefficient of linear expansion in a region higher than Tg) were obtained from the strain-temperature curve obtained under the following conditions.
<TMA: Tension>
Measuring device: TMA SS7100 / Hitachi High-Tech Science Atmosphere: N ₂
Temperature range: 1st heat / 0 ℃ ~ 250 ℃
2nd heat / 00C ~ 250 ℃
20 minutes standby at the start temperature Temperature rise rate: 5 ° C / min
Measured load: 20mN

Examples 2-4
As shown in Table 1 below, a curable composition was obtained in the same manner as in Example 1 except that the type of mica to be added was changed, and a dry coating film / copper foil laminate, a cured product / copper foil laminate, and A cured product was obtained.

Comparative Example 1
A curable composition was obtained in the same manner as in Examples except that mica was not added, and a dry coating film / copper foil laminate, a cured product / copper foil laminate, and a cured product were obtained.

The following evaluations were performed on the dry coating film / copper foil laminate and the cured product / copper foil laminate obtained in Examples and Comparative Examples.

(Curl resistance evaluation)
The cured product / copper foil laminate (10 cm × 10 cm) was placed on a flat plate with the cured product surface facing up, and allowed to stand in an oven set at 200 ° C. for 60 minutes, after which the laminate was placed. The height of the four corners of the laminate was measured from the surface of the flat plate after 5 minutes had passed since the product was placed on the flat plate in an environment of room temperature (25 ° C.) and the curl amount was measured from the average value. Then, the curl resistance was evaluated according to the following criteria. If the evaluation result is ◯, it means that the CTE of the cured product is equivalent to the CTE of the copper foil (about 17 / ppm).
<Evaluation criteria>
○ (Good): Average curl amount is 2 cm or less △ (Normal): Average curl amount is more than 2 cm, 5 cm or less × (Poor): Average curl amount is more than 5 cm, or curled until it becomes tubular

(Flexibility evaluation)
For the cured product / copper foil laminate (10 cm x 10 cm), in accordance with JIS K5600-5-1 (bending resistance (cylindrical mandrel)), bending tester (trade name "mandrel bending tester", Co., Ltd.) ) Toyo Seiki Seisakusho) was used to wrap the laminate around a mandrel with a diameter of 5 mm so that the cured product layer was on the outside, and the flexibility was evaluated according to the following criteria.
<Evaluation criteria>
○ (Good): No crack × (Bad): With crack

(Heat resistance evaluation)
The dry coating film / copper foil laminate was heated at 250 ° C. for 1 hour under vacuum conditions, and the color change of the coating film before and after heating was visually observed, and the heat resistance was evaluated according to the following criteria.
<Evaluation criteria>
○ (Good): No discoloration × (Bad): Discoloration

NK-8G: Synthetic mica, trade name "NK-8G", MAE manufactured by Nippon Koken Kogyo Co., Ltd .: Dimethyldialkylammonium modified synthetic mica, trade name "Somasif MAE", ME100 manufactured by Katakura Corp. Agri Co., Ltd .: Synthetic mica , Product name "Somasif ME100", MK200 manufactured by Katakura Corp. Agri Co., Ltd .: Synthetic mica, Product name "Micromica MK200", manufactured by Katakura Corp. Agri Co., Ltd.

The mica used in the examples was subjected to the following test to confirm its characteristics. The results are summarized in Table 2 below.

(Particle shape)
Using SEM, electron microscope images of 10 mica particles were taken, and the maximum diameter L ₁ , cross diameter L ₂ , and thickness W of these particulate matter were calculated by arithmetic mean (FIGS. 5 to 8). ).

(Elemental analysis)
The constituent elements were identified by irradiating with X-rays and measuring the generated unique fluorescent X-rays, and the content (% by weight) of the elements was analyzed.

(Mica PVC ring test 1)
Fill the PVC ring for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface with mica until the height from the upper flat surface of the vinyl chloride ring reaches 5.0 mm, and apply for 3 minutes at a maximum pressure of 7 MPa. The surface of the vinyl chloride ring was smoothed by pressing, and it was visually observed whether or not the surface of the vinyl chloride ring was raised 5 minutes after the decompression. The case where the swelling occurred was described as "+", and the case where the swelling did not occur was described as "-".

(Mica PVC ring test 2)
Fill the PVC ring for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface with mica until the height from the upper flat surface of the vinyl chloride ring reaches 3.0 mm, and apply for 3 minutes at a maximum pressure of 5 MPa. The surface of the vinyl chloride ring was smoothed by pressing, and it was visually observed whether or not the surface of the vinyl chloride ring was raised 5 minutes after the decompression. The case where the swelling occurred was described as "+", and the case where the swelling did not occur was described as "-".

As a summary of the above, the configuration and variations thereof of the present disclosure are added below.
[1] A curable composition containing a curable compound and a silicate, wherein the content of the silicate is 0.01 to 95 parts by weight with respect to 100 parts by weight of the curable compound.
[2] The curable composition according to [1], wherein the silicate is a flaky silicate.
[3] The curable composition according to [1] or [2], wherein the silicate has the following characteristics 1 and 2.
Characteristic 1: A PVC ring for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface is filled with silicate until the height from the upper flat surface of the vinyl chloride ring reaches 5.0 mm, and the maximum pressurization is performed. Pressurize at 7 MPa for 3 minutes to smooth the PVC ring surface, and 5 minutes after decompression, the PVC ring surface rises. Characteristic 2: Salt for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface. The billing is filled with silicate until the height from the upper plane of the vinyl chloride ring reaches 3.0 mm, and the surface of the vinyl chloride ring is smoothed by pressurizing at a maximum pressurization of 5 MPa for 3 minutes. [4] The maximum diameter L ₁ of the silicate, the diameter L ₂ orthogonal to the maximum diameter L ₁ , and the thickness W satisfy the following formulas (a) and (b), [1] ] To [3]. The curable composition according to any one of.
0.2L ₁ ≤ L ₂ ≤ L ₁ (a)
0.001L ₁ ≤ W ≤ 0.08L ₁ (b)
[5] The curable composition according to any one of [1] to [4], wherein the silicate is a lipophilic silicate.
[6] The curable composition according to any one of [1] to [5], wherein the silicate contains an alkali metal.
[7] The curable composition according to any one of [1] to [6], wherein the silicate is a non-swelling silicate.
[8] silicate, the maximum diameter _{L 1,} the maximum diameter _{L 1} diameter _{L 2} and a thickness W which is orthogonal to the following formula (a), in satisfying the (b), the non-swelling silicate The curable composition according to any one of [1] to [7].
0.2L ₁ ≤ L ₂ ≤ L ₁ (a)
0.001L ₁ ≤ W ≤ 0.08L ₁ (b)
[9] The curable composition according to any one of [1] to [8], wherein the magnesium content of the silicate is 10% by weight or more.
[10] The curability according to any one of [1] to [9], wherein the sodium content of the silicate is less than 3.0% by weight and the potassium content is 1.0% by weight or more. Composition.
[11] The curable composition according to any one of [1] to [10], wherein the silicate is a flaky silicate and the sodium content is less than 3.0% by weight.
[12] The curable composition according to any one of [1] to [11], wherein the silicate is a flaky silicate and the potassium content is 1.0% by weight or more.
[13] The curable composition according to any one of [1] to [12], wherein the silicate is a flaky silicate and the aluminum content is 0.5% by weight or more.
[14] The curable composition according to any one of [1] to [13], wherein the silicate contains a fluorine atom.
[15] Any one of [1] to [14], wherein the silicate is a silicate containing a fluorine atom, and the content of the fluorine atom is 0.5% by weight or more of the total amount of the silicate. The curable composition according to 1.
[16] The curable composition according to any one of [1] to [15], wherein the silicate is mica.
[17] The curable compound has the following formula (1).

[In the formula, R ¹ and R ² indicate the same or different curable functional groups, and D ¹ and D ² indicate the same or different single bond or linking group. L represents a divalent group having a repeating unit including a structure represented by the following formula (I) and a structure represented by the following formula (II).

(In the formula, Ar ¹ to Ar ³ are the same or different, and represent an arylene group or a group in which two or more arylene groups are bonded via a single bond or a linking group. X indicates -CO-, -S-. , Or -SO _2- , Y indicates the same or different, -S-, -SO _2- , -O-, -CO-, -COO-, or -CONH-. N is 0 or more. Indicates an integer)]
The curable composition according to any one of [1] to [16], which is a compound represented by.
^{[18] The curable composition according to [17], wherein R 1} and R ² in the formula (1) are the same or different curable functional groups having a cyclic imide structure.
^{[19] The curable composition according to [17], wherein R 1} and R ² in the formula (1) are groups represented by the following formula (r).

(In the formula, Q indicates C or CH. Two Qs in the formula are bonded via a single bond or a double bond. N'is an integer of 0 or more. R ³ to R ⁶ are the same. Or differently, a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or two or more groups selected from the saturated or unsaturated aliphatic hydrocarbon group and an aromatic hydrocarbon group. Indicates a bonded group. ^{Two groups selected from R 3} to R ⁶ may be bonded to each other to form a ring with adjacent carbon atoms. The bond extending from the nitrogen atom in the equation is Combine with D ¹ or D ² )
^{[20] R 1} and R ² in the formula (1) are the same or different groups selected from the groups represented by the following formulas (r-1) to (r-6), [17] The curable composition according to.

(The bond extending from the nitrogen atom in the formula bonds with D ¹ or D ² )
^{[21] The curability according to [17], wherein R 1} and R ² in the formula (1) are the same or different and are groups represented by the following formula (r-1) or (r-5). Composition.

(The bond extending from the nitrogen atom in the formula bonds with D ¹ or D ² )
[22] A group represented by the following formula (rd-1) or (rd-2) in which ^{the R 1-} D ¹ -group and the R ^2- D ^2- group in the formula (1) are the same or different. The curable composition according to [17], which is a group containing.

(The bond extending from the phenylene group in the formula binds to the L side in the formula (1))
^{[23] The R 1-} D ¹ -group and the R ^2- D ^2- group in the formula (1) are the same or different, and are represented by the following formula (rd-1-1) or (rd-2-1). The curable composition according to [17], which is the group represented.

(The bond extending from the oxygen atom in the formula bonds with L in the formula (1))
[24] The curable composition according to any one of [17] to [23], wherein L in the formula (1) is a divalent group represented by the following formula (L-1).

(In the formula, Ar ¹ to Ar ³ are the same or different, and represent an arylene group or a group in which two or more arylene groups are bonded via a single bond or a linking group. X indicates -CO-, -S-. , Or -SO _2- , Y indicates the same or different, -S-, -SO _2- , -O-, -CO-, -COO-, or -CONH-. N "is 0 or more. Indicates an integer of, and m indicates a number from 2 to 50)
[25] Any one of [17] to [23], wherein L in the formula (1) is a divalent group represented by the following formula (L-1-1) or (L-1-2). The curable composition according to one.

(In the formula, m1 and m2 indicate numbers from 2 to 50)
[26] The curable composition according to any one of [1] to [25], wherein the curable compound has a standard polystyrene-equivalent number average molecular weight of 1000 to 15000, which is determined by GPC measurement.
[27] The curable composition according to any one of [1] to [26], wherein the glass transition temperature of the curable compound is 80 to 280 ° C.
[28] The cured product of the curable composition according to any one of [1] to [27].
[29] The semi-cured product of the curable composition according to any one of [1] to [27].
[30] A laminated body having a structure in which the cured product according to [29] is laminated on a substrate.
[31] The laminate according to [30], wherein the substrate is a copper substrate.
[32] The curable composition according to any one of [1] to [27] is applied onto a substrate and heat-treated to cure the curable composition. A method for manufacturing a laminate, which comprises producing a laminate having a structure in which a cured product of a product is laminated on a substrate.
[33] The semi-cured product of the curable composition according to any one of [1] to [27] is placed on a substrate and heat-treated to cure the semi-cured product. A method for producing a laminate, which comprises producing a laminate having a structure in which a cured product of a curable composition is laminated on a substrate.
[34] A printed circuit board having conductor wiring on the substrate, wherein the substrate is a substrate made of a cured product of the curable composition according to any one of [1] to [27].
[35] A method for manufacturing a printed circuit board having conductor wiring on a substrate, wherein the conductor wiring is formed on a substrate made of a cured product of the curable composition according to any one of [1] to [27]. A method of manufacturing a printed circuit board, which includes a step of making a printed circuit board.
[36] An electronic device having a printed circuit board, wherein the printed circuit board is provided with conductor wiring on a substrate made of a cured product of the curable composition according to any one of [1] to [27]. An electronic device that is a substrate.
[37] A method for manufacturing an electronic device including a printed circuit board, wherein the printed circuit board is provided with conductor wiring on the substrate, and the curable composition according to any one of [1] to [27]. A method for manufacturing an electronic device, which comprises a step of forming a conductor wiring on a substrate made of a cured product of an object.

The curable composition of the present disclosure can be heated to obtain a cured product having heat resistance and flexibility. Further, the cured product preferably has a low CTE and has a heat ray expansion integer comparable to that of copper. Therefore, the curable composition can be suitably used as a raw material for an electronic circuit substrate to which copper wiring is applied.

Claims (20)

1. A curable composition containing a curable compound and a silicate, wherein the content of the silicate is 0.01 to 95 parts by weight with respect to 100 parts by weight of the curable compound.
2. The curable composition according to claim 1, wherein the silicate is a flaky silicate.
3. The curable composition according to claim 1 or 2, wherein the silicate has the following properties 1 and 2.
   Characteristic 1: A PVC ring for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface is filled with silicate until the height from the upper flat surface of the vinyl chloride ring reaches 5.0 mm, and the maximum pressurization is performed. Pressurize at 7 MPa for 3 minutes to smooth the PVC ring surface, and 5 minutes after decompression, the PVC ring surface rises. Characteristic 2: Salt for powder samples with a height of 5.0 mm and a diameter of 10 mm installed on a flat surface. The billing is filled with silicate until the height from the upper plane of the vinyl chloride ring reaches 3.0 mm, and the surface of the vinyl chloride ring is smoothed by pressurizing at a maximum pressurization of 5 MPa for 3 minutes. Does not cause swelling on the surface of
4. The maximum diameter L ₁ of the silicate, the maximum diameter L ₁ diameter L ₂ and a thickness W which is orthogonal to the following formula (a), satisfies the (b), according to any one of claims 1 to 3 Curable composition.
   0.2L ₁ ≤ L ₂ ≤ L ₁ (a)
   0.001L ₁ ≤ W ≤ 0.08L ₁ (b)
5. The curable composition according to claim 1, wherein the silicate is a lipophilic silicate.
6. The curable composition according to any one of claims 1 to 5, wherein the silicate contains an alkali metal.
7. The curable composition according to any one of claims 1 to 6, wherein the magnesium content of the silicate is 10% by weight or more.
8. The curable composition according to any one of claims 1 to 7, wherein the silicate is a flaky silicate and the sodium content is less than 3.0% by weight.
9. The curable composition according to any one of claims 1 to 4, 6 to 8, wherein the silicate is a flaky silicate and the potassium content is 1.0% by weight or more.
10. The curable composition according to any one of claims 1 to 4, 6 to 9, wherein the silicate is a flaky silicate and the aluminum content is 0.5% by weight or more.
11. The curable composition according to any one of claims 1 to 10, wherein the silicate contains a fluorine atom.
12. The curable composition according to any one of claims 1 to 11, wherein the silicate is mica.
13. The curable compound has the following formula (1)
    

    

    [In the formula, R ¹ and R ² indicate the same or different curable functional groups, and D ¹ and D ² indicate the same or different single bond or linking group. L represents a divalent group having a repeating unit including a structure represented by the following formula (I) and a structure represented by the following formula (II).
    

    

    (In the formula, Ar ¹ to Ar ³ are the same or different, and represent an arylene group or a group in which two or more arylene groups are bonded via a single bond or a linking group. X indicates -CO-, -S-. , Or -SO _2- , Y indicates the same or different, -S-, -SO _2- , -O-, -CO-, -COO-, or -CONH-. N is 0 or more. Indicates an integer)]
    The curable composition according to any one of claims 1 to 12, which is a compound represented by.
14. ^{The curable composition according to claim 13, wherein R 1} and R ² in the formula (1) are the same or different curable functional groups having a cyclic imide structure.
15. ^{The thirteenth aspect of the present invention, wherein R 1} and R ² in the formula (1) are the same or different groups selected from the groups represented by the following formulas (r-1) to (r-6). Curable composition.
    

    

    (The bond extending from the nitrogen atom in the formula bonds with D ¹ or D ² )
16. A cured product of the curable composition according to any one of claims 1 to 15.
17. A semi-cured product of the curable composition according to any one of claims 1 to 15.
18. A laminated body having a structure in which the cured product according to claim 16 is laminated on a substrate.
19. The laminate according to claim 18, wherein the substrate is a copper substrate.
20. An electronic device having a printed circuit board having conductor wiring on a substrate made of a cured product of the curable composition according to any one of claims 1 to 15.

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