JPWO2020031935A1 - Curable resin mixture, curable resin composition and cured product thereof - Google Patents

Abstract

Provided is a curable resin mixture having excellent heat resistance and electrical properties, and a curable resin composition thereof. A curable resin mixture having at least one of the cyclopentadiene structures represented by the following formulas (1) to (4). [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4]

Description

TECHNICAL FIELD The present invention relates to a curable resin mixture containing a cyclopentadiene structure, a curable resin composition and a cured product thereof, and a semiconductor element sealing material, a liquid crystal display element sealing material, an organic EL element sealing material. It is preferably used for electric/electronic parts such as materials, printed wiring boards, and build-up laminated boards, and composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

2. Description of the Related Art In recent years, laminated boards on which electric/electronic components are mounted have been required to have a wide range of required characteristics due to the expansion of fields of use. The conventional semiconductor chips were mainly mounted on a metal lead frame, but recent semiconductor chips with high processing capacity such as a central processing unit (hereinafter referred to as CPU) are laminated by a polymer material. It is often mounted on a board.

In particular, in semiconductor packages (hereinafter referred to as PKG) used in smartphones and the like, in order to meet the demands for downsizing, thinning, and high density, thinning of the PKG substrate is required. As the thickness decreases, the rigidity decreases, so that heating when soldering the PKG on the motherboard (PCB) causes a large amount of warpage, which causes a problem. In order to reduce this, a PKG substrate material having a high Tg higher than the solder mounting temperature is required. In addition, in the fifth-generation communication system "5G", which is currently under development, it is expected that the capacity will be further increased and high-speed communication will be advanced. The need for low dielectric loss tangent materials is increasing, and a dielectric loss tangent of 0.005 or less at least at 1 GHz is required.

Further, in the field of automobiles, computerization has progressed, and precision electronic devices may be placed near the engine drive part, so higher levels of heat resistance and humidity resistance are required. Since SiC semiconductors have begun to be used in electric trains, air conditioners, etc., and extremely high heat resistance is required for the sealing material of semiconductor elements, so that conventional epoxy resin sealing materials cannot be used.

Under such circumstances, polymer materials capable of satisfying both heat resistance and low dielectric loss tangent properties have been studied. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenol resin. However, since the phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, it cannot be said that the electrical characteristics are sufficient.
Further, Patent Document 2 discloses an allyl ether resin in which a hydroxyl group is substituted with an allyl group. However, it has been shown that Claisen rearrangement occurs at 190° C., and at 200° C., which is a general substrate molding temperature, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so that it is considered that electrical characteristics can be satisfied. Hard to say.

JP-A-04-359911 International publication 2016/002704

The present invention has been made in view of such circumstances, and provides a curable resin mixture having excellent heat resistance and electrical characteristics and good curability, a curable resin composition, and a cured product thereof. The purpose is to

As a result of intensive studies by the present inventors to solve the above problems, a curable resin mixture containing a cyclopentadiene structure as a curable functional group exhibits good curability, and the cured product has heat resistance and electrical characteristics. They have found that they are excellent and have completed the present invention.

That is, the present invention relates to the following [1] to [13].
[1]
A curable resin mixture having at least one of the cyclopentadiene structures represented by the following formulas (1) to (4).

(In the formula (1), a plurality of A's represent a hydrogen atom or an arbitrary organic group. A plurality of R ^1's each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number 1). A halogenated alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. alkyl group having 1 to 20 carbon atoms which is substituted with a silyl group having, ^-NR _{2 2} group, -SR ² group, -OSiR ² ₃ group, or ^-PR ₂ represents a ₂ group. multiple present ^{R 2} is a hydrogen atom, It represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and a represents a natural number of 1 to 3.)

(In the formula (2), A and R ¹ have the same meanings as described above. b represents a natural number of 1 to 4.)

(In the formula (3), A and R ¹ have the same meanings as described above. c and d each represent a natural number of 1 to 4.)

(In the formula (4), a plurality of B's represent a hydrogen atom or an arbitrary organic group. A plurality of R ¹ , a, and b's have the same meanings as described above. n represents a natural number of 1 or more, and a dotted line indicates A bond may be present or may not be present. C represents any one or more of the following formula (5).)

(In the formula (5), * represents that it is bonded to a cyclopentadienyl group. Multiple R ³ , s, and t are independently present, and R ³ is a hydrogen atom, a halogen atom, or a carbon atom. A silyl group having an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. , an alkyl group having 1 to 20 carbon atoms which is substituted by a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, ^-NR _{4 2} group, -SR ⁴ group, -OSiR ⁴ ₃ group or ^-PR _{4 2} group ( R ⁴ present in plural numbers represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, s represents 1 to 7, and t represents 1 to 4. Even if dotted lines are bonded to each other to form a ring structure. Show good things.)
[2]
The curable resin mixture according to item [1], which is represented by the formulas (1) to (3) and A is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
[3]
The curable resin mixture according to item [1], which is represented by the formula (4) and B is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
[4]
The curable resin mixture according to any one of the above items [1] to [3], which is composed of only carbon atoms and hydrogen atoms.
[5]
The curable resin mixture according to any one of the above items [1] to [4], wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.1 to 1,000. ..
[6]
Hydroxyl equivalent is 125 g/eq. The curable resin mixture as described in any one of the above items [1] to [5].
[7]
The above-mentioned [1] to [6] obtained by reacting a cyclopentadiene compound represented by at least one of the following formulas (6) to (8) with an electrophile represented by the following formula (9). ] The curable resin mixture as described in any one of these.

(In the formula (6), A represents a hydrogen atom or any organic group. R ¹ and a represent the same meaning as described above.)

(In the formula (7), R ¹ and b have the same meanings as described above.)

(In the formula (8), R ¹ , c and d have the same meanings as described above.)

(In formula (9), a plurality of R ^5's are independently present and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The dotted line indicates that they may be bonded to each other to form a ring structure. .)
[8]
The above-mentioned [1] to [7] obtained by reacting a cyclopentadiene compound represented by the following formula (10) with an electrophile represented by at least one of the following formulas (11) to (13). ] The curable resin mixture as described in any one of these.

(In the formula (10), R ¹ , a and b have the same meanings as described above, and the dotted line represents that a bond may or may not be present.)

(In formula (11), a plurality of R ^{5 s} have the same meanings as described above. The dotted line indicates that they may be bonded to each other to form a ring structure.)

(In the formula (12), a plurality of R ³ , R ⁵ and t have the same meanings as described above.)

(In the formula (13), a plurality of R ³ and s have the same meanings as described above.)
[9]
A curable resin composition containing the curable resin mixture according to any one of the above items [1] to [8] and a curing agent.
[10]
The curable resin composition according to the above item [9], wherein the curing agent is an active alkene-containing resin.
[11]
The curable resin composition according to the above item [9], wherein the curing agent is a maleimide resin.
[12]
A radical polymerization initiator is further added to the curable resin mixture according to any one of the above items [1] to [8] or the curable resin composition according to any one of the above items [9] to [11]. Curable resin composition containing.
[13]
A cured product obtained by curing the curable resin composition according to any one of [9] to [12].

The curable resin mixture of the present invention has excellent curability, and the cured product has excellent heat resistance and electrical characteristics. Therefore, insulating materials for electrical and electronic parts (high reliability semiconductor encapsulation materials, etc.) and laminated boards (printed wiring boards, ball grid array (BGA) substrates, build-up boards, etc.), liquid crystal encapsulation materials, organic EL encapsulation materials. It can be used for various composite materials such as adhesives (conductive adhesives) and carbon fiber reinforced plastics (CFRP), paints, and the like.

1 shows an MS spectrum of a compound represented by the formula (16-a) obtained in Example 1 by GC-MS analysis. 1 shows an MS spectrum of a compound represented by the formula (16-b) obtained in Example 1 by GC-MS analysis. 1 shows an MS spectrum of a compound represented by the formula (17-a) obtained in Example 2 by GC-MS analysis. 1 shows an MS spectrum of a compound represented by the formula (17-b) obtained in Example 2 by GC-MS analysis. 1 shows an MS spectrum of a compound represented by the formula (18) obtained in Example 3 by GC-MS analysis. 1 shows an MS spectrum of a compound represented by the formula (19-a) obtained in Example 4 by GC-MS analysis. 1 shows an MS spectrum of a compound represented by the formula (19-b) obtained in Example 4 by GC-MS analysis. 2 shows an MS spectrum obtained by GC-MS analysis of a compound represented by the formula (20-a) obtained in Example 5. 1 shows an MS spectrum of a compound represented by the formula (20-b) obtained in Example 5 by GC-MS analysis. 1 shows an MS spectrum of a compound represented by the formula (21) obtained in Example 6 by GC-MS analysis. 2 shows an MS spectrum of a compound represented by the formula (22) obtained in Example 7 by GC-MS analysis. 8 shows an MS spectrum of a compound represented by the formula (23-a) obtained in Example 8 by GC-MS analysis. 9 shows an MS spectrum of the compound represented by the formula (23-b) obtained in Example 8 by GC-MS analysis. 1 shows a GPC spectrum of the indene-benzaldehyde resin mixture obtained in Example 1. 3 shows a GPC spectrum of the indene-acetophenone resin mixture obtained in Example 2. 3 shows a GPC spectrum of the fluorene-benzaldehyde resin mixture obtained in Example 3. 3 shows a GPC spectrum of the methylcyclopentadiene-acetophenone resin mixture obtained in Example 4. 5 shows a GPC spectrum of the indene aralkyl resin mixture obtained in Example 5. 9 shows a GPC spectrum of the indene biphenyl aralkyl resin mixture obtained in Example 6. 9 shows the GPC spectrum of the methylcyclopentadiene biphenylaralkyl fat mixture obtained in Example 7. 9 shows a GPC spectrum of the indene-benzaldehyde resin mixture obtained in Example 8.

Hereinafter, the curable resin mixture of the present invention will be described in detail. The curable resin mixture of the present invention has excellent curability, and the cured product has excellent heat resistance and electrical characteristics. Further, since it becomes a cured product having low polarity and high crosslinking, it has low water absorption, high elasticity and low thermal expansion properties. In addition, since it has a bonding group capable of relaxing stress between the crosslinked structures, it has excellent toughness.
A compound having a cyclopentadiene structure has been conventionally used for agricultural chemicals and catalysts, but has never been used as a curable resin. The present invention makes it possible to provide a curable resin mixture having a cyclopentadiene structure which is industrially applicable.

The curable resin mixture of the present invention has at least one or more of the cyclopentadiene structures represented by the following formulas (1) to (4).

(In the formula (1), a plurality of A's represent a hydrogen atom or an arbitrary organic group. A plurality of R ^1's each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number 1). A halogenated alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. alkyl group having 1 to 20 carbon atoms which is substituted with a silyl group having, ^-NR _{2 2} group, -SR ² group, -OSiR ² ₃ group, or ^-PR ₂ represents a ₂ group. multiple present ^{R 2} is a hydrogen atom, It represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and a represents a natural number of 1 to 3.)

（式（２）中、Ａ、Ｒ^１は前記と同じ意味を表す。ｂは１〜４の自然数を表す。）

(In the formula (2), A and R ¹ have the same meanings as described above. b represents a natural number of 1 to 4.)

(In the formula (3), A and R ¹ have the same meanings as described above. c and d each represent a natural number of 1 to 4.)

(In the formula (4), a plurality of B's represent a hydrogen atom or an arbitrary organic group. A plurality of R ¹ , a, and b's have the same meanings as described above. n represents a natural number of 1 or more, and a dotted line indicates A bond may be present or may not be present. C represents any one or more of the following formula (5).)

(In the formula (5), * represents that it is bonded to a cyclopentadienyl group. Multiple R ³ , s, and t are independently present, and R ³ is a hydrogen atom, a halogen atom, or a carbon atom. A silyl group having an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. , an alkyl group having 1 to 20 carbon atoms which is substituted by a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, ^-NR _{4 2} group, -SR ⁴ group, -OSiR ⁴ ₃ group or ^-PR _{4 2} group ( R ⁴ present in plural numbers represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, s represents 1 to 7, and t represents 1 to 4. Even if dotted lines are bonded to each other to form a ring structure. Show good things.)

The curable resin mixture of the present invention may have at least one or more of the cyclopentadiene structures represented by the formulas (1) to (4), and may have one kind alone or a plurality of kinds. Alternatively, it may have a component that cannot be represented by the formulas (1) to (4) generated in the synthesis process.

The curable resin mixture having the structure represented by the formulas (1) to (3) can control the crystallinity of the product and improve the solubility in a solvent, and has a low viscosity so that it has fluidity and moldability. It is preferable to have a structure represented by formula (1) or formula (2) from the viewpoint of improving the heat resistance, and it is more preferable to have a structure represented by formula (2) from the viewpoint of heat resistance and pot life. From the viewpoint of electric properties, it is preferable that the polar group is not contained, and R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and a hydrogen atom or methyl in terms of solvent solubility. More preferred are groups. A is usually a hydrogen atom or any organic group, but is preferably a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. It is particularly preferable to contain at least one hydrogen atom because the curability is improved.

The curable resin mixture having the structure represented by the formula (4) has good curability, and the cured product has excellent heat resistance and electrical characteristics. Further, since the curable resin has a low polarity and is a highly crosslinked cured product, it has low water absorption, high elasticity and low thermal expansion properties. In addition, since it has a bonding group capable of relaxing stress between the crosslinked structures, it has excellent toughness.
The curable resin mixture of the present invention may have the structure represented by the formula (4) either alone or in combination. From the viewpoint of electric properties, it is preferable that the polar group is not contained, and R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and a hydrogen atom or methyl in terms of solvent solubility. More preferred are groups. n is preferably a natural number of 1 to 100, more preferably a natural number of 1 to 50, and particularly preferably 1 to 10. The bonding group is not particularly limited as long as it has the structure represented by the formula (5), but it is preferable to contain an aralkyl structure from the viewpoint of electrical characteristics and toughness. B is usually a hydrogen atom or any organic group, but is preferably a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms is particularly preferable. R ³ is preferably a hydrogen atom or an alkyl group having a prime number of 1 to 10.

The curable resin mixture of the present invention can be synthesized by a known method. A method of reacting a cyclopentadiene compound with an electrophile is preferably used.
In the curable resin mixture having the structure represented by the formulas (1) to (3), the cyclopentadiene compound is at least one of the compounds represented by the following formulas (6) to (8).

(In the formula (6), A represents a hydrogen atom or any organic group. R ¹ and a represent the same meaning as described above.)

(In the formula (7), R ¹ and b have the same meanings as described above.)

(In the formula (8), R ¹ , c and d have the same meanings as described above.)

As the compounds represented by the formulas (6) to (8), any raw materials may be used, and only one kind may be used, or two or more kinds may be used in combination. Specifically, the compounds listed below can be exemplified, but not limited thereto.

Examples of the compound represented by the formula (6) include 1,3-cyclopentadiene, 1-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclopentadiene, 1,2,3,4-tetra Examples include methyl-1,3-cyclopentadiene and 1,2,3,4,5-pentamethyl-1,3-cyclopentadiene.

Examples of the compound represented by the formula (7) include indene, 2-methylindene, 3-methylindene, 4-methylindene, 5-methylindene, 6-methylindene, 7-methylindene, 2-ethylindene, and 3 -Ethylindene, 4-ethylindene, 5-ethylindene, 6-ethylindene, 7-ethylindene, 2,3-dimethylindene, 2,4-dimethylindene, 2,6-dimethylindene, 2,7-dimethyl Indene, 3,4-dimethylindene, 3,5-dimethylindene, 3,6-dimethylindene, 3,7-dimethylindene, 4,5-dimethylindene, 4,6-dimethylindene, 4,7-dimethylindene , 5,6-dimethylindene, 5,7-dimethylindene, 6,7-dimethylindene, 4,5,6,7-tetramethylindene, 2-ethenylindene, 3-ethenylindene, 5-ethenylindene, 4-ethynylindene , 6-ethynylindene, 2-propylindene 3-propylindene, 5-propylindene, 7-propylindene, 2-isopropylindene, 3-isopropylindene, 4-isopropylindene, 5-isopropylindene, 7-isopropylindene, 2-tert-butyl indene, 3-tert-butyl indene, 4-tert-butyl indene, 6-tert-butyl indene, 2-(2-methylpropl)indene, 5-(2-methylpropl)indene, 2-(1 -Methylethenyl)indene, 3-(1-methylethenyl)indene, 2-allylindene, 2-ethyl-4-methylindene, 4-ethyl-2-methylindene, 4-phenylindene, 6-phenylindene, 2-hydroxy Indene, 3-hydroxyindene, 4-hydroxyindene, 5-hydroxyindene, 6-hydroxyindene, 7-hydroxyindene, 2-aminoindene, 4-aminoindene, 5-aminoindene, 6-aminoindene, 7-amino Indene, 2-bromoindene, 4-bromoindene, 5-bromoindene, 6-bromoindene, 7-bromoindene, 2-chloroindene, 4-chloroindene, 5-chloroindene, 6-chloroindene, 3-fluoro Indene, 4-fluoroindene, 5-fluoroindene, 6-fluoroindene, 2-iodoindene, 6-iodoindene, 2-phosphanylindene, 6-thio- Ruindene, 1H-indene-2-methanamine, 1H-indene-3-methanamine, 1H-indene-4-methanamine, 1H-indene-5-methanamine, 1H-indene-6-methanamine, 1H-indene-7-methanamine, 1H-indene-2-carbonitrile, 1H-indene-3-carbonitrile, 1H-indene-4-carbonitrile, 1H-indene-5-carbonitrile, 1H-indene-7-carbonitrile, 1H-indene-2 -Carbaldehyde, 1H-indene-4-carbaldehyde, 1H-indene-5-carbaldehyde, 1H-indene-6-carbaldehyde, 1H-indene-7-carbaldehyde, 1H-indene-2-methanol, 1H -Indene-3-methanol, 1H-indene-4-methanol, 1H-indene-5-methanol, 2-bromomethylindene, 3-bromomethylindene, 4-bromomethylindene, 6-bromomethylindene, 7-Bromomethylindene, 2-chloromethylindene, 3-chloromethylindene, 2-fluoromethylindene, 4-methoxyindene, 5-methoxyindene, 6-methoxyindene, 2-methyl-6-aminoindene, 4- Examples include hydroxy-6-methylindene and 5-bromo-2-methylindene.

As the compound represented by the formula (8), fluorene, 1-methylfluorene, 2-methylfluorene, 3-methylfluorene, 4-methylfluorene, 1,6-dimethylfluorene, 1,7-dimethylfluorene, 1, 8-dimethylfluorene, 2,3-dimethylfluorene, 2,5-dimethylfluorene, 2,6-dimethylfluorene, 2,7-dimethylfluorene, 3,6-dimethylfluorene, 4,5-dimethylfluorene, 1-ethyl Fluorene, 2-ethylfluorene, 3-ethylfluorene, 4-ethylfluorene, 1-hydroxyfluorene, 2-hydroxyfluorene, 3-hydroxyfluorene, 4-hydroxyfluorene, 1-aminofluorene, 2-aminofluorene, 3-amino Fluorene, 4-aminofluorene, 2-thiolfluorene, 2-ethynylfluorene, 3-ethynylfluorene, 2-ethenylfluorene, 2-fluorofluorene, 3-fluorofluorene, 4-fluorofluorene, 2-chlorofluorene, 3- Examples include chlorofluorene, 4-chlorofluorene, 2-bromofluorene, 3-bromofluorene, 4-bromofluorene, 2-iodofluorene, 3-iodofluorene, 4-iodofluorene and 2-cyanofluorene.

Of the cyclopentadiene compounds, 1,3-cyclopentadiene, 1-methyl-1,3-cyclopentadiene, indene and fluorene are preferable from the viewpoint of solubility and viscosity reduction, in order to obtain heat resistance and sufficient pot life. Is more preferably indene.

In the curable resin mixture having the structure represented by formula (1) to formula (3), the electrophile is a compound represented by the following formula (9).

(In formula (9), a plurality of R ^5's are independently present and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The dotted line indicates that they may be bonded to each other to form a ring structure. .)

The electrophile may be used alone or in combination of two or more. Specifically, the compounds listed below can be exemplified, but not limited thereto.

Electrophiles include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chlorbenzaldehyde, brombenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelinaldehyde, sebacine. Aldehydes such as aldehydes, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, furfural, tolualdehyde, α-naphthaldehyde, β-naphthaldehyde, acetone, methyl ethyl ketone, diethyl ketone, benzyl, acetyl acetone, methyl isopropyl ketone, Methyl isobutyl ketone, acetophenone, ethyl phenyl ketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone, 4-hydroxyacetophenone, acenaphthenequinone, quinone, benzoylacetone, adamantaneone , And diacetyl.

Of the electrophiles, formaldehyde, acetaldehyde, benzaldehyde, acetone, methyl ethyl ketone, acetophenone, cyclohexanone, cyclopentanone, and benzophenone are preferable in terms of heat resistance, and benzaldehyde, acetophenone, and benzophenone are more preferable from the viewpoint of obtaining a low-viscosity material by reaction control. preferable.

In the curable resin mixture having the structure represented by the formula (4), any material may be used as the cyclopentadiene compound as long as it is a known compound represented by the following formula (10), and only one kind is used. Alternatively, two or more kinds may be used in combination.

(In the formula (10), R ¹ , a and b have the same meanings as described above, and the dotted line represents that a bond may or may not be present.)

Specific examples of the compound represented by the formula (10) include 1,3-cyclopentadiene, 1-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclopentadiene, 1,2,3. 4-tetramethyl-1,3-cyclopentadiene, 1,2,3,4,5-pentamethyl-1,3-cyclopentadiene, indene, 2-methylindene, 3-methylindene, 4-methylindene, 5- Methylindene, 6-methylindene, 7-methylindene, 2-ethylindene, 3-ethylindene, 4-ethylindene, 5-ethylindene, 6-ethylindene, 7-ethylindene, 2,3-dimethylindene, 2,4-dimethylindene, 2,6-dimethylindene, 2,7-dimethylindene, 3,4-dimethylindene, 3,5-dimethylindene, 3,6-dimethylindene, 3,7-dimethylindene, 4 ,5-Dimethylindene, 4,6-dimethylindene, 4,7-dimethylindene, 5,6-dimethylindene, 5,7-dimethylindene, 6,7-dimethylindene, 4,5,6,7-tetra Methylindene, 2-ethenylindene, 3-ethenylindene, 5-ethenylindene, 4-ethynylindene, 6-ethynylindene, 2-propylindene 3-propylindene, 5-propylindene, 7-propylindene, 2-isopropylindene, 3 -Isopropylindene, 4-isopropylindene, 5-isopropylindene, 7-isopropylindene, 2-tert-butylindene, 3-tert-butylindene, 4-tert-butylindene, 6-tert-butylindene, 2-( 2-methylpropyl)indene, 5-(2-methylpropyl)indene, 2-(1-methylethenyl)indene, 3-(1-methylethenyl)indene, 2-allylindene, 2-ethyl-4-methylindene, 4-ethyl 2-methylindene, 4-phenylindene, 6-phenylindene, 2-hydroxyindene, 3-hydroxyindene, 4-hydroxyindene, 5-hydroxyindene, 6-hydroxyindene, 7-hydroxyindene, 2-aminoindene , 4-aminoindene, 5-aminoindene, 6-aminoindene, 7-aminoindene, 2-bromoindene, 4-bromoindene, 5-bromoindene, 6-bromoindene, 7-bromoindene, 2-ku Loroindene, 4-chloroindene, 5-chloroindene, 6-chloroindene, 3-fluoroindene, 4-fluoroindene, 5-fluoroindene, 6-fluoroindene, 2-iodoindene, 6-iodoindene, 2-phos Fanylindene, 6-thiolindene, 1H-indene-2-methanamine, 1H-indene-3-methanamine, 1H-indene-4-methanamine, 1H-indene-5-methanamine, 1H-indene-6-methanamine, 1H- Indene-7-methanamine, 1H-indene-2-carbonitrile, 1H-indene-3-carbonitrile, 1H-indene-4-carbonitrile, 1H-indene-5-carbonitrile, 1H-indene-7-carbonitrile 1H-indene-2-carbaldehyde, 1H-indene-4-carbaldehyde, 1H-indene-5-carbaldehyde, 1H-indene-6-carbaldehyde, 1H-indene-7-carbaldehyde, 1H-indene- 2-methanol, 1H-indene-3-methanol, 1H-indene-4-methanol, 1H-indene-5-methanol, 2-bromomethylindene, 3-bromomethylindene, 4-bromomethylindene, 6-bromomethylindene, 7-bromomethylindene, 2-chloromethylindene, 3-chloromethylindene, 2-fluoromethylindene, 4-methoxyindene, 5-methoxyindene, 6-methoxyindene, 2-methyl-6 -Aminoindene, 4-hydroxy-6-methylindene, and 5-bromo-2-methylindene.

Among the cyclopentadiene compounds, 1,3-cyclopentadiene and indene are preferable because they have few polar groups and motile alkyl groups and excellent electrical characteristics are obtained, and indene is more preferable because heat resistance is obtained.

In the curable resin mixture having the structure represented by the formula (4), the electrophile is represented by any one of the following formulas (11) to (13), and even if only one type is used, two or more types are used. You may use together.

(In formula (11), a plurality of R ^{5 s} have the same meanings as described above. The dotted line indicates that they may be bonded to each other to form a ring structure.)

(In the formula (12), a plurality of R ³ , R ⁵ and t have the same meanings as described above.)

(In formula (13), a plurality of R ^3's have the same meanings as described above, and s represents 1 to 7.)

Specific examples of the electrophile represented by any of the formulas (11) to (13) include the compounds listed below, but the electrophilic reagent is not limited thereto.

Examples of the compound represented by the formula (11) include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chlorbenzaldehyde, brombenzaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipinealdehyde. , Pimelinaldehyde, sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, furfural, tolualdehyde, α-naphthaldehyde, β-naphthaldehyde and other aldehydes, acetone, methyl ethyl ketone, diethyl ketone, benzyl, Acetylacetone, methylisopropylketone, methylisobutylketone, acetophenone, ethylphenylketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone, 4-hydroxyacetophenone, acenaphthenequinone, quinone , Benzoylacetone, adamantane, and diacetyl.

Examples of the compound represented by the formula (12) include o-dichloromethylbenzene, o-dibromomethylbenzene, o-xylylene glycol, o-dimethoxymethylbenzene, m-dichloromethylbenzene, m-dibromomethylbenzene and m-. Xylylene glycol, m-dimethoxymethylbenzene, p-dichloromethylbenzene, p-dibromomethylbenzene, p-xylylene glycol, p-dimethoxymethylbenzene, 2,2'-dichloromethyldiphenyl, 2,2'-dibromomethyl Diphenyl, 2,2'-dimethoxymethyldiphenyl, 2,2'-dimethyloldiphenyl, 2,4'-dichloromethyldiphenyl, 2,4'-dibromomethyldiphenyl, 2,4'-dimethoxymethyldiphenyl, 2,4 '-Dimethyloldiphenyl, 3,3'-dichloromethyldiphenyl, 3,3'-dibromomethyldiphenyl, 3,3'-dimethoxymethyldiphenyl, 3,3'-dimethyloldiphenyl, 4,4'-dichloromethyldiphenyl , 4,4'-dibromomethyldiphenyl, 4,4'-dimethoxymethyldiphenyl, 4,4'-dimethyloldiphenyl, 3,3',4,4'-tetrachloromethyldiphenyl, 3,3',4 4'-tetrabromomethyldiphenyl, 3,3',4,4'-tetramethoxymethyldiphenyl, 3,3',4,4'-tetramethyloldiphenyl, 3,3',5,5'-tetrachloromethyl Diphenyl, 3,3′,5,5′-tetrabromomethyldiphenyl, 3,3′,5,5′-tetramethoxymethyldiphenyl, 3,3′,5,5′-tetramethyloldiphenyl, 3,3′ ,5,5'-Tetrachloromethyl-4,4'-dihydroxydiphenyl, 3,3',5,5'-tetrabromomethyl-4,4'-dihydroxymethyldiphenyl, 3,3',5,5' -Tetramethoxymethyl-4,4'-dihydroxydiphenyl and 3,3',5,5'-tetramethylol-4,4'-dihydroxymethyldiphenyl.

Examples of the compound represented by the formula (13) include cyclopentadiene, 1-methylcyclopentadiene, and 3,9-dimethyltricyclodeca-3,8-diene.

From the viewpoint of heat resistance and electric properties, as the electrophile, formaldehyde, acetone, benzaldehyde, acetophenone, p-dichloromethylbenzene and 4,4′-dichloromethyldiphenyl are preferable, and p-dichloromethylbenzene and 4,4′- Dichloromethyldiphenyl is especially preferred.

When the cyclopentadiene compound and the electrophile are reacted in the curable resin composition of the present invention, a catalyst may be added. The catalyst to be used is not particularly limited, but in the case of an acidic catalyst, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropoly acid such as tungstic acid, activated clay, inorganic acid , Known acid catalysts such as stannic chloride, zinc chloride, ferric chloride, and other organic and inorganic acid salts showing acidity. In the case of basic catalysts, lithium hydroxide, sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, magnesium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, sodium methoxide, sodium ethoxide, Examples thereof include alkali metal alkoxides such as potassium methoxide, potassium ethoxide and potassium-tert-butoxide, and alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide. Further, an amine-based catalyst can be used, and examples thereof include triethylamine, ethanolamine, pyridine, piperidine, and morpholine. Especially when an amine-based catalyst is used, it can also serve as a solvent. These catalysts may be used alone or in combination of two or more. A basic catalyst is also preferably used to generate a cyclopentadienyl anion and accelerate the reaction of the electrophile. The amount of the catalyst used is usually in the range of 0.001 to 10 times mol, preferably 0.01 to 2 times mol, of the cyclopentadiene compound. When the catalyst is used as a solvent, it is preferably added in an amount of about 10 to 200% by mass based on the cyclopentadiene compound.

In the reaction for obtaining the curable resin mixture of the present invention, a solvent may be used if necessary. As the solvent that can be used, known solvents such as ketones, alcohols, aprotic polar solvents, and aromatic hydrocarbons can be used, but they must not be reactive with cyclopentadiene compounds and electrophiles. Therefore, aprotic polar solvents and aromatic hydrocarbons are preferable. Aromatic hydrocarbons are more preferable in view of the fact that the resin having a fulvenyl group has low polarity and thus the generated resin is easily dissolved.

The amount of the solvent used is not particularly limited, but for example, it can be used in an amount of 10 to 1000% by mass based on the cyclopentadiene compound.
The reaction temperature is usually 0 to 200°C, preferably 30 to 180°C, and it is particularly preferable to react at 50°C to 150°C. The reaction time is usually 0.5 to 20 hours, but it is not limited to this because the reactivity varies depending on the kind of the raw material compound.

In order to obtain the curable resin mixture of the present invention, after completion of the reaction of the cyclopentadiene compound and the electrophile, the reaction may proceed at a high temperature as a second step. By carrying out the high temperature reaction, polar groups such as a hydroxyl group and a halogen group contained in the reaction intermediate of the cyclopentadiene compound and the electrophile are eliminated, and electrical characteristics and water absorption can be reduced, and heat resistance can be improved. it can. The high temperature reaction in the second stage is preferably performed at 80°C to 200°C. At this time, it is preferable to remove water by-produced by azeotropic distillation or the like in order to complete the reaction. If it is lower than 80° C., the reaction may not be completed, and if it is higher than 200° C., there is a concern that self-polymerization of the curable resin mixture may occur.

When the cyclopentadiene compound is not completely consumed, the reaction efficiency may be improved by adding an electrophile. When performing any reaction, the reaction temperature is usually 0 to 200° C., preferably 30 to 180° C., and it is particularly preferable to react at 50° C. to 150° C. The reaction time is usually 0.5 to 20 hours, but it is not limited to this because the reactivity varies depending on the kind of the raw material compound.

When the reaction is not completed at high temperature, the reaction solution may be neutralized with an acidic compound, and the reaction may be carried out under acidic conditions. By carrying out the reaction under acidic conditions, it is possible to further reduce the hydroxyl groups remaining in the fulvenyl group-containing resin. Specific examples of acidic catalysts that can be used include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropolyacids such as tungstic acid, activated clay, inorganic acids and stannic chloride. , Known acid catalysts such as zinc chloride, ferric chloride, and other organic or inorganic acid salts showing acidity. These catalysts may be used alone or in combination of two or more. Although the amount of the catalyst used depends on the pH in the reaction in the first step, it is usually added in an amount of 0.001 to 10 times mol, preferably 0.01 to 2 times mol, relative to the neutralized cyclopentadiene compound. To use. The reaction temperature is usually 0 to 200°C, preferably 30 to 180°C, and it is particularly preferable to react at 50°C to 150°C. The reaction time is usually 0.5 to 20 hours, but it is not limited to this because the reactivity varies depending on the kind of the raw material compound.

After completion of the reaction, the catalyst is neutralized with acid or base. The neutralizing agent is not particularly limited, but in the case of acid, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropoly acid such as tungstic acid, activated clay, inorganic acid , Stannic chloride, zinc chloride, ferric chloride, etc., and other organic and inorganic acid salts showing acidity. In the case of base, sodium hydroxide, sodium carbonate, 5 sodium tripolyphosphate, ammonia, etc. are exemplified. To be done. At this time, in order to uniformly disperse the neutralizing agent, it is preferable to gradually add it as an aqueous solution.

The curable resin mixture of the present invention can also be precipitated as crystals by a known method such as dropping a reaction liquid in a large amount of water, but in the present invention, the reaction product is heated under reduced pressure after or without water washing. From the viewpoint of simplicity, stability, yield, cost, etc., it is preferable to use a method in which unreacted substances, a solvent and the like can be taken out as a resin by removing from the reaction solution.

Since the curable resin mixture of the present invention has a molecular weight distribution, it has no crystal structure. Many of the compounds having a cyclopentadienyl group, which have been conventionally used for agricultural chemicals and catalysts, have a crystal structure, and therefore have poor solvent solubility and difficulty in handling. Since the resin mixture does not have a crystal structure but becomes liquid or semi-solid, it is easy to handle.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the curable resin mixture of the present invention is usually 1.1 to 1,000, preferably 1.2 to 100. , And more preferably 1.5 to 50. Since the mother skeleton is bonded to the curable resin mixture having a molecular weight distribution within the above range, it has high heat resistance and can reduce volatilization at high temperatures. In addition, the toughness is improved, and further, the crystallinity can be reduced to contribute to the improvement of the solvent solubility.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured by gel permeation (GPC) analysis.

The curable resin mixture of the present invention can be represented by the following reaction formula.

(In the above reaction formula, a plurality of R ^5's have the same meanings as described above. The dotted line indicates that they may be bonded to each other to form a ring structure.)

As shown in the above reaction formula, the reaction intermediate and the by-product contain a hydroxyl group, which tends to deteriorate the electrical characteristics. Since the polarity in the molecule is reduced and the electrical properties and low water absorption properties are improved, the hydroxyl equivalent is usually 125 g/eq. Or more, preferably 500 g/eq. Or more, more preferably 1,500 g/eq. That is all.

In the step of obtaining the curable resin mixture represented by Formula (1) to Formula (3) of the present invention, as a cyclopentadiene compound, a compound represented by Formula (4) or Formula (5), and an electrophile When a compound represented by the following formula (14) is used, a compound represented by the following formula (15) is produced.

(In the formula (14), R ⁵ has the same meaning as described above. A plurality of R ⁶ and e are independently present, and R ⁶ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Fluoroalkyl group, aryl group having 6 to 20 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, alkylaryl having 7 to 40 carbon atoms Group or an arylalkenyl group having 8 to 40 carbon atoms, and e represents a natural number of 1 to 4.)

(In the formula (15), R ¹ , R ⁵ , R ⁶ , b, and e have the same meanings as described above. The dotted line indicates that a bond may or may not be present.)

By including the compound represented by the formula (15), the conjugated system is expanded to the entire molecule, and thus the absorption wavelength can be increased. In the thin-layer substrate, the energy of h-line and i-line used for photo-curing the resist mounted on the surface can be absorbed, so that the influence on the back-side resist can be reduced and the productivity can be improved.

The curable resin composition of the present invention may contain a curing agent. As the curing agent, any known material may be used as long as it is a compound capable of reacting with the curable resin mixture of the present invention. Specific examples thereof include phenol resin, epoxy resin, amine resin, propenyl resin, methallyl resin, isocyanate resin, cyanate ester resin, active alkene-containing resin, polyamide resin, and polyimide resin. be able to. These curing agents may be used alone or in combination of two or more.

Phenolic resins include phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl Polycondensation products with aldehydes, benzaldehydes, alkyl-substituted benzaldehydes, hydroxybenzaldehydes, naphthaldehydes, glutaraldehydes, phthalaldehydes, crotonaldehydes, cinnamaldehydes, furfurals, etc., phenols and various diene compounds (dicyclopentadiene, terpenes, vinyl) Polymers of cyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.) A polycondensation product with, phenols and substituted biphenyls (4,4′-bis(chloromethyl)-1,1′-biphenyl and 4,4′-bis(methoxymethyl)-1,1′-biphenyl, etc.), Alternatively, a phenol resin obtained by polycondensation with substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), Examples thereof include polycondensates of bisphenols and various aldehydes, and polyphenylene ether.

As the epoxy resin, the above-mentioned phenol resin, glycidyl ether-based epoxy resin obtained by glycidylating alcohols, 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexylmethyl-3,4′-epoxycyclohexanecarboxylate Examples thereof include alicyclic epoxy resins represented by the above, glycidylamine-based epoxy resins represented by tetraglycidyldiaminodiphenylmethane (TGDDM), triglycidyl-p-aminophenol, and the like, and glycidyl ester-based epoxy resins.

As the amine resin, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac, orthoethylaniline novolac, aniline resin obtained by reaction of aniline and xylylene chloride, aniline and substituted biphenyls (4,4' -Bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1 , 4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene).

As the isocyanate resin, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene Aromatic diisocyanates such as diisocyanates; Isophorone diisocyanates, hexamethylene diisocyanates, 4,4'-dicyclohexylmethane diisocyanates, hydrogenated xylene diisocyanates, norbornene diisocyanates, lysine diisocyanates, and other aliphatic or alicyclic diisocyanates; one of the isocyanate monomers Examples include polyisocyanates such as burettes of more than one kind or isocyanates obtained by trimerizing the above diisocyanate compound; and polyisocyanates obtained by urethanization reaction of the above isocyanate compound and a polyol compound.

Examples of the cyanate ester resin include a cyanate ester compound obtained by reacting a phenol resin with a cyanogen halide.

Examples of the active alkene-containing resin include a polycondensation product of the above-mentioned phenol resin and an active alkene-containing halogen compound (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, allyl chloride, etc.), and active alkene-containing phenols ( 2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc. and halogen compounds (4,4′-bis(methoxymethyl)-1,1′-biphenyl, 1 , 4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.) polycondensate, epoxy resin or alcohol Alternatively, polycondensates of unsubstituted acrylates (acrylates, methacrylates, etc.), maleimide resins (4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2′-bis[4-( 4-maleimidophenoxy)phenyl]propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4′-diphenyl ether Examples thereof include bismaleimide, 4,4′-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and 1,3-bis(4-maleimidophenoxy)benzene.

Examples of the polyamide resin include amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanelactam, ω-laurolactam) and “diamines”. (Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, Aliphatic diamines such as hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane; cyclohexanediamine, bis- Alicyclic diamines such as (4-aminocyclohexyl)methane and bis(3-methyl-4-aminocyclohexyl)methane; aromatic diamines such as xylylenediamine and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid) Acids, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid Aromatic dicarboxylic acids such as acids, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters of these dicarboxylic acids, and mixtures with dichloride) A polymer obtained by using at least one selected as a main raw material can be mentioned.

Examples of the polyimide resin include the above-mentioned diamine and tetracarboxylic dianhydride (4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3- Methyl-cyclohexene-1,2 dicarboxylic acid anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride Anhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl Sulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'- Diphthalic acid dianhydride, 2,2'-propylidene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4 '-Diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4'-oxydiphthalic acid Acid dianhydride, thio-4,4′-diphthalic acid dianhydride, sulfonyl-4,4′-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4 -Dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4) -Dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl ] Propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3- Bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 1,2 ,5,6-Naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7 ,8-Phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride ), cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3′, 4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2) -Dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1) ,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2) -Dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride , Bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,2] 1] Octane-2,4-dione-6-spiro-3′-(tetrahydrofuran-2′,5′-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3 ,4-Tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4′-biphenylbis (trimellitic acid monoester acid anhydride) , 9,9′-bis(3,4-dicarboxyphenyl)fluorene dianhydride).

The curable resin composition of the present invention preferably contains an epoxy resin, a cyanate ester resin, and an active alkene-containing resin from the viewpoint of the balance of heat resistance, adhesion and dielectric properties. In order to further improve heat resistance, it is particularly preferable to use a maleimide resin. By containing the curing agent, the brittleness of the cured product and the adhesion to the metal can be improved, and the crack of the package in the reliability test such as the solder reflow or the heat cycle can be suppressed. In particular, when an active alkene-containing resin containing an active alkene such as a maleimide resin or an acrylate resin is contained as a curing agent, a cyclopentadienyl group-containing resin and a low-polarity and uniform cured product are easily obtained, and dielectric properties and toughness Excellent in terms of aspect.

The amount of the curing agent used is usually 10 times or less, preferably 5 times or less, more preferably 3 times or less the mass of the addition amount of the curable resin mixture of the present invention. When the amount of the curing agent used is 10 times or more, the concentration of the curable resin mixture of the present invention becomes low, and sufficient heat resistance and dielectric properties may not be obtained.

In the curable resin composition of the present invention, radical polymerization initiation in order to react fulvenyl groups of the curable resin mixture of the present invention with each other, or an active alkene selected from a fulvenyl group and a maleimide group, an acrylate group, a propenyl group, or the like. It is preferable to use agents. Examples of the radical polymerization initiator that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis-(t-butylperoxy). Isopropyl)-benzene and other dialkyl peroxides, t-butyl peroxybenzoate, 1,1-di-t-butyl peroxycyclohexane and other peroxy ketals, α-cumyl peroxyneodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy Alkyl peresters such as benzoate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyisopropyl carbonate, 1,6-bis(t-butyl percarbonate) Peroxycarbonates such as (oxycarbonyloxy)hexane, organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate and lauroyl peroxide, and azobisisobutyronitrile, 4 , 4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile) and other known accelerating accelerators for azo compounds are mentioned, but are not particularly limited thereto. Not a thing. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates and the like are preferable, and dialkyl peroxides are more preferable. The addition amount of the radical polymerization initiator is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the curable resin composition. When the amount of the radical polymerization initiator used is large, the molecular weight does not extend sufficiently during the polymerization reaction.

If necessary, a curing accelerator (curing catalyst) may be used in combination with the curable resin composition of the present invention. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo( 5,4,0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl Quaternary ammonium salt such as ammonium hydroxide, quaternary phosphonium salt such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutylphosphonium salt (the counter ion of the quaternary salt is halogen, Organic acid ions, hydroxide ions, etc. are not particularly specified, but organic acid ions and hydroxide ions are particularly preferable.), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behen). Examples thereof include transition metal compounds (transition metal salts) such as zinc compounds such as zinc acid salt, zinc mistylate) and zinc phosphate ester (zinc octyl phosphate, zinc stearyl phosphate, etc.). The curing accelerator may be used in an amount of 0.01 to 5.0 parts by weight based on the epoxy resin 100, if necessary.

The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reaction type or an addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylene bis( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylene bis(dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Examples include phosphanes such as -10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and red phosphorus. Acid esters and phosphanes are preferable, 1,3-phenylene bis(dixylylenyl phosphate), 1,4-phenylene bis(dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) Is particularly preferable. The content of the phosphorus-containing compound is preferably phosphorus-containing compound/curable resin composition=0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it is more than 0.6, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

Further, an antioxidant may be added to the curable resin composition of the present invention, if necessary. Examples of the antioxidant that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. The antioxidants may be used alone or in combination of two or more. The amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component in the curable resin composition of the present invention. Is.

Examples of antioxidants include phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like. Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3. ,5-Di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)- Monophenols such as 6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine and 2,4-bis[(octylthio)methyl]-o-cresol; 2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol) ), 4,4′-butylidene bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6 -Hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzyl Phosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl] 2,4,8 ,10-Tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl-4-hydroxybenzylsulfonate)calcium and other bisphenols; 1,1,3-tris(2-methyl) -4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[ Methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl) Butyric acid]glycol ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-iso Cyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocophenol Polymeric phenols such as
Specific examples of the sulfur antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like. ..

Specific examples of phosphorus-based antioxidants include triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris(nonylphenyl)phosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t- Butylphenyl)phosphite, cyclic neopentanetetraylbis(octadecyl)phosphite, cyclic neopentanetetraylbi(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbi(2,4) Phosphites such as -di-t-butyl-4-methylphenyl)phosphite and bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogenphosphite 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa- Examples thereof include 10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and other oxaphosphaphenanthrene oxides.
These antioxidants can be used alone, but two or more kinds may be used in combination. Particularly, phosphorus-based antioxidants are preferable in the present invention.

Further, a light stabilizer may be added to the curable resin composition of the present invention, if necessary. As the light stabilizer, a hindered amine-based light stabilizer, particularly HALS, is suitable. The HALS is not particularly limited, but a typical one is dibutylamine.1,3,5-triazine.N,N'-bis(2,2,6,6-tetramethyl-4-). Polycondensate of piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy succinate -2,2,6,6-Tetramethylpiperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], bis(1,2,2,2) 6,6-Pentamethyl-4-piperidyl) [{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butyl malonate, bis(2,2,6,6-tetramethyl -4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), and the like. HALS may be used alone or in combination of two or more.

Furthermore, the curable resin composition of the present invention may contain a binder resin, if necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, and silicone resin. , But is not limited to these. The content of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the resin component. Parts by weight are used as needed.

Further, the curable resin composition of the present invention contains fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, if necessary. , Aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or a spherical or crushed inorganic filler. You can Further, particularly when a curable resin composition for semiconductor encapsulation is obtained, the amount of the above-mentioned inorganic filler used is usually 80 to 92% by mass, preferably 83 to 90% by mass in the curable resin composition. is there.

Known additives can be added to the curable resin composition of the present invention, if necessary. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and filling such as silane coupling agent. Examples include surface treatment agents for materials, release agents, colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The blending amount of these additives is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less with respect to 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention may be made into a varnish composition (hereinafter simply referred to as varnish) by adding an organic solvent. By the addition of a solvent, the viscosity of the curable resin composition at the time of preparation tends to be lowered, the handling property is improved, and the impregnating property into a substrate such as glass cloth tends to be further improved. Examples of the solvent used include amide solvents such as γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, and tetramethylene sulfone. Sulfones, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone Examples of the solvent include aromatic solvents such as toluene and xylene. Further, when the laminated plate is produced, if the boiling point of the solvent used is too high, it may remain as a residual solvent. The boiling point of the solvent used is preferably 200° C. or lower, more preferably 180° C. or lower. The solvent is used in such a range that the solid content concentration excluding the solvent in the obtained varnish is usually 10 to 80% by mass, preferably 20 to 70% by mass.

The method for preparing the curable resin composition of the present invention is not particularly limited, but each component may be uniformly mixed or prepolymerized. For example, the fulvenyl group-containing compound used in the present invention is prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, in addition to the curable resin mixture of the present invention, an epoxy resin and, if necessary, a curing agent such as an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin and an acid anhydride compound, and other additives are added to the prepolymer. It may be polymerized. In the absence of a solvent, for example, an extruder, a kneader, a roll, or a planetary mixer is used for mixing or prepolymerization of each component, and in the presence of a solvent, a reaction kettle equipped with a stirrer is used.

When using a kneader, roll, or planetary mixer for uniform mixing, the mixture is kneaded at a temperature within the range of 50 to 100° C. so that a uniform resin composition is obtained. The obtained resin composition is crushed and then molded into a cylindrical tablet shape by a molding machine such as a tablet machine, or a granular powder or a powdered molded body, or these compositions are placed on a surface support. A curable resin composition molding can be obtained by melting and molding into a sheet having a thickness of 0.05 mm to 10 mm. The obtained molded product becomes a non-sticky molded product at 0 to 20° C., and even if it is stored at −25 to 0° C. for 1 week or more, the fluidity and the curability are hardly reduced.

The obtained molded body can be molded into a cured product by a transfer molding machine or a compression molding machine. In order to completely cure the molded product, heat of 65 to 300°C, preferably 100 to 270°C, more preferably 120 to 240°C may be applied.

The curable resin composition of the present invention can be heat-melted to lower the viscosity and impregnated with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include, for example, glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, and further inorganic fibers other than glass and poly fibers. Paraphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), wholly aromatic polyamide, polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fiber, but are not particularly limited thereto. Not done. The shape of the base material is not particularly limited, and examples thereof include woven cloth, non-woven cloth, roving, and chopped strand mat. Further, as the weaving method of the woven cloth, a plain weave, a satin weave, a twill weave, etc. are known and can be appropriately selected from these known ones depending on the intended use and performance. Further, a woven fabric which is subjected to an opening treatment and a glass woven fabric whose surface is treated with a silane coupling agent or the like are preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Further, a prepreg can be obtained by impregnating the varnish with a reinforcing fiber and heating and drying.

When used as a laminated plate, it is provided with one or more of the above prepregs. The laminated plate is not particularly limited as long as it has at least one prepreg, and may have any other layer. As a method for manufacturing the laminated plate, a generally known method can be appropriately applied and is not particularly limited. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used at the time of forming the metal foil-clad laminate, and the prepregs are laminated to each other, and the laminate is formed by heat and pressure molding. Obtainable. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300°C, more preferably 120 to 270°C. Further, the pressure to be applied is not particularly limited, but if the pressure is too large, it is difficult to adjust the solid content of the resin of the laminated plate and the quality is not stable. Since it becomes worse, 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable. The laminated board of the present embodiment can be suitably used as a metal foil-clad laminated board described later by including a layer made of a metal foil.

By cutting the above prepreg into a desired shape and, if necessary, laminating with a copper foil or the like, by heating and curing the curable resin composition while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. A laminated board for electric/electronics (printed wiring board) and a carbon fiber reinforced material can be obtained.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials and paints. In particular, the cured product of the curable resin mixture containing the cyclopentadiene structure of the present invention exhibits excellent heat resistance and dielectric properties. Therefore, a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, a sealing material for organic EL elements. It is preferably used for electric/electronic parts such as materials, printed wiring boards, and build-up laminated boards, and composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

The curable resin composition of the present invention can be used in a wide range of fields where moisture resistance, heat resistance and high adhesiveness are required. Specifically, it is useful as a material for all electric/electronic components such as an insulating material, a laminated board (printed wiring board, BGA substrate, build-up substrate, etc.), a sealing material and a resist. In addition to molding materials and composite materials, they can also be used in fields such as coating materials and adhesives. In particular, it can be suitably used for a semiconductor laminated plate.

Next, the present invention will be described in more detail with reference to Examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analytical methods used in the examples are described below.

・Compliant with ICI melt viscosity JIS K7117-2 (ISO3219) ・Compliant with softening point JIS K7234 ・GPC
Column: (Shodex KF-603, KF-602x2, KF-601x2)
Connected eluent: Tetrahydrofuran Flow rate: 1.0 ml/min.
Column temperature: 40°C
Detection: RI (differential refraction detector)
・GC-MS
Equipment: Shimadzu Corporation GCMS-QP2010
Column: HP-5 (30m)
Carrier: Helium Flow rate: 1 mL/min
Column temperature: 80°C (2 min)-5°C/min-300°C (60 min)
Injection: Auto injector 1 μL, split 30:1, 300°C
Ionization: EI

[Example 1: Indene-benzaldehyde resin mixture]
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 73.2 parts of indene, 143.6 parts of toluene, and 6.7 parts of potassium-tert-butoxide were added while performing a nitrogen purge, and the temperature was raised to 70°C. 63.7 parts of benzaldehyde was added dropwise over 30 minutes. The solution turned black while generating heat, and the reaction was carried out at 70 to 75° C. for 2 hours.
Then, the mixture was cooled to room temperature, 35% hydrochloric acid was added dropwise over 30 minutes, and the mixture was heated to 95° C. while dehydrating and reacted for 5 hours. After completion of the reaction, the solution was cooled to room temperature and neutralized with 30% aqueous sodium hydroxide solution. Subsequently, water was added, and the mixture was washed with water until the aqueous layer became neutral, and the obtained organic layer was evaporated under reduced pressure at 110° C. on a rotary evaporator to obtain 115 parts of a solvent. The fulvenyl group-containing resin (hereinafter referred to as FR-1) obtained was a dark brown semi-solid resin and had a hydroxyl group equivalent of 5,400 g/eq. , Mw/Mn was 8.31. The compound represented by formula (16-a) and the compound represented by formula (16-b) were confirmed by GC-MS analysis.

[Example 2: Indene-acetophenone resin mixture]
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 24.4 parts of indene, 50.7 parts of toluene, and 4.5 parts of potassium-tert-butoxide were added while performing a nitrogen purge, and the temperature was raised to 80°C. 24.0 parts of acetophenone was added dropwise over 30 minutes. The solution turned black while generating heat, and the reaction was carried out at 80 to 85° C. for 2 hours. Then, the Dean Stark was attached to the flask, and while dehydrating, the temperature was raised to 120° C. and the reaction was carried out for 5 hours. After completion of the reaction, the mixture was cooled to room temperature and the solution was neutralized with 4.2 parts of 30% hydrochloric acid. Subsequently, water was added and the mixture was washed with water until the aqueous layer became neutral, and the obtained organic layer was distilled off the solvent under reduced pressure at 120° C. on a rotary evaporator to obtain 40 parts. The obtained fulvenyl group resin (hereinafter, referred to as FR-2) was a dark brown liquid resin, the hydroxyl group equivalent was the detection limit (30,000 g/eq.) or more, and the Mw/Mn was 1.79. .. The compound represented by formula (17-a) and the compound represented by formula (17-b) were confirmed by GC-MS analysis.

[Example 3: Fluorene-benzaldehyde resin mixture]
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 34.9 parts of fluorene, 78.6 parts of toluene, and 22.4 parts of potassium-tert-butoxide were added while performing a nitrogen purge, and the temperature was raised to 80°C. 21.2 parts of benzaldehyde was added dropwise over 30 minutes. The solution turned black and reacted at 80 to 85° C. for 2 hours. Then, a Dean Stark was attached to the flask, and the reaction was carried out at 120° C. for 5 hours and at 150° C. for 2 hours while dehydrating. After completion of the reaction, the solution was cooled to room temperature, and the solution was neutralized with 24.3 parts of 30% hydrochloric acid. Subsequently, water was added and washed with water until the aqueous layer became neutral, and the obtained organic layer was steam distilled under reduced pressure at 130° C. with a rotary evaporator while adding water to remove the solvent and residual fluorene. By removing, 35 parts were obtained. The fulvenyl-based resin (hereinafter referred to as FR-3) obtained was a red-orange semi-solid resin and had a hydroxyl equivalent of not less than the detection limit (30,000 g/eq.) and Mw/Mn of 5.81. there were. The compound represented by the formula (18) was confirmed by GC-MS analysis.

[Example 4: Methylcyclopentadiene-acetophenone resin mixture]
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean Stark was added 50.0 parts of methyldicyclopentadiene (MDCPD manufactured by Maruzen Petrochemical Co., Ltd.) while purging with nitrogen, and the mixture was heated to 160° C. and distilled. The portion was collected. 33.7 parts of the obtained distillate, 44.9 parts of potassium-tert-butoxide, and 126.6 parts of toluene were added, the temperature was raised to 80° C., and 48.1 parts of acetophenone was added dropwise over 30 minutes. The solution turned black and reacted at 80 to 85° C. for 5 hours. Then, while dehydrating, the temperature was raised to 120° C. and the reaction was performed for 2 hours. After completion of the reaction, the solution was cooled to room temperature and neutralized with 48.6 parts of 30% hydrochloric acid. Subsequently, water was added, and the mixture was washed with water until the aqueous layer became neutral, and the obtained organic layer was distilled off the solvent under reduced pressure at 120° C. on a rotary evaporator to obtain 72 parts. The resulting fulvenyl group resin (hereinafter referred to as FR-4) is a dark brown semi-solid resin and has a hydroxyl group equivalent of 12,000 g/eq. , Mw/Mn was 1.22. The compound represented by formula (19-a) and the compound represented by formula (19-b) were confirmed by GC-MS analysis.

[Example 5: Indene aralkyl resin mixture]
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 34.9 parts of indene, 66.5 parts of toluene, and 18.1 parts of potassium-tert-butoxide while carrying out a nitrogen purge, and the temperature was raised to 80°C. 13.1 parts of p-xylylene dichloride was added portionwise over 30 minutes. The solution turned black with vigorous heat generation, and the reaction was carried out at 80 to 90° C. for 3 hours. Then, 15.9 parts of benzaldehyde was added dropwise at 80° C. over 30 minutes, and the reaction was performed for 2 hours. After cooling to room temperature, 31.3 parts of 35% hydrochloric acid was added dropwise over 30 minutes, and while dehydrating, the temperature was raised to 95° C. and the reaction was carried out for 5 hours. After completion of the reaction, the solution was cooled to room temperature and neutralized with 38.0 parts of 30% sodium hydroxide aqueous solution. Water was added, and the mixture was washed with water until the aqueous layer became neutral, and the obtained organic layer was distilled off the solvent under reduced pressure at 110° C. on a rotary evaporator to obtain 55 parts. The obtained cyclopentadienyl group-containing resin mixture (hereinafter referred to as CP-1) was a dark brown semi-solid resin, and Mw/Mn was 8.00. The compound represented by formula (20-a) and the compound represented by formula (20-b) were confirmed by GC-MS analysis.

[Example 6: Indene biphenyl aralkyl resin mixture]
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 23.2 parts of indene, 38.2 parts of toluene, and 7.4 parts of potassium-tert-butoxide were added while performing a nitrogen purge, and the temperature was raised to 80°C. 7.5 parts of 4,4′-bischloromethylbiphenyl was added portionwise over 30 minutes. The solution turned black with vigorous heat generation, and the reaction was carried out at 80 to 90° C. for 3 hours. Then, 14.9 parts of benzaldehyde was added dropwise at 80° C. over 30 minutes, and the reaction was performed for 2 hours. After cooling to room temperature, 20.8 parts of 35% hydrochloric acid was added dropwise over 30 minutes, and while dehydrating, the temperature was raised to 95° C. and the reaction was carried out for 5 hours. After completion of the reaction, the solution was cooled to room temperature and neutralized with 25.9 parts of 30% aqueous sodium hydroxide solution. Water was added, and the mixture was washed with water until the aqueous layer became neutral, and the organic layer obtained was distilled off the solvent under reduced pressure at 110° C. on a rotary evaporator to obtain 38 parts. The resulting cyclopentadienyl group-containing resin mixture (hereinafter referred to as CP-2) was a dark brown semi-solid resin, and Mw/Mn was 10.41. The compound represented by the formula (21) was confirmed by GC-MS analysis.

[Example 7: Methylcyclopentadiene biphenylaralkyl resin]
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean Stark was added 50.0 parts of methyldicyclopentadiene (MDCPD manufactured by Maruzen Petrochemical Co., Ltd.) while purging with nitrogen, and the mixture was heated to 160° C. and distilled. The portion was collected. 32.1 parts of the obtained distillate, 82.7 parts of toluene, and 29.6 parts of potassium-tert-butoxide were added, the temperature was raised to 80° C., and 13.1 parts of p-xylylenedichloride was added over 30 minutes. Added in portions. The solution turned black with vigorous heat generation, and the reaction was carried out at 80 to 90° C. for 2 hours. Then, the mixture was cooled to room temperature, neutralized with 2.5 parts of 35% hydrochloric acid, added with water, and washed with water until the aqueous layer became neutral. The organic layer thus obtained was evaporated under reduced pressure at 110° C. with a rotary evaporator to remove 36 parts of the solvent. The obtained cyclopentadienyl group-containing resin mixture (hereinafter referred to as CP-3) was a dark brown semi-solid resin, and Mw/Mn was 5.21. The compound represented by the formula (22) was confirmed by GC-MS analysis.

[Example 8: Indene-benzaldehyde resin mixture]
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 73.2 parts of indene, 143.6 parts of toluene, and 6.7 parts of potassium-tert-butoxide were added while performing a nitrogen purge, and the temperature was raised to 70°C. 63.7 parts of benzaldehyde was added dropwise over 30 minutes. The solution turned black while generating heat, and the reaction was carried out at 70 to 75° C. for 2 hours.
Then, it cooled to room temperature and neutralized using 35% hydrochloric acid. Subsequently, water was added, and the mixture was washed with water until the aqueous layer became neutral, and the obtained organic layer was evaporated under reduced pressure at 110° C. in a rotary evaporator to obtain 116 parts of the solvent. The fulvenyl group-containing resin (hereinafter referred to as FR-1) obtained was a dark brown semi-solid resin having a hydroxyl group equivalent of 1,100 g/eq. , Mw/Mn was 2.50. The compound represented by formula (23-a) and the compound represented by formula (23-b) were confirmed by GC-MS analysis.

[Examples 9 to 16, Comparative Examples 1 to 3]
The obtained compound and a maleimide resin, etc. were blended in the proportions (parts by weight) shown in Table 1, kneaded with a mixing roll, tabletted, and then transfer-molded to prepare a resin molded body, which was heated at 200° C. for 2 hours and at 220° C. It was cured at 300° C. for 2 hours.
The physical properties of the obtained cured product were measured for the following items, and the results are shown in Table 1.

<Heat resistance test>
-Glass transition temperature: The temperature when tan δ is the maximum value, measured by a dynamic viscoelasticity tester.
Dynamic viscoelasticity measuring instrument: DMA-2980 manufactured by TA-instruments
Temperature rising rate: 2°C/min <Dielectric constant test/Dielectric loss tangent test>
-A test was performed by a cavity resonator perturbation method using a 1 GHz cavity resonator manufactured by Kanto Electronics Co., Ltd. However, the sample size was set to 1.7 mm in width×100 mm in length, and the thickness was 1.7 mm in the test.
Measured at 1 GHz according to JIS C2565.

From Table 1, it was confirmed that the curable resin mixture of the present invention was excellent in heat resistance and electric characteristics.

[Example 17]
To a flask equipped with a stirrer, a reflux condenser and a stirrer was added 95.6 parts of toluene and 0.5 part of boron trifluoride diethyl ether complex while carrying out a nitrogen purge, and the FR obtained in Example 1 was obtained at room temperature. -1 was added portionwise over 28.7 parts over 30 minutes. After continuing stirring at room temperature for 5 hours, the temperature was raised to 80° C. and the reaction was continued for further 5 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, and the mixture was washed with water until the aqueous layer became neutral, and the obtained organic layer was evaporated under reduced pressure at 120°C on a rotary evaporator to remove the solvent FR-. Polymer 1 was obtained. Further, 10 parts of toluene was added to adjust the varnish, and the resulting varnish was coated on a release PET film and dried at 120° C. to obtain a polymer film of FR-1.

[Comparative Example 4]
A polymerized film of an indene monomer was obtained in the same manner as in Example 17, except that an indene monomer was used instead of FR-1.

<Heat resistance test>
The residual carbon rate at 500° C. was measured using the polymer films obtained in Example 17 and Comparative Example 4.
Measuring device: TG-DTA 6220 (manufactured by Seiko Instruments Inc.)
Measurement temperature: 30 to 580°C
Temperature rising rate: 10°C/min
Gas: Nitrogen gas 200 ml/min

From Table 2, it was confirmed that the curable resin mixture of the present invention had excellent heat resistance.

Therefore, the curable resin mixture of the present invention is used as an encapsulant for semiconductor elements, an encapsulant for liquid crystal display elements, an encapsulant for organic EL elements, a printed wiring board, a build-up laminated board, carbon fiber and the like. It is useful for applications such as lightweight and high-strength composite materials for structural materials such as reinforced plastics and glass fiber reinforced plastics.

Claims (13)

A curable resin mixture having at least one of the cyclopentadiene structures represented by the following formulas (1) to (4).

(In the formula (1), a plurality of A's represent a hydrogen atom or an arbitrary organic group. A plurality of R ^1's each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number 1). A halogenated alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. alkyl group having 1 to 20 carbon atoms which is substituted with a silyl group having, ^-NR _{2 2} group, -SR ² group, -OSiR ² ₃ group, or ^-PR ₂ represents a ₂ group. multiple present ^{R 2} is a hydrogen atom, It represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and a represents a natural number of 1 to 3.)

(In the formula (2), A and R ¹ have the same meanings as described above. b represents a natural number of 1 to 4.)

(In the formula (3), A and R ¹ have the same meanings as described above. c and d each represent a natural number of 1 to 4.)

(In the formula (4), a plurality of B's represent a hydrogen atom or an arbitrary organic group. A plurality of R ¹ , a, and b's have the same meanings as described above. n represents a natural number of 1 or more, and a dotted line indicates A bond may be present or may not be present. C represents any one or more of the following formula (5).)

(In the formula (5), * represents that it is bonded to a cyclopentadienyl group. Multiple R ³ , s, and t are independently present, and R ³ is a hydrogen atom, a halogen atom, or a carbon atom. A silyl group having an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydrocarbon group having 1 to 6 carbon atoms. , an alkyl group having 1 to 20 carbon atoms which is substituted by a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, ^-NR _{4 2} group, -SR ⁴ group, -OSiR ⁴ ₃ group or ^-PR _{4 2} group ( R ⁴ present in plural numbers represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, s represents 1 to 7, and t represents 1 to 4. Even if dotted lines are bonded to each other to form a ring structure. Show good things.) The curable resin mixture according to claim 1, which is represented by the formulas (1) to (3) and A is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The curable resin mixture according to claim 1, which is represented by the formula (4) and B is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. The curable resin mixture according to any one of claims 1 to 3, which is composed of only carbon atoms and hydrogen atoms. The curable resin mixture according to any one of claims 1 to 4, wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 1.1 to 1,000. Hydroxyl equivalent is 125 g/eq. It is above, The curable resin mixture as described in any one of Claim 1 thru|or 5. Any of claims 1 to 6 obtained by reacting a cyclopentadiene compound represented by at least one of the following formulas (6) to (8) with an electrophile represented by the following formula (9). The curable resin mixture as described in 1 above.

(In the formula (6), A represents a hydrogen atom or any organic group. R ¹ and a represent the same meaning as described above.)

(In the formula (7), R ¹ and b have the same meanings as described above.)

(In the formula (8), R ¹ , c and d have the same meanings as described above.)

(In formula (9), a plurality of R ^5's are independently present and represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The dotted line indicates that they may be bonded to each other to form a ring structure. .) Any of claims 1 to 7 obtained by reacting a cyclopentadiene compound represented by the following formula (10) with an electrophilic reagent represented by at least one of the following formulas (11) to (13). The curable resin mixture as described in 1 above.

(In the formula (10), R ¹ , a and b have the same meanings as described above, and the dotted line represents that a bond may or may not be present.)

(In formula (11), a plurality of R ^{5 s} have the same meanings as described above. The dotted line indicates that they may be bonded to each other to form a ring structure.)

(In the formula (12), a plurality of R ³ , R ⁵ and t have the same meanings as described above.)

(In the formula (13), a plurality of R ³ and s have the same meanings as described above.) A curable resin composition comprising the curable resin mixture according to claim 1 and a curing agent. The curable resin composition according to claim 9, wherein the curing agent is an active alkene-containing resin. The curable resin composition according to claim 9, wherein the curing agent is a maleimide resin. A curable resin composition according to any one of claims 1 to 8, or a curable resin composition according to any one of claims 9 to 11, which further contains a radical polymerization initiator. Stuff. A cured product obtained by curing the curable resin composition according to any one of claims 9 to 12.

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