JP2023020066A - Allyl group-containing polycarbonate resin and curable resin composition - Google Patents

Abstract

To provide a polycarbonate resin which exhibits a low dielectric constant and a low dielectric loss tangent, and a curable resin composition which includes the polycarbonate resin and exhibits a low dielectric constant and a low dielectric loss tangent.SOLUTION: A polycarbonate resin is provided, which contains a specific bisphenol-based constitutional unit (A) having a substituent and a specific bisphenol-based constitutional unit (B) having an allyl group, has a ratio of the (A) in the total constitutional unit of 70 mol% or more, and satisfies the following (a) to (c). (a) A weight average molecular weight obtained by measuring the polycarbonate resin by a gel permeation chromatography method is 15,000 to 45,000. (b) A relative dielectric constant at a frequency of 10 GHz obtained by measuring the polycarbonate resin according to a cavity resonator perturbation method is 2.3 to 2.7, and a dielectric loss tangent is 0.0001 to 0.0030. (c) A ratio of the (B) in the total constitutional unit of the polycarbonate resin is 1 mol% or more and 10 mol% or less.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an allyl group-containing polycarbonate resin exhibiting a low dielectric constant and a low dielectric loss tangent. The present invention also relates to a curable resin composition that uses an allyl group-containing polycarbonate resin as a curing agent and exhibits a low dielectric constant and a low dielectric loss tangent.

Mobile wireless communication services typified by mobile phones, which have been used for voice calls, are now being used as a means of accessing the Internet due to the development of communication and information processing technology. In addition, full-scale operation is about to start for the purpose of control, sensing, and monitoring, from communication between people to communication between machines and things. The next-generation wireless communication standard 5G system (hereinafter referred to as 5G) has been put into operation in order to cope with a significant increase in network traffic. Conventional communication systems (eg, 4GLTE) have used a low frequency band of 2.5 GHz or lower, but 5G uses a high frequency band of 6 GHz or higher. Therefore, future 5G-compatible devices are required to be compatible with high-frequency signals. For example, reduction of transmission loss is mentioned as a high-frequency countermeasure for a printed wiring board (hereinafter referred to as PCB). The transmission loss referred to here means conductor loss derived from a conductor (for example, a copper circuit) that constitutes a PCB, and dielectric loss derived from a dielectric (insulating material around the circuit). The former countermeasure is to smooth the surface of the conductor, but it can be said that a large improvement cannot be expected as an improvement effect. Therefore, the latter countermeasure is important. Specifically, dielectric loss depends on the frequency of the current and the dielectric constant and dielectric loss tangent of the insulating material around the circuit. there is In addition, there is a need for an insulating material that has workability and physical properties (eg, heat resistance, adhesiveness, insulating properties, etc.) equivalent to those of conventional substrate materials.

The types of PCBs are divided into package substrates directly under chips such as mobile processors, rigid substrates for main boards on which the package substrates are mounted, and flexible printed substrates used as LCD drivers, camera modules, and film antennas. Thermosetting resins are used for these insulating materials, and the resin composition includes (i) thermosetting and cross-linking components such as epoxy resins and maleimide resins, (ii) flame retardancy, heat resistance, and low linear expansion. It is composed of a filler component for imparting modulus, and (iii) a polymer used for improving flexibility and adhesiveness. Heat resistance, adhesiveness, workability, flexibility and compatibility are generally essential for polymers used as insulating materials for PCBs. Carboxyl-modified acrylonitrile-butadiene copolymer rubber, acrylic polymer, urethane polymer, etc. have been used as conventional polymers for PCBs. However, there is no material that has the low dielectric properties required for high frequency applications, and new materials are currently being sought.

Therefore, a curable resin composition containing a predetermined amount of a polycarbonate resin has been studied for the purpose of lowering the dielectric and improving flexibility and adhesiveness. For example, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, a polycarbonate resin, and an inorganic filler. However, even if the polycarbonate resin is added to the curable resin composition, it becomes incompatible at the time of curing, so that the addition effect of the polycarbonate resin is difficult to manifest, and there is a problem that the addition amount is limited. Further, Patent Documents 2, 3 and 4 disclose a method of adding an allyl group-containing aliphatic polycarbonate resin to a curable resin composition. However, although the compatibility of the curable resin composition is improved by containing an allyl group, the problem is that the dielectric loss tangent is increased by copolymerizing the aliphatic diol.

JP 2019-35056 A JP 2019-89965 A JP 2019-89966 A JP 2019-89967 A

An object of the present invention is to provide a polycarbonate resin exhibiting a low dielectric constant and a low dielectric loss tangent. Another object of the present invention is to provide a curable resin composition containing the polycarbonate resin and exhibiting a low dielectric constant and a low dielectric loss tangent, and a cured product thereof.

As a result of extensive studies, the present inventors have surprisingly found that the above object can be achieved by using an allyl group-containing polycarbonate resin containing a specific structural unit. As a result of advancing studies based on such findings, the present invention was completed.

That is, according to the present invention, the following (configuration 1) to (configuration 12) are provided.
(Configuration 1)
Containing a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2), and the proportion of the structural unit (A) in all structural units is 70 mol% or more and a polycarbonate resin that satisfies the following (a) to (c).
(a) the weight average molecular weight of the polycarbonate resin measured by gel permeation chromatography is in the range of 15,000 to 45,000;
(b) The dielectric constant at a frequency of 10 GHz measured according to the cavity resonator perturbation method of polycarbonate resin is in the range of 2.3 to 2.7, and the dielectric loss tangent is in the range of 0.0001 to 0.0030. matter,
(c) the ratio of the structural unit (B) in all structural units of the polycarbonate resin is 1 mol% or more and 10 mol% or less;

(In formula (1), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, Alternatively, it represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R ₃ and R ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or an unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, X is a single bond, substituted or unsubstituted 1 to 20 alkylene group, substituted or unsubstituted alkylidene group having 2 to 20 carbon atoms, substituted or unsubstituted sulfur atom, or oxygen atom.)

(In general formula (2), R ₅ to R ₈ each independently represent a hydrogen atom or an allyl group having 3 to 20 carbon atoms, provided that at least one of R ₅ to R ₈ is a carbon atom an allyl group having a number of 3 to 20. Y is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 20 carbon atoms, a substituted or unsubstituted represents a sulfur atom or an oxygen atom.)

(Configuration 2)
The polycarbonate according to Configuration 1, wherein the terminal structure of the polycarbonate resin contains a structure (C) derived from a monohydroxy compound represented by the following formula (3), and accounts for 10 mol% or more of all terminal structures constituting the polycarbonate resin. resin.

(In formula (3), R ₉ is a hydrogen atom, a straight or branched alkyl group having 1 to 9 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, or 1 to 20 carbon atoms. is a linear or branched phenyl-substituted alkyl group, and R ₁₀ is an allyl group having 3 to 20 carbon atoms.)

(Composition 3)
The polycarbonate resin according to Structure 1 or 2, wherein X in Formula (1) is at least one group selected from the group consisting of Formula (4) below.

(R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and Z represents a substituted or unsubstituted alkylene group having 4 to 12 carbon atoms.)

(Composition 4)
Configuration 1 wherein Y in the formula (2) is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 12 carbon atoms, or a substituted or unsubstituted sulfur atom. 4. The polycarbonate resin according to any one of 1 to 3.
(Composition 5)
The polycarbonate resin according to any one of Structures 1 to 4, wherein the proportion of the structural unit (A) in all structural units of the polycarbonate resin is 80 mol% or more.
(Composition 6)
6. The polycarbonate resin according to any one of Structures 1 to 5, wherein the proportion of the structural unit (B) in all structural units of the polycarbonate resin is 2 mol % or more and 8 mol % or less.
(Composition 7)
R ₁ and R ₂ in the above formula (1) are each at least one group selected from the group consisting of a methyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and a phenyl group, and R ₃ and R ₄ are The polycarbonate resin according to any one of Structures 1 to 6, each of which is a hydrogen atom or a methyl group.
(Composition 8)
The polycarbonate resin according to any one of structures 1 to 7, wherein R ₅ and R ₆ in formula (2) are allyl groups having 3 to 10 carbon atoms, and R ₇ and R ₈ are hydrogen atoms.
(Composition 9)
The polycarbonate resin according to any one of structures 1 to 8, wherein Y in formula (2) is a sulfide group, a sulfone group or an isopropyl group.
(Configuration 10)
10. The polycarbonate resin according to any one of structures 1 to 9, which is a polycarbonate resin produced by interfacial polycondensation of a dihydroxy compound and carbonyl chloride.
(Composition 11)
A curable resin composition comprising the polycarbonate resin according to any one of structures 1 to 10, a maleimide compound and an inorganic filler.
(Composition 12)
The resin composition according to Structure 11, which is for forming an insulating layer of a printed wiring board.

The allyl group-containing polycarbonate resin of the present invention exhibits a low dielectric constant and a low dielectric loss tangent. It can be obtained and is suitably used as a material for high frequency substrates.

The details of the present invention will be described below.

<Polycarbonate resin>
The polycarbonate resin of the present invention contains a structural unit (A) represented by the following formula (1).

Here, in formula (1), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms. or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ₃ and R ₄ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms , a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

Examples of substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms in R ₁ and R ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group and the like. Examples of the substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl group, benzyl group, tolyl group, 4-methylphenyl group, naphthyl group and the like.

Among these, each of R ₁ and R ₂ is preferably a methyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group or a phenyl group, and particularly preferably a methyl group.

Examples of substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms in R ₃ and R ₄ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group and the like. The substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms includes cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl group, benzyl group, tolyl group, 4-methylphenyl group, naphthyl group and the like.

Among these, R ₃ and R ₄ are each preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or a 4-methylphenyl group, particularly preferably a hydrogen atom or a methyl group. Here, the bonding positions of R ₁ , R ₂ , R ₃ and R ₄ in formula (1) are arbitrary selected from 2-position, 3-position, 5-position and 6-position with respect to X on each phenyl ring. position, preferably 3- and 5-positions.

In formula (1), X is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 20 carbon atoms, a substituted or unsubstituted sulfur atom, or represents an oxygen atom. Examples of substituted or unsubstituted sulfur atoms include -S- and -SO ₂ -. Also, the substituted or unsubstituted alkylidene group having 2 to 20 carbon atoms is preferably at least one group selected from the group consisting of the following formula (4).

R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and Z is It represents a substituted or unsubstituted alkylene group having 4 to 12 carbon atoms.

Examples of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms in R ₁₁ and R ₁₂ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group. group, tert-butyl group, n-pentyl group, sec-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl group, benzyl group, tolyl group, 4-methylphenyl group, naphthyl group and the like.

Among these, each of R ₁₁ and R ₁₂ is preferably a methyl group, an ethyl group, an n-propyl group or a 4-methylphenyl group, particularly preferably a methyl group.

In formula (1), Z is bonded to the carbon bonding two phenyl groups to form a substituted or unsubstituted divalent carbocyclic ring. Examples of divalent carbocyclic rings include cycloalkylidene groups (preferably having 5 carbon atoms) such as cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclododecylidene, and adamantylidene. to 8), and substituted ones include those having a methyl substituent or an ethyl substituent. Among these, a cyclohexylidene group and a methyl-substituted cyclohexylidene group are preferred.

The polycarbonate resin of the present invention needs to contain the structural unit (A) represented by formula (1). The ratio of the structural unit (A) in the total structural units of the polycarbonate resin is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. . If the structural unit (A) of the formula (1) is less than 70 mol %, the dielectric properties will deteriorate, which is not preferable.

The polycarbonate resin of the present invention contains a structural unit (B) represented by the following formula (2).

Here, in formula (2), R ₅ to R ₈ each independently represent a hydrogen atom or an allyl group having 3 to 20 carbon atoms. However, at least one of R ₅ to R ₈ is preferably an allyl group, and two or more are preferably allyl groups. In particular, it is preferred that R ₅ and R ₆ are allyl groups having 3 to 10 carbon atoms, and R ₇ and R ₈ are hydrogen atoms. Here, the bonding position of R ₅ to R ₈ in formula (2) is any position selected from 2-position, 3-position, 5-position and 6-position with respect to Y on each phenyl ring, preferably 3rd and 5th.

Y represents a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 20 carbon atoms, a substituted or unsubstituted sulfur atom, or an oxygen atom.

The specific structure of Y is the same as the specific structure of X described for X in formula (1) above. Among them, Y is preferably a sulfide group, a sulfone group or an isopropyl group.

Dihydroxy compounds from which the structural unit (B) is derived include, for example, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)methane, 2 ,2-bis(3-allyl-4-hydroxyphenyl)sulfone and the like, and among them 2,2-bis(3-allyl-4-hydroxyphenyl)propane or 2,2-bis(3-allyl-4- hydroxyphenyl)sulfone is preferred. Moreover, these may be used alone or in combination of two or more.

The polycarbonate resin of the present invention needs to contain the structural unit (B) represented by formula (2). The ratio of the structural unit (B) in the total structural units of the polycarbonate resin is 1 mol% or more and 10 mol% or less, preferably 2 mol% or more and 8 mol% or less, more preferably 2 mol% or more and 5 mol% or less. is. If the proportion of the structural unit (B) is less than 1 mol %, the reactivity between the polycarbonate resin and the maleimide compound is poor, and if it exceeds 10 mol %, the dielectric properties are poor, which is not preferred.

The polycarbonate resin used in the present invention can usually be obtained by reacting a dihydroxy compound with a carbonyl compound. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a monohydric phenol terminal terminator is usually used. Branched polycarbonates obtained by polymerizing trifunctional components may also be used, and copolymerized polycarbonates obtained by copolymerizing aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and vinyl monomers may also be used.

The polycarbonate resin of the present invention is produced by a reaction means known per se for producing ordinary polycarbonate resins, for example, a method of reacting a dihydroxy compound with a carbonyl compound such as carbonyl chloride (phosgene) or diester carbonate. Next, the basic means of these manufacturing methods will be briefly described.

In reactions using, for example, carbonyl chloride (phosgene) as the carbonyl compound, the reaction is usually carried out in the presence of an acid-binding agent and a solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Examples of the solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene. A catalyst such as a tertiary amine or a quaternary ammonium salt may also be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40° C., and the reaction time is several minutes to 5 hours.

The polycarbonate resin of the present invention may contain a structure (C) derived from a monohydroxy compound represented by the following formula (3), which is used as a terminal terminator in the polymerization reaction.

In formula (3), R ₉ is a hydrogen atom, a straight or branched alkyl group having 1 to 9 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, or a A linear or branched phenyl-substituted alkyl group, and R ₁₀ is an allyl group having 3 to 20 carbon atoms. Here, the bonding position of R ₁₀ in formula (3) is any position selected relative to the OH group on each phenyl ring, preferably the ortho position.

Specific examples of the monohydroxy compound include 2-allylphenol, funicol, and eugenol. Moreover, these may be used alone or in combination of two or more.

The terminal structure derived from these monohydroxy compounds is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% of the total terminal structure constituting the obtained polycarbonate resin. That's it. By introducing a terminal structure derived from these monohydroxy compounds to the terminal, the reactivity between the polycarbonate resin and the maleimide compound is further improved.

Moreover, the polycarbonate resin of this invention can use monofunctional phenols normally used as a terminal terminator. Monofunctional phenols are commonly used as end-stoppers for molecular weight control, especially in the case of reactions using phosgene as the carbonate precursor, and the resulting polycarbonate resins are terminally based on monofunctional phenols. Since it is blocked by a group, it has excellent thermal stability compared to those that are not.

Such monofunctional phenols may be those used as terminal terminating agents for polycarbonate resins, and are generally phenols or lower alkyl-substituted phenols, and monofunctional phenols represented by the following formula (5): can indicate the type.

In formula (5), A is a linear or branched alkyl group or arylalkyl group having 1 to 9 carbon atoms, and r is an integer of 1 to 5, preferably an integer of 1 to 3.

Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, as other monofunctional phenols, phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic ester group as a substituent, or long-chain alkylcarboxylic acid chlorides can be used. When these are used to block the ends of a polycarbonate polymer, they not only function as a terminal terminator or a molecular weight modifier, but also improve the melt fluidity of the resin, facilitating molding and processing, as well as forming molded products. It has the effect of lowering the physical properties, especially the water absorption of the resin, and also has the effect of reducing the birefringence of the molded product, so it is preferably used. Among them, phenols having long-chain alkyl groups represented by the following formulas (6) and (7) as substituents are preferably used.

In formula (7), Z is -R-O-, -R-CO-O- or -R-O-CO-, where R is a single bond or 1 to 10 carbon atoms, preferably carbon atoms It represents a divalent aliphatic hydrocarbon group of number 1-5, and n represents an integer of 10-50.

The substituted phenols of formula (6) preferably have n of 10 to 30, particularly preferably 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and octadecylphenol. , eicosylphenol, docosylphenol and triacontylphenol.

Further, as the substituted phenols of the formula (7), Z is -R-CO-O-, and R is preferably a single bond, and n is 10 to 30, particularly n is 10 to 26. Preferred examples include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

These monofunctional phenols are desirably introduced at least 5 mol%, more preferably at least 10 mol%, of all terminals of the polycarbonate resin obtained. You may use it individually or in mixture of 2 or more types.

Moreover, the amount of terminal OH groups with respect to all structural units of the polycarbonate resin is preferably 300 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less. When it is 300 ppm or less, the heat stability of the polycarbonate resin is excellent.

Reaction by the melt polymerization method is typically a transesterification reaction between a dihydric phenol and a carbonate ester, in which the dihydric phenol and the carbonate ester are mixed while heating in the presence of an inert gas, and the resulting alcohol Alternatively, it is carried out by a method of distilling phenol. Although the reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, it is usually in the range of 120 to 350°C. At the latter stage of the reaction, the system is evacuated to about 10 to 0.1 Torr (1,300 Pa to 13 Pa) to facilitate distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

Carbonate esters include esters of optionally substituted aryl groups of 6 to 10 carbon atoms, aralkyl groups and alkyl groups of 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and diphenyl carbonate. is preferred.

In addition, a polymerization catalyst can be used to accelerate the polymerization rate, and examples of such polymerization catalysts include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, potassium salt; calcium hydroxide; alkaline earth metal compounds such as barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals; alkali metals and alkaline earth metal organic acid salts; other zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese Catalysts such as compounds, titanium compounds and zirconium compounds which are usually used for esterification reactions and transesterification reactions can be used. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably 1×10 ⁻⁸ to 1×10 ⁻³ equivalents, more preferably 1×10 ⁻⁷ to 5×10 ⁻⁴ equivalents, relative to 1 mol of dihydric phenol as a raw material. selected in the range.

Also, in such polymerization reactions, for example, bis(chlorophenyl) carbonate, bis(bromophenyl) carbonate, bis(nitrophenyl) carbonate, bis(phenyl) carbonate, bis(chlorophenyl) carbonate, bis(bromophenyl) carbonate, bis(nitrophenyl) carbonate, bis(phenyl) carbonate, etc., are added later or after the end of the polycondensation reaction to reduce phenolic end groups. It is preferred to add compounds such as phenyl)carbonate, chlorophenylphenylcarbonate, bromophenylphenylcarbonate, nitrophenylphenylcarbonate, phenylphenylcarbonate, methoxycarbonylphenylphenylcarbonate and ethoxycarbonylphenylphenylcarbonate. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

In the polycarbonate resin of the present invention, the structural unit (A) and the structural unit (B) preferably contain 75 mol% or more of all structural units, more preferably 80 mol% or more, and contain 85 mol% or more. It is more preferable to contain 90 mol % or more.

The structural unit (Z) other than the structural unit (A) and the structural unit (B) is preferably 25 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less, and particularly preferably 10 mol% or less. , may be contained within a range that does not impair the effects of the present invention.

Other dihydroxy components from which the structural unit (Z) is derived include, for example, hydroquinone, resorcinol, 4,4'-biphenol, 4,4'-bis(2,6-dimethyl)diphenol, 2,4'-dihydroxydiphenylmethane. , bis(2-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)ethane , 1,1-bis(4-hydroxy-2-chlorophenyl)ethane, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)decane, 1,1 -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-(p-phenylenediisopropylidene)diphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9 -bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 ,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide and the like. These can be used alone or in combination of two or more.

Other diol components from which the structural unit (Z) is derived include, for example, isosorbide: 1,4:3,6-dianhydro-D-sorbitol, tricyclodecanedimethanol (TCDDM), 4,8-bis(hydroxymethyl ) tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis/trans-1,4-cyclohexanedimethanol (CHDM), cis/trans-1,4-bis(hydroxymethyl)cyclohexane, cyclohex-1,4-ylenedimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane , cis-1,4-cyclohexanedimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1′-bi(cyclohexyl)-4,4 '-diols, spiroglycols, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol). These can be used alone or in combination of two or more.

(Characteristics of polycarbonate resin)
The number average molecular weight and weight average molecular weight of the polycarbonate resin of the present invention can be measured by a gel permeation chromatography method based on standard polystyrene. The weight average molecular weight of the polycarbonate resin of the present invention is in the range of 15,000 to 45,000, preferably in the range of 18,000 to 42,000, more preferably in the range of 20,000 to 35,000. 000 to 33,000 is more preferred. Within this range, the compatibility with the maleimide compound is improved, the strength of the resin composition after curing is improved, and a low dielectric constant and low dielectric loss tangent are exhibited. Further, the number average molecular weight of the polycarbonate resin of the present invention is preferably in the range of 5,000 to 15,000, more preferably in the range of 8,000 to 14,000, even more preferably in the range of 9,000 to 12,000. .

The polycarbonate resin of the present invention has a dielectric constant of 2.3 to 2.7, preferably 2.40 to 2.68 at a frequency of 10 GHz, measured by a perturbation method using a cavity resonator. , more preferably in the range of 2.45 to 2.66. Also, the dielectric loss tangent at a frequency of 10 GHz measured by the same method is in the range of 0.0001 to 0.0030, preferably in the range of 0.0005 to 0.0025. If the dielectric constant and dielectric loss tangent are within the above ranges, the dielectric loss of the insulating material is reduced, which is preferable.

The allyl group equivalent of the polycarbonate resin of the present invention is preferably in the range of 50 to 1000 eq/ton, more preferably in the range of 100 to 700 eq/ton, still more preferably in the range of 130 to 500 eq/ton, and in the range of 150 to 400 eq/ton. is particularly preferred. When the allyl group equivalent is at least the lower limit, the dielectric properties are more excellent. Reactivity with a maleimide compound is more excellent in allyl group equivalent being below the said upper limit.

(Curable resin composition)
Since the polycarbonate resin of the present invention has an allyl group, it can be used as a curing agent (maleimide curing agent) for curing a maleimide compound. Curing of the maleimide compound can be performed by heating.

Moreover, a cured product obtained by curing a maleimide compound using the polycarbonate resin of the present invention exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low coefficient of linear thermal expansion due to the use of the maleimide compound.

The curable resin composition of the present invention contains a polycarbonate resin. Polycarbonate resin is excellent in mechanical strength due to its excellent impact resistance. Therefore, it exhibits the effect of increasing the toughness of the cured product.

The content of the polycarbonate resin component is preferably 0.1% by weight or more, more preferably 1% by weight or more, and still more preferably 2% by weight or more, when the resin component of the resin composition is 100% by weight. The upper limit is preferably 30% by weight or less, more preferably 20% by weight or less, and even more preferably 10% by weight or less. By setting the content of the polycarbonate resin component within the above range, the toughness of the cured product can be improved.

In addition, since the polycarbonate resin of the present invention is used, the curable resin of the present invention is compared to a cured product obtained by curing a maleimide compound with an allylphenol resin or a cured product obtained by curing an epoxy resin with a phenol novolak resin. A cured product obtained from the composition has a lower dielectric constant and a lower dielectric loss tangent.

When the polycarbonate resin of the present invention is used to cure the maleimide compound, it is believed that the following reactions (1) to (3) occur and cure occurs.
(1) Reaction between a maleimide group and an allyl group.
(2) Reaction between maleimide groups.
(3) Reaction between allyl groups.

Furthermore, the polycarbonate resin of the present invention has excellent solubility in solvents generally used for dissolving maleimide compounds. Therefore, it is possible to obtain a resin varnish in which the polycarbonate resin and the maleimide compound of the present invention and, if necessary, the epoxy resin described below are both dissolved in a solvent.

As the solvent, a polar solvent such as methyl ethyl ketone is generally used.
The polycarbonate resin of the present invention can be cured by itself by the reaction (3) without being combined with a maleimide compound. However, by combining with a maleimide compound, the curing temperature can be lowered and the thermal properties such as the glass transition temperature can be improved as compared with the case of curing alone. Therefore, it is preferable to subject them to the curing reaction in combination with a maleimide compound or an epoxy resin.

Applications of the curable resin composition of the present invention are not particularly limited. For example, the applications may be the same as those of known thermosetting molding materials, such as sealing materials, film materials, laminate materials, and the like. More specific examples of applications include interlayer insulating layers of printed wiring boards, semiconductor sealing materials, resin materials for sealing electronic parts, electrical insulating materials, resin materials for copper-clad laminates, build-up laminate materials, Examples include resist materials, resin materials for liquid crystal color filters, paints, various coating agents, adhesives, and fiber reinforced plastic (FRP) materials.

<Maleimide compound>
The maleimide compound is not particularly limited as long as it is a compound having two or more maleimide groups, and examples thereof include bismaleimide compounds and polyphenylmethane maleimide. Examples of bismaleimide compounds include 4,4′-diphenylmethanebismaleimide (eg BMI-1100 from Daiwa Kasei Kogyo Co., Ltd.), alkylbismaleimide, diphenylmethanebismaleimide, phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide (eg Daiwa Kasei Kogyo Co., Ltd. BMI-4000), 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide (for example, Daiwa Kasei Kogyo Co., Ltd. BMI-5100), 4-methyl- 1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3- bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene and the like.

Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with maleimide groups are linked via methylene groups, and examples thereof include BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd. These maleimide compounds may be used singly or in combination of two or more.

The content of the maleimide compound in the curable resin composition of the present invention is preferably 10 to 300 parts by weight, more preferably 15 to 200 parts by weight, even more preferably 20 to 150 parts by weight, with respect to 100 parts by weight of the polycarbonate resin. . When the content of the maleimide compound is within the above range, the gelling temperature of the curable resin composition can be lowered, for example, 200° C. or less. Moreover, the cured product of the curable resin composition exhibits a higher glass transition temperature, a higher thermal decomposition temperature, a lower coefficient of linear expansion, a lower dielectric constant, and a lower dielectric loss tangent.

<Epoxy resin>
The curable resin composition of the present invention can contain an epoxy resin as needed. Since the polycarbonate resin used in the present invention may have phenolic hydroxyl groups, it can also be used as a curing agent for curing epoxy resin (epoxy resin curing agent). Curing of the epoxy resin can be performed by heating.

When the polycarbonate resin of the present invention is used to cure the epoxy resin, it is believed that the above reaction (3) and the following reactions (4) to (5) occur to cause curing.
(4) Reaction between epoxy groups and hydroxyl groups.
(5) Reaction between epoxy groups.

Examples of epoxy resins include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type Epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

<Solvent>
The solvent is not particularly limited as long as it dissolves the components contained in the curable resin composition of the present invention (polycarbonate resin of the present invention, maleimide compound, epoxy resin, curing reaction catalyst, etc. as necessary). A polar solvent is typically used as the solvent. Polar solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, isophorone, diisobutyl ketone, diacetone alcohol, ketone solvents such as cyclohexanone, N,N-dimethylformamide, N- Methyl-2-pyrrolidone, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran and the like. Any one of these solvents may be used alone, or two or more may be used in combination. Among these, ketone-based solvents are preferable, and methyl ethyl ketone is more preferable.

<Curing reaction catalyst>
The curing reaction catalyst (curing accelerator) preferably contains a catalyst (hereinafter also referred to as “catalyst (1)”) that has the action of promoting the reaction between the allyl group and the maleimide group. Examples of the catalyst (1) include imidazole compounds and organic peroxides. Examples of imidazole compounds include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole , 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl -2-phenylimidazole and the like. Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates and peroxyesters. In the dialkyl peroxide, the alkyl group may be substituted with a phenyl group or the like. Such dialkyl peroxides include, for example, dicumyl peroxide.

When the curable resin composition of the present invention contains an epoxy resin, it contains, as a curing reaction catalyst, a catalyst (hereinafter also referred to as "catalyst (2)") having a function of promoting the reaction between hydroxyl groups and epoxy groups. You can Examples of the catalyst (2) include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts and the like. Phosphorus compounds include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, triphenyl phosphite and the like. Tertiary amines include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo[5.4.0]undecene-7 and the like. Examples of the imidazole compound include those similar to those described above.

<Inorganic filler>
The curable resin composition of the present invention contains an inorganic filler. The inorganic filler can reduce the coefficient of linear expansion of the cured product of the curable resin composition.

The material of the inorganic filler is not particularly limited as long as it is an inorganic compound. Examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and hydrotal. Site, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Examples include bismuth oxide, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle size of the inorganic filler is usually 5 μm or less, preferably 2.5 μm or less, more preferably 1.5 μm or less, and even more preferably 1 μm or less. The lower limit of the average particle diameter is not particularly limited, but may be 1 nm (0.001 μm) or more, 5 nm or more, or 10 nm or more. The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory.

The inorganic filler is preferably treated with a surface treatment agent such as a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, It is more preferably treated with one or more surface treatment agents such as an alkoxysilane compound, an organosilazane compound, and a titanate-based coupling agent, and more preferably treated with an aminosilane-based silane coupling agent. The surface treatment agent preferably has a functional group, such as an epoxy group, an amino group, or a mercapto group, which reacts with other components such as a resin, and more preferably the functional group is bonded to the terminal group.

From the viewpoint of reducing the average linear expansion coefficient of the cured product of the resin composition and improving the dielectric performance, the content of the inorganic filler component is, when the non-volatile content in the resin composition is 100 parts by weight, It is preferably 45 parts by weight or more, more preferably 50 parts by weight or more, and still more preferably 60 parts by weight or more. Although the upper limit is not particularly limited, it is preferably 85 parts by weight or less, more preferably 80 parts by weight or less, and still more preferably 75 parts by weight or less.

<Flame retardant>
The curable resin composition of the present invention can contain a flame retardant. Examples of flame retardants include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

When the curable resin composition contains a flame retardant, the content of the flame retardant is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight, based on 100 parts by weight of the non-volatile matter in the resin composition. It is at least 0.7 part by weight, more preferably at least 0.7 part by weight. Thereby, remarkable flame retardancy can be imparted to the resin composition and its cured product. The upper limit is preferably 5 parts by weight or less, more preferably 4 parts by weight or less, and even more preferably 3 parts by weight or less.

<Optional additives>
If necessary, the resin composition of the present invention may contain other additives. Such other additives include, for example, thermoplastic resins, organic fillers, organic copper compounds, organic zinc compounds, and organometallic compounds such as organocobalt compounds, and resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents.

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, A polyester resin etc. are mentioned. However, the thermoplastic resin referred to here does not include the polycarbonate resin of the present invention.

Any organic filler that can be used in forming the insulating layer of a printed wiring board may be used as the organic filler, and examples thereof include rubber particles, polyamide fine particles, silicone particles, and the like.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, the methods for measuring each property are as follows.

(1) weight average molecular weight (Mw)
Using the obtained polycarbonate resin as a measurement sample, the weight-average molecular weight Mw was measured by gel permeation chromatography (GPC) and determined by the polystyrene conversion method. A calibration curve was prepared using standard polystyrenes with known molecular weights (12 types from Tosoh PS Oligomer Kit A-500 to F-128). For the measurement, "HLC-8220GPC" manufactured by Tosoh Corporation was used, and three columns of "TSK-gel SuperHZ4000/3000/2000" manufactured by Tosoh Corporation were used. The sample used was obtained by dissolving 10 mg of a polycarbonate copolymer in 5 mL of chloroform (containing 0.05% internal standard toluene) and filtering using Millex LG4 manufactured by Millipore. Measurement was performed at 40° C. and a flow rate of 0.35 mL/min. Chloroform for high-performance liquid chromatography manufactured by Wako Pure Chemical Industries, Ltd. was used as an eluent.

(2) Allyl Group Equivalent and Terminal Ratio of Structure (C) Using the obtained polycarbonate resin as a measurement sample, ¹ H-NMR spectrum at room temperature was measured using JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL Ltd. , the allyl group equivalent in the polymer was calculated from the signal intensity ratio based on the structural unit derived from each compound. In addition, the value of the allyl group equivalent in the table indicates the total value of the skeleton portion and the terminal portion.

In addition, the signal intensity ratio based on the structural unit derived from the allyl group-containing monohydroxy group constituting the terminal, the monohydroxy group not containing the allyl group, and the OH group that is the unreacted terminal is calculated, and the signal intensity ratio at the terminal is calculated. The total was taken as the total terminal, and the ratio of the signal intensity ratio of the allyl group-containing monohydroxy group was calculated as the terminal ratio (mol%).
Amount of polymer 40 mg
Solvent deuterated chloroform 0.6 mL
Accumulated times: 256 times

(3) Glass transition temperature Using the obtained polycarbonate resin as a measurement sample, using a thermal analysis system DSC-2910 manufactured by TA Instruments, under a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) according to JIS K7121, Temperature rising rate: Measured under the condition of 20°C/min.

(4) Preparation of laminate For 100 g of the obtained polycarbonate resin, BMI-2300 (polyphenylmethane maleimide, maleimide equivalent: 186.0 g / eq) manufactured by Daiwa Kasei Kogyo as a maleimide compound is added by the following formula (1). In addition to the calculated amount, 1.2 g (1% of the total resin amount) of dicumyl peroxide as a curing reaction catalyst was dissolved in methyl ethyl ketone so that the solid content was 60%, and the resin varnish was applied. Obtained.

A glass cloth (E glass) was impregnated with the obtained resin varnish so that the resin content was 40% by weight, dried at 100° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six sheets of this prepreg were stacked, press-molded at 180° C., and after-baked at 230° C. for 5 hours to obtain a molded product (laminate) having a thickness of 1.5 mm. The resin content indicates the ratio of the resin (cured product) to the total weight of the molded product.
Amount of maleimide compound (g) = Maleimide equivalent (g/eq)/Allyl group equivalent of polycarbonate resin (eq/ton) x 10 ⁶ x 100 g/5 x 10 ^-6 (Formula 1)

(5) Coefficient of Linear Expansion A test piece of 5 mm square and 1.5 mm thick was cut out from the laminate. The coefficient of linear expansion at 30° C. was measured at a heating rate of 2° C./min using a linear expansion coefficient measuring device “TMA4000SE” manufactured by NETZSCH.

(6) Relative permittivity and dielectric loss tangent Using the polycarbonate resin and the laminate prepared in (4) above as a sample, a permittivity meter (Anritsu Network Analyzer MS46122B, AET Co. for cavity resonator 10 GHz) was used to determine the frequency of 10 GHz. Relative permittivity and dielectric loss tangent were measured.

[Example 1]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 4190 parts of a 25% aqueous sodium hydroxide solution and 8754 parts of ion-exchanged water, and bisphenol C (indicated as BPC in the table, manufactured by Honshu Kagaku Kogyo S -BOC) 1820 parts of diallyl bisphenol A (denoted as DAL-A in the table, BPA-CA manufactured by Konishi Chemical Industry Co., Ltd.) 115 parts, and 3.9 parts of sodium hydrosulfite (manufactured by Fujifilm Wako Pure Chemical) were dissolved. After that, 8,904 parts of methylene chloride was added, and 1,000 parts of phosgene was blown in at 15 to 25° C. over about 75 minutes while stirring. After the completion of the phosgene blowing, 599 parts of a 25% sodium hydroxide aqueous solution and 73 parts of p-tert-butylphenol (indicated as PTBP in the table, manufactured by DIC) were added, stirring was resumed, and after emulsification, 2.6 parts of triethylamine was added. and further stirred at 26-33° C. for 1 hour to complete the reaction.

After the completion of the reaction, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water. The washing with water was repeated until the conductivity of the aqueous phase became approximately the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter with a mesh size of 0.3 μm, and is added dropwise to hot water in a kneader with an isolated chamber having a foreign matter removal port in the bearing, and the polycarbonate resin is flaked while distilling off the methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. Each property was measured and the results are listed in Table 1.

[Example 2]
The same operation as in Example 1 except that 1858 parts of bisphenol C and 74 parts of diallyl bisphenol S (represented as DAL-S in the table, manufactured by Nippon Kayaku Kogyo Co., Ltd.) were used instead of diallyl bisphenol A. was performed to obtain a polycarbonate resin powder. Each property was measured and the results are listed in Table 1.

[Example 3]
1858 parts of bisphenol C, 74 parts of diallyl bisphenol S (TG-SH (H) manufactured by Nippon Kayaku Kogyo Co., Ltd.) instead of diallyl bisphenol A, o-allylphenol (o-AP in the table) instead of p-tert-butylphenol A polycarbonate resin powder was obtained in the same manner as in Example 1, except that 82 parts of the resin (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used. Each property was measured and the results are listed in Table 1.

[Example 4]
Instead of bisphenol C, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (indicated as BP-OCZ in the table, manufactured by Honshu Chemical Industry) 2038 parts, diallyl bisphenol A 184 parts, p- A polycarbonate resin powder was obtained in the same manner as in Example 1 except that 67 parts of tert-butylphenol was used. Each property was measured and the results are listed in Table 1.

[Example 5]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 5016 parts of a 25% aqueous sodium hydroxide solution and 4013 parts of ion-exchanged water. Hydroxy-3-tert-butylphenyl)propane (denoted as BP-OTBPA in the table, manufactured by Honshu Chemical Industry) 1894 parts, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5- After dissolving 296 parts of trimethylcyclohexane (denoted as BP-TMC in the table, manufactured by Honshu Chemical Industry Co., Ltd.) and 4.6 parts of sodium hydrosulfite, 17760 parts of methylene chloride and tetrabutylammonium bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 112 g was added, and 1000 parts of phosgene was blown in at 15 to 25° C. over about 75 minutes while stirring. After the completion of the phosgene blowing, 317 parts of a 25% aqueous sodium hydroxide solution, 31 parts of p-tert-butylphenol and 30 parts of o-allylphenol were added, stirring was resumed, and after emulsification 4.8 parts of triethylamine was added, followed by 26-33 parts. The reaction was completed by stirring at ℃ for 1 hour.

After the completion of the reaction, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water. The washing with water was repeated until the conductivity of the aqueous phase became approximately the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter with a mesh size of 0.3 μm, and is added dropwise to hot water in a kneader with an isolated chamber having a foreign matter removal port in the bearing, and the polycarbonate resin is flaked while distilling off the methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. Each property was measured and the results are listed in Table 1.

[Example 6]
69 parts of diallyl bisphenol S, 303 parts of bisphenol C instead of 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) - 2184 parts of 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane (denoted as BP-OCHPA in the table, manufactured by Honshu Chemical Industry) instead of 3,3,5-trimethylcyclohexane, 1,1- Bis (4-hydroxy-3-methylphenyl) cyclohexane (manufactured by Honshu Kagaku) 2062 parts, p-tert-butylphenol was not added and o-AP was changed to 65 parts, but the same operation as in Example 5 was performed to obtain a polycarbonate. A resin powder was obtained. Each property was measured and the results are listed in Table 1.

[Comparative Example 1]
A reactor equipped with a thermometer, stirrer and reflux condenser was charged with 4190 parts of a 25% aqueous sodium hydroxide solution and 8754 parts of ion-exchanged water, and 1915 parts of bisphenol C and 4.4 parts of sodium hydrosulfite were charged. was dissolved, 8904 parts of methylene chloride was added, and 1000 parts of phosgene was blown in at 15 to 25° C. over about 75 minutes while stirring. After the completion of blowing of phosgene, 599 parts of a 25% aqueous sodium hydroxide solution and 71 parts of p-tert-butylphenol were added, and stirring was resumed. to terminate the reaction.

After the completion of the reaction, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water. The washing with water was repeated until the conductivity of the aqueous phase became approximately the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter with a mesh size of 0.3 μm, and is added dropwise to hot water in a kneader with an isolated chamber having a foreign matter removal port in the bearing, and the polycarbonate resin is flaked while distilling off the methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder. Each property was measured and the results are listed in Table 2.

[Comparative Example 2]
A polycarbonate resin powder was obtained in the same manner as in Example 1 except that 1628 parts of bisphenol C and 346 parts of diallyl bisphenol A were used. Each property was measured and the results are listed in Table 2.

[Comparative Example 3]
The procedure of Example 1 was repeated except that 1858 parts of bisphenol C, 74 parts of diallyl bisphenol S instead of diallyl bisphenol A, and 31 parts of o-allylphenol instead of p-tert-butylphenol were used to obtain a polycarbonate resin powder. got Each property was measured and the results are listed in Table 2.

[Comparative Example 4]
The same operation as in Example 1 was performed except that 1535 parts of bisphenol A (represented as BPA in the table, manufactured by Nippon Steel Chemical), 227 parts of diallyl bisphenol A, and 58 parts of p-tert-butylphenol were used instead of bisphenol C. to obtain a polycarbonate resin powder. Each property was measured and the results are listed in Table 2.

According to the present invention, a polycarbonate resin having a low dielectric constant and a low dielectric loss tangent can be obtained. Furthermore, a cured product having a low coefficient of linear expansion and high strength can be obtained using the polycarbonate resin. Such a cured product is extremely useful as a highly functional polymer material, and as an electrically and thermally excellent material, it is used as an interlayer insulating layer of a printed wiring board, a semiconductor encapsulant, an electrical insulating material, and a copper-clad laminate. It can be used for a wide range of applications such as resins, resists, sealing resins for electronic parts, resins for liquid crystal color filters, paints, various coating agents, adhesives, build-up laminate materials, and FRP.

Claims (12)

Containing a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2), and the proportion of the structural unit (A) in all structural units is 70 mol% or more and a polycarbonate resin that satisfies the following (a) to (c).
(a) the weight average molecular weight of the polycarbonate resin measured by gel permeation chromatography is in the range of 15,000 to 45,000;
(b) The dielectric constant at a frequency of 10 GHz measured according to the cavity resonator perturbation method of polycarbonate resin is in the range of 2.3 to 2.7, and the dielectric loss tangent is in the range of 0.0001 to 0.0030. matter,
(c) the ratio of the structural unit (B) in all structural units of the polycarbonate resin is 1 mol% or more and 10 mol% or less;

(In formula (1), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, Alternatively, it represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R ₃ and R ₄ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or an unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, X is a single bond, substituted or unsubstituted 1 to 20 alkylene group, substituted or unsubstituted alkylidene group having 2 to 20 carbon atoms, substituted or unsubstituted sulfur atom, or oxygen atom.)

(In general formula (2), R ₅ to R ₈ each independently represent a hydrogen atom or an allyl group having 3 to 20 carbon atoms, provided that at least one of R ₅ to R ₈ is a carbon atom an allyl group having a number of 3 to 20. Y is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 20 carbon atoms, a substituted or unsubstituted represents a sulfur atom or an oxygen atom.) The polycarbonate resin according to claim 1, wherein the terminal structure of the polycarbonate resin contains a structure (C) derived from a monohydroxy compound represented by the following formula (3) and accounts for 10 mol% or more of all terminal structures constituting the polycarbonate resin. resin.

(In formula (3), R ₉ is a hydrogen atom, a straight or branched alkyl group having 1 to 9 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, or 1 to 20 carbon atoms. is a linear or branched phenyl-substituted alkyl group, and R ₁₀ is an allyl group having 3 to 20 carbon atoms.) 3. The polycarbonate resin according to claim 1, wherein X in formula (1) is at least one group selected from the group consisting of formula (4) below.

(R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and Z represents a substituted or unsubstituted alkylene group having 4 to 12 carbon atoms.) Y in formula (2) is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, a substituted or unsubstituted alkylidene group having 2 to 12 carbon atoms, or a substituted or unsubstituted sulfur atom. 4. The polycarbonate resin according to any one of 1 to 3. 5. The polycarbonate resin according to any one of claims 1 to 4, wherein the proportion of the structural unit (A) in all structural units of the polycarbonate resin is 80 mol% or more. 6. The polycarbonate resin according to any one of claims 1 to 5, wherein the proportion of the structural unit (B) in all structural units of the polycarbonate resin is 2 mol% or more and 8 mol% or less. R ₁ and R ₂ in the above formula (1) are each at least one group selected from the group consisting of a methyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group and a phenyl group, and R ₃ and R ₄ are The polycarbonate resin according to any one of claims 1 to 6, each of which is a hydrogen atom or a methyl group. The polycarbonate according to any one of claims 1 to 7, wherein R ₅ and R ₆ in formula (2) are allyl groups having 3 to 10 carbon atoms, and R ₇ and R ₈ are hydrogen atoms. resin. The polycarbonate resin according to any one of claims 1 to 8, wherein Y in formula (2) is a sulfide group, a sulfone group or an isopropyl group. The polycarbonate resin according to any one of claims 1 to 9, which is a polycarbonate resin produced by interfacial polycondensation of a dihydroxy compound and carbonyl chloride. A curable resin composition comprising the polycarbonate resin according to any one of claims 1 to 10, a maleimide compound and an inorganic filler. 12. The resin composition according to claim 11, which is used for forming an insulating layer of a printed wiring board.