WO2023181838A1 - Composition for resin starting material, organic solvent solution, curable resin composition, varnish, prepreg, and cured product - Google Patents

Abstract

The present invention addresses the problem of providing a composition for a resin starting material, in order to obtain a cured product that exhibits excellent dielectric characteristics and also a satisfactory mechanical strength and an excellent heat resistance. Provided, as a solution to the problem, is a composition for a resin starting material, comprising 2,2-bis(4-acetoxy-3-allylphenyl)propane (compound (1)) and having a solvent content of not more than 5 weight% and a refractive index at 25°C in the range from 1.546 to 1.551.

Description

Compositions for resin raw materials, organic solvent solutions, curable resin compositions, varnishes, prepregs, cured products

The present invention relates to compositions for resin raw materials, organic solvent solutions, curable resin compositions, varnishes, prepregs, and their curing to obtain cured products having excellent dielectric properties, sufficient mechanical strength, and excellent heat resistance. relating to things.

BACKGROUND ART Bisphenol compounds having an allyl group are used as raw materials for resin materials such as phenol resins, epoxy resins, bismaleimide resins, and polyphenylene ether resins, and for example, diallylbisphenol A is conventionally known.
A compound obtained by modifying the hydroxyl group of a bisphenol compound having an allyl group is also used as such a raw material. For example, it is known that diallyl bisphenol A having an acetyl group is used as a curing agent for epoxy resin (Patent Document 1). ing.

International Publication No. 2008/124797

An object of the present invention is to provide a resin raw material composition for obtaining a cured product having excellent dielectric properties, sufficient mechanical strength, and excellent heat resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have discovered that 2,2-bis(4-acetoxy-3- A composition containing (arylphenyl)propane has excellent dielectric properties, and by using this as a curing agent for curing polyphenylene ether resin, a cured product having sufficient mechanical strength and excellent heat resistance can be obtained. They discovered this and completed the present invention.

The invention is as follows.
1. Contains 2,2-bis(4-acetoxy-3-allylphenyl)propane (compound (1)), has a solvent content of 5% by weight or less, and has a refractive index of 1.546 at 25°C A composition for a resin raw material having a value of 1.551 or less.
2.2-(4-hydroxy-3-allylphenyl)-2-(4-acetoxy-3-allylphenyl)propane (compound (2)) and 2,2-bis(4-hydroxy-3-allylphenyl) ) containing propane (compound (3)); 1. The composition for resin raw materials described in .
3. Based on the area percentage of each peak of the compound (1), compound (2), and compound (3) detected by analyzing the composition for resin raw material by high performance liquid chromatography, according to the following [calculation formula] 2. The calculated acetylation rate is in the range of 60% to 99%. The composition for resin raw materials described in .
[a formula]
Acetylation rate = [(a×2+b)×100×0.5]÷(a+b+c)
a: Area% of compound (1)
b: Area% of compound (2)
c: Area% of compound (3)
4. The total amount of the compounds (1), (2) and (3) contained in the resin raw material composition is relative to the total area of the peaks of all components detected when analyzed by high performance liquid chromatography. , the ratio of the total area of peaks in which compounds (1), (2), and (3) were detected is 75 area% or more; 3. The composition for resin raw materials described in .
5.1. ~4. An organic solvent solution of the resin raw material composition according to any one of the above.
6. A curable resin composition containing component (A) and component (B).
(A): Polyphenylene ether resin (B): At least 1. ~4. 7. A curing agent comprising the resin raw material composition according to any one of 7. 6. Contains component (C). The curable resin composition described in .
(C): Reaction initiator8. 7. further containing component (D); The curable resin composition described in .
(D): Filler 9.6. A varnish containing the curable resin composition described above and component (E).
(E): Solvent 10.6. A prepreg containing the curable resin composition described above and component (F).
(F): Reinforced fiber 11.6. A cured product obtained by curing the curable resin composition described in .
12.10. A cured product obtained by curing the prepreg described in .

The resin raw material composition of the present invention has excellent dielectric properties. When a curing agent containing this is used for curing polyphenylene ether resin, a cured product having sufficient mechanical strength and excellent heat resistance can be obtained. Further, the curable resin composition of the present invention using a curing agent containing this composition for resin raw materials having excellent dielectric properties can provide a cured product having sufficient mechanical strength and excellent heat resistance.

1 is a graph showing the relationship between the refractive index of each of the resin raw material compositions of Examples 1 to 4 and the glass transition temperature of a resin film obtained from them.

The resin raw material composition of the present invention contains 2,2-bis(4-acetoxy-3-allylphenyl)propane (compound (1)), has a solvent content of 5% by weight or less, and has 25% by weight or less. The refractive index at °C is in the range of 1.546 or more and 1.551 or less.
The solvent content in the present invention means a value calculated by HS-GC (headspace gas chromatography) analysis, as explained in the Examples below. The solvent content of the resin raw material composition of the present invention is preferably 3% by weight or less, more preferably 2% by weight or less, and particularly preferably 1% by weight or less.
The refractive index in the present invention means a value measured using a refractometer at 25° C. without a solvent (neat state) of the resin raw material composition, as explained in the examples below. Note that "solvent-free (neat)" does not mean that it is completely free of organic solvents, and it does not mean that it is completely free of organic solvents. It means that the solvent content calculated by is less than 1% by weight. In the examples, the calibration curve created for quantifying the solvent was explained for toluene, but other solvents can also be quantified based on the calibration curve created in the same way.
When a plurality of solvents are contained in the resin raw material composition, the total solvent content that can be quantified by such an analysis method is the solvent content.
The resin raw material composition of the present invention preferably has a refractive index at 25° C. in a range of 1.546 or more and 1.550 or less, more preferably in a range of 1.546 or more and 1.549 or less, and 1.546 Particularly preferred is a range of 1.548 or more.
When measuring the refractive index of the composition for resin raw materials of the present invention, if it is not solvent-free (neat), use HS-GC (headspace gas chromatography) by distillation or evaporation of the solvent. The solvent may be removed so that the solvent content calculated by analysis is less than 1% by weight.

The resin raw material composition of the present invention is a compound of 2-(4-hydroxy-3-allylphenyl)-2-(4-acetoxy-3-allylphenyl)propane (compound (2), which is an intermediate in the acetylation reaction described below). )) or 2,2-bis(4-hydroxy-3-allylphenyl)propane (compound (3)), which is a raw material, may be contained, and the content thereof is determined at 25°C There is no restriction as long as the refractive index is within the above range.
The present inventors have found that the refractive index in the present invention correlates with the content ratio of compounds (1), (2), and (3) each having a different refractive index, and that compound (1), which is a diacetyl compound, and compound (1), which is a monoacetylated compound, It was revealed that the larger the content ratio (acetylation ratio) of a certain compound (2), the lower the refractive index. The acetylation rate in the present invention refers to the compounds (1) and (2) detected by analyzing the resin raw material composition by high performance liquid chromatography (HPLC) under the analysis conditions described in detail in the examples below. , (3) is calculated using the following "calculation formula" based on the area percentage of each peak.
[a formula]
Acetylation rate = [(a×2+b)×100×0.5]÷(a+b+c)
a: Area% of compound (1)
b: Area% of compound (2)
c: Area% of compound (3)
The acetylation rate at which the resin raw material composition of the present invention has a refractive index of 1.546 or more and 1.551 or less at 25° C. is in the range of 60% to 99%. This acetylation rate is preferably in the range of 70% to 99%, more preferably in the range of 80% to 99%, even more preferably in the range of 85 to 99%, and even more preferably in the range of 90% to 99%. Particularly preferred is a range of %.
In addition, the total amount of compounds (1), (2), and (3) contained in the resin raw material composition of the present invention is the peak of all components detected when performing the same HPLC analysis as the acetylated product rate. The ratio of the total area of peaks where compounds (1), (2), and (3) are detected to the total area, preferably 75 area% or more, more preferably 80 area% or more .

As a method for producing the resin raw material composition of the present invention, for example, as shown in the reaction formula below, compound (3) and acetic anhydride are subjected to an acetylation reaction under predetermined conditions to obtain compound (2) as an intermediate. Next, there is a method for obtaining compound (1).
In order to produce the resin raw material composition of the present invention, the conditions for the acetylation reaction described below can be adjusted as appropriate.
The amount of acetic anhydride used is 4,4'-(propane-2,2-diyl)-bis(2-allylphenol)(2,2-bis(4-hydroxy-3-allylphenyl)propane: Compound (3) )) It is generally used in an amount of 2 moles or more, preferably 2 to 5 moles, more preferably 3 to 5 moles, even more preferably 4 to 5 moles, per mole.
During the reaction, a solvent may not be used unless there is a problem with the operability or reaction rate during industrial production. Not only is it economically advantageous to carry out the process without a solvent, but it is also preferable in terms of reducing the solvent content in the resin raw material composition of the present invention. When a solvent is used, there is no particular restriction on the amount of the solvent used, but usually the raw material 4,4'-(propane-2,2-diyl)-bis(2-allylphenol) (2,2-bis( 4-Hydroxy-3-allylphenyl)propane: 0.3 to 10 parts by weight or less, preferably 0.5 to 6 parts by weight, per 1 part by weight of compound (3)). The solvent to be used is not particularly limited as long as it does not adversely affect the reaction, but in order to reduce the solvent content in the resin raw material composition of the present invention, a solvent that can be easily removed by vacuum distillation or the like is preferred. Specifically, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, halogenated hydrocarbons such as dichloroethane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran, cyclopentyl methyl ether, and diphenyl ether. can be mentioned. Such solvents may be used alone or in combination of two or more.
The temperature of the acetylation reaction is usually in the range of 120 to 150°C, preferably in the range of 130 to 140°C. It is preferable to carry out the reaction within this range because the reaction proceeds quickly and is therefore efficient.
The reaction is usually carried out under normal pressure, but depending on the boiling point of the solvent used, the reaction may be carried out under increased pressure or reduced pressure so that the reaction temperature is within the above range.
The acetylation reaction time is in the range of 0.5 to 10 hours.

After the completion of the reaction, the obtained reaction mixture can be used to obtain a resin raw material composition containing the target compound (1) by a known method, and is subjected to water washing, crystallization, filtration, distillation, and column treatment. Purification and isolation can be achieved by performing post-treatment operations such as separation by chromatography.
For example, the resulting reaction mixture is first dissolved in an organic solvent that dissolves the reaction mixture and separates it from water. The organic solvent that can be used may be the solvent used in the above reaction step, the same type of solvent may be added or added, and aliphatic hydrocarbons such as cyclohexane and n-heptane may be used. can be used. In order to reduce the solvent content in the resin raw material composition of the present invention, it is preferable to use a solvent that is easily removed by vacuum distillation or the like, and among them, it is more preferable to use toluene.
The amount of solvent used is in the range of 1 to 5 times the weight of the compound (3) used during the reaction.
An alkaline aqueous solution in which alkaline compounds such as sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate, and potassium carbonate are dissolved is added to the oil layer of the organic solvent solution to produce acetic anhydride, which is a raw material, and a by-product. After sufficient stirring to remove acetic acid from the organic solvent layer, the aqueous layer consisting of an alkaline aqueous solution is separated and removed from the oil layer by standing.
The amount of basic water used is in the range of 1 to 5 times the weight of the compound (3) used during the reaction.
Next, an acid such as phosphoric acid or hydrochloric acid and water are added to the oil layer to neutralize it, and after separating the aqueous layer, water is added and the operations of stirring, standing still, and separating and removing the aqueous layer are performed multiple times. Clean the oil layer.
The solvent is removed from the oil layer that has been sufficiently washed with water by distillation to obtain the desired composition for resin raw material having a solvent content reduced to 5% by weight or less.
In addition to the production method described above, the composition for resin raw materials of the present invention may be prepared by mixing two or more types of compositions for resin raw materials having different refractive indexes, or the composition for resin raw materials of the present invention may be prepared by mixing separately produced compound (1). It may also be prepared by mixing it into a composition.

As described later, the composition for resin raw materials of the present invention can be used as a curing agent for polyphenylene ether resin, and since it has an allyloxy group, it can be used as a raw material for bismaleimide resin, a curable resin that is cured by reaction with a polythiol compound and enethiol. It can be used as a raw material, etc.

The resin raw material composition of the present invention can be made into an organic solvent solution. Examples of organic solvents that can be used include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, halogenated hydrocarbons such as dichloroethane, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε. - Ester solvents such as caprolactone, α-methyl-γ-butyrolactone, butyl acetate, ethyl acetate, and isobutyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; glycols such as diethylene glycol dimethyl ether, triethylene glycol, and triethylene glycol dimethyl ether; Ketone solvents such as cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, diethoxyethane, dibutyl ether, cyclopentyl methyl ether, diphenyl ether, etc. Ether solvents and other general-purpose solvents include acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate. , chloroform, turpentine, mineral spirits, petroleum naphtha-based solvents, etc., and two or more of these may be used as a mixture.

The composition ratio of the composition for resin raw materials and the organic solvent is determined depending on the use of the organic solvent solution as the solid content concentration when the composition for resin raw materials of the present invention is dissolved in an organic solvent to form a solution. There is no particular restriction as it can be selected as appropriate.
Since the resin raw material composition of the present invention is oily, its organic solvent solution must be transported into and discharged from the manufacturing equipment, as well as when the organic solvent solution is packed in a container and stored or transported. In addition, handling becomes easier. It can also be used when preparing a curable resin composition, which will be described later, by uniformly mixing it, or when producing a varnish containing a curable resin composition.

<Component (A)>
The curable resin composition of the present invention contains a polyphenylene ether resin as component (A), and the polyphenylene ether resin that can be used is not particularly limited.
Specific examples of such polyphenylene ether resins include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2- methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g. trimethylphenol, 2-methyl-6-butylphenol, etc.), polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols, bisphenols, or trisphenols, 2,6- Examples include polyphenylene ether copolymers obtained by coupling dimethylphenol and other phenols with biphenols, bisphenols, or trisphenols.
Furthermore, a polyphenylene ether in which the terminal hydroxyl group of the polyphenylene ether resin is modified with a functional group having an unsaturated double bond such as allyl ether, acryloyl, methacryloyl, vinyl ether, etc. may be used, among which, for example, 2, An acrylated product of polyphenylene ether, which is a copolymer of 6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, is preferred.

<Component (B)>
The curable resin composition of the present invention contains at least the composition for resin raw materials of the present invention as a curing agent as component (B), but it is also possible to use only the composition for resin raw materials of the present invention. Alternatively, other conventionally known curing agents may be used in combination, but it is preferable to use only the resin raw material composition of the present invention.
Examples of curing agents that can be used in combination include trialkenyl isocyanurate compounds such as triallylisocyanurate, polyfunctional allyl ether compounds having two or more allyl ether groups in the molecule, and polyfunctional methacrylates having two or more methacrylic groups in the molecule. compounds, polyfunctional acrylate compounds with two or more acrylic groups in the molecule, vinyl compounds (polyfunctional vinyl compounds) with two or more vinyl groups in the molecule, such as polybutadiene, and 2 vinylbenzyl groups in the molecule. Examples include vinylbenzyl compounds having at least 100%.
The content of component (B) in the curable resin composition of the present invention is preferably in the range of 1 to 20 parts by weight, and preferably in the range of 1 to 10 parts by weight, based on 100 parts by weight of component (A). More preferably, the amount is in the range of 1 to 7 parts by weight, and particularly preferably in the range of 1 to 6 parts by weight.

<Component (C)>
The curable resin composition of the present invention preferably contains a reaction initiator as component (C) in addition to component (A) and component (B). Component (C) is added to promote the crosslinking reaction of the curable resin composition containing component (A) and component (B).
Component (C) is not particularly limited as long as it promotes the crosslinking reaction, and examples thereof include imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, and organophosphines. , ionic catalysts such as organophosphonium salts, organic peroxides, hydroperoxides, radical polymerization initiators such as azoisobutyronitrile, and the like. Among these, it is preferable to use organic peroxides.
Examples of organic peroxides include di-t-butyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,2-bis(t-butyl peroxide). fats such as oxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne, di-n-propylperoxydicarbonate, etc. Group organic peroxides, dibenzoyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate, t-butylcumyl peroxide, bis(1-t-butylperoxy-1-methylethyl) ) benzene, 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane, α,α'-di(t-butylperoxy)diisopropylbenzene, α,α'-bis(t-butyl Examples include aromatic organic peroxides containing an aromatic ring, such as peroxy-m-isopropyl)benzene and di-t-butylperoxyisophthalate. Among these, it is preferable to use aromatic organic peroxides.
Examples of aromatic organic peroxides include dicumyl peroxide, t-butylcumyl peroxide, bis(1-t-butylperoxy-1-methylethyl)benzene, 2-phenyl-2-[(2-phenylpropane- 2-yl)peroxy]propane is more preferred, and 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane is particularly preferred.

The curable resin composition of the present invention preferably contains component (C) in an amount of 0.05 to 0.9% by weight based on the total amount of the curable resin composition, and preferably 0.15 to 0.8% by weight. %, more preferably 0.3 to 0.7% by weight, particularly preferably 0.35 to 0.6% by weight.
Component (C) may be used alone or in combination of two or more.

<Component (D)>
The curable resin composition of the present invention preferably contains a filler as component (D) in addition to component (A), component (B), and optionally component (C).
It is preferable to contain component (D) in a range of 10 to 150 parts by weight, more preferably in a range of 10 to 100 parts by weight, based on 100 parts by weight of the curable resin composition.
Component (D) is not particularly limited as long as it is a filler that is normally used in curable resin compositions, and includes, for example, silicon oxide, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, Inorganic fillers such as silicon carbide and hexagonal boron nitride can be used in combination.

<Component (E)>
The curable resin composition of the present invention may contain a solvent as component (E), and is particularly preferably in the form of a varnish in which component (E) is dissolved or dispersed.
Component (E) is not particularly limited as long as it dissolves or disperses the curable resin composition of the present invention, and examples thereof include aromatic compounds such as toluene and xylene, methyl ethyl ketone, cyclopentanone, and cyclohexanone. Examples include ketone compounds and chlorine organic solvents such as chloroform.
Among these, aromatic compounds such as toluene and xylene, ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone are preferred, aromatic compounds such as toluene and xylene are more preferred, and toluene is particularly preferred.
It is preferable to contain component (E) in a range of 50 to 200 parts by weight, more preferably in a range of 70 to 150 parts by weight, based on 100 parts by weight of the curable resin composition.

The method for preparing the curable resin composition of the present invention is not particularly limited, and includes, for example, a method in which the above-mentioned components are mixed and mixed or dispersed using a stirrer.

<Prepreg>
The prepreg of the present invention comprises a curable resin composition containing component (A) and component (B), optionally containing component (C) and further component (D), and a reinforcing component (F). It can be obtained by mixing it with fibers. Examples of the mixing method include a method of applying a varnish containing a curable resin composition to the reinforcing fiber as component (F), a method of impregnating the reinforcing fiber, and the like.

<Component (F)>
Component (F) in the present invention is not particularly limited as long as it is a reinforcing fiber that is normally used in prepregs, and examples include carbon fiber, aramid fiber, nylon fiber, high-strength polyester fiber, glass fiber, boron fiber, Various inorganic fibers or organic fibers such as alumina fibers and silicon nitride fibers can be used. Among these, from the viewpoint of specific strength and specific elasticity, carbon fibers, aramid fibers, glass fibers, boron fibers, alumina fibers, and silicon nitride fibers may be mentioned. Among these, carbon fiber is preferred from the viewpoint of mechanical properties and weight reduction. When using carbon fiber as the reinforcing fiber, surface treatment with metal may be performed.
The thickness of the fiber base material is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.1 mm or less.
Component (F) may be used alone or in combination of two or more.

<Method for producing cured product>
The cured product in the present invention can be obtained by curing the curable resin composition of the present invention.
The method for producing the cured product of the present invention includes, for example, a film of a curable resin composition formed by casting a varnish onto a support such as a polyimide or polyester film or a glass substrate and drying it, or a film of the above-mentioned prepreg. A method of curing by heating to a predetermined temperature, filling a mold etc. with the curable resin composition of the present invention, or heating and melting the curable resin composition of the present invention and injecting it into a mold etc. After that, a method of curing by heating to a predetermined temperature can be mentioned.
The heat curing temperature can be appropriately determined within the range of 105 to 270°C.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
The analysis method in the present invention is as follows.
<Analysis method>
(1) Solvent content of resin raw material composition 0.5 g of the resin raw material composition was weighed, and a solution was prepared by adding 9.5 g of N-methylpyrrolidone (NMP). 3g of it was weighed and put into an HS vial, and analyzed using HS-GC as described below. A calibration curve for toluene was also created from the following analysis conditions, and the solvent content in the resin raw material composition was determined.
(HS-GC analysis conditions)
GC conditions Equipment: Shimadzu Corporation: GC-2010plus
Column: Inert-CaP1 60m x 0.25mmΦ, film thickness 0.25μm
Detector: FID
INJ temperature: 300℃, FID temperature: 310℃
Temperature rising conditions: 40℃ (10 minutes) → 20℃/min → 300℃ (5 minutes)
Column linear velocity: 19.9 cm/sec HS conditions Equipment: PerkinElmer: TurboMatrix HS 40
Carrier gas pressure: 154kPa
Vial heating temperature: 100℃
Injection time: 0.05 minutes

(2) Measurement of refractive index of composition for resin raw material The refractive index of the composition for resin raw material was measured without solvent (neat state) at 25° C. using the following apparatus.
Equipment: Refractometer RA-500 manufactured by Kyoto Electronics Industry Co., Ltd.
(3) Heat resistance evaluation of cured product of curable resin composition: Glass transition temperature (Tg)
The resin film obtained by curing the curable resin composition was measured using the following equipment under the following conditions, and the glass transition temperature (Tg ) was calculated.
Equipment: TMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.
Sample size: width 3mm, length 20mm
Conditions: Under nitrogen atmosphere, load 200 mN, temperature range 30°C to 300°C, heating rate 4°C/min Measurement mode: Tension

(4) Measurement of the acetylated product ratio of the resin raw material composition The acetylated product ratio in the present invention is the compound detected by analyzing the resin raw material composition by high performance liquid chromatography (HPLC) under the following analysis conditions. It was calculated using the following "calculation formula" based on the area percentages of each peak (1), (2), and (3).
[a formula]
Acetylation rate = [(a×2+b)×100×0.5]÷(a+b+c)
a: Area% of compound (1)
b: Area% of compound (2)
c: Area% of compound (3)
<HPLC analysis conditions>
0.1 g of the resin raw material composition was weighed into a 50 mL volumetric flask and diluted with methanol. Perform purity analysis of the prepared sample by high performance liquid chromatography as described below, determine the area percentage of each peak of compound (1), compound (2), and compound (3), and calculate the acetylation rate using the above "calculation formula". was calculated.
Purity analysis (analysis value is area percentage)
Measuring device: High performance liquid chromatography analyzer Prominence UFLC (manufactured by Shimadzu Corporation)
Pump: LC-20AD
Column oven: CTO-20A
Detector: SPD-20A
Column: HALO-C18 (inner diameter 3mm, length 75mm)
Oven temperature: 50℃
Flow rate: 0.7mL/min
Mobile phase: (A) 0.1 volume % acetic acid aqueous solution, (B) methanol Gradient conditions: (A) Volume % (time from start of analysis) 50% (0 min) → 100% (7.5 min) → 100% ( 20min)
Sample injection volume: 5μL
Detection wavelength: 280nm

<Example 1>
(a) Production of a resin raw material composition containing compound (1) 2.0 g of 2,2-bis(4-hydroxy-3-allylphenyl)propane (3) was placed in a test tube and the mixture was heated at 38 to 42°C. While maintaining the temperature, 2.6 g of acetic anhydride was added, and then the reaction temperature was raised to 138 to 142°C, and the mixture was stirred at the same temperature for 3.5 hours. After the reaction was completed, the mixture was cooled to 40° C., and 2.0 g of toluene as a solvent and 10.3 g of a 20% aqueous sodium carbonate solution for washing the oil layer were added and stirred. After standing still, the aqueous layer was removed. The inorganic salts were removed by adding 2.0 g of water to the obtained oil layer, stirring it, allowing it to stand, and then removing the aqueous layer twice. The solvent of the obtained oil layer was removed by vacuum distillation to obtain an oily resin raw material composition containing 2,2-bis(4-acetoxy-3-allylphenyl)propane (1).
The analysis results based on the above analysis method are shown below.
Amount of remaining solvent: 0.1% by weight or less Acetic anhydride as a raw material and acetic acid as a by-product were not detected, and toluene used for post-reaction treatment was 0.1% by weight or less.
Refractive index: 1.5462
Acetylated product rate: 97.3% (HPLC area %: compound (1) 77.8%, compound (2) 3.4%, compound (3) 0.5%)

(b) Production of a curable resin composition and its cured product Component (A) is a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane. 100 parts by weight of an acrylate of a certain polyphenylene ether (hereinafter referred to as PPE resin A), 100 parts by weight of toluene as component (E), and 5 parts of the resin raw material composition produced in the above (a) as component (B). .5 parts by weight, and 0.68 parts by weight of dicumyl peroxide, a peroxide (manufactured by NOF Corporation: trade name "Percumyl D") as a reaction initiator for component (C), and stirred with a magnetic stirrer. The mixture was stirred at room temperature to prepare a varnish.
The prepared varnish was applied to a thickness of 0.2 mm on a 20 cm square polyimide film (manufactured by Ube Industries, Ltd., trade name "Upilex") and dried at room temperature. The solvent remaining on the coating film of the curable resin composition was removed by drying at 105° C. for 1 hour using a vacuum dryer, thereby obtaining a semi-cured product of the curable resin composition.
After that, a formwork of aluminum foil (thickness: 0.12mm) with a hole of 9cm x 4cm was made, the semi-cured product was sandwiched from both sides, and both sides were covered with another two polyimide films. It was sandwiched between two 25 cm x 25 cm metal plates from both sides. Thereafter, curing was performed using a vacuum heat press machine (manufactured by Toyo Seiki Co., Ltd.) (heating temperature 105°C, pressure 10MPa, 30 minutes; heating temperature 150°C, pressure 10MPa, 1 hour; heating temperature 200°C, pressure 10MPa, 1 hour). Time: heating temperature 250°C, pressure 10MPa, 1 hour; heating temperature 270°C, pressure 10MPa, 1 hour). The polyimide film adhering to the obtained cured product was removed to obtain a resin film.
The glass transition temperature (Tg) of the obtained resin film was measured based on the above analysis method and was found to be 200.9°C.

<Example 2>
A resin raw material composition was obtained by the same manufacturing method as in Example 1 (a) except that the stirring time after heating was changed to 1 hour. Further, a resin film was obtained based on the same manufacturing method as in Example 1 (b) above.
The analysis results based on the above analysis method are shown below.
Amount of remaining solvent: 0.1% by weight or less Acetic anhydride as a raw material and acetic acid as a by-product were not detected, and toluene used for post-reaction treatment was 0.1% by weight or less.
Refractive index: 1.5474
Acetylated product rate: 82.0% (HPLC area %: compound (1) 54.8%, compound (2) 26.5%, compound (3) 1.7%)
Glass transition temperature (Tg) of resin film: 170.8°C

<Example 3>
Using the resin raw material compositions obtained in Example 1 and Example 2 above, resin raw material compositions having the following refractive index were prepared. Using this, a resin film was obtained by the same manufacturing method as in Example 1 (b) above.
The analysis results based on the above analysis method are shown below.
Amount of remaining solvent: 0.1% by weight or less Acetic anhydride as a raw material and acetic acid as a by-product were not detected, and toluene used for post-reaction treatment was 0.1% by weight or less.
Refractive index: 1.5467
Acetylated product rate: 88.5% (HPLC area %: compound (1) 67.1%, compound (2) 16.0%, compound (3) 1.8%)
Glass transition temperature (Tg) of resin film: 181.7°C

<Example 4>
A resin raw material composition was obtained by the same manufacturing method as in Example 1 (a) except that the stirring time after heating was changed to 30 minutes. Further, a resin film was obtained based on the same manufacturing method as in Example 1 (b) above.
The analysis results based on the above analysis method are shown below.
Amount of remaining solvent: 0.1% by weight or less Acetic anhydride as a raw material and acetic acid as a by-product were not detected, and toluene used for post-reaction treatment was 0.1% by weight or less.
Refractive index: 1.5504
Acetylated product rate: 61.0% (HPLC area %: compound (1) 27.9%, compound (2) 56.7%, compound (3) 7.7%)
Glass transition temperature (Tg) of resin film: 160.9°C

<Comparative example 1>
A resin raw material composition was obtained by the same manufacturing method as in Example 1 (a) except that the stirring time after temperature rise was set to 0 minutes. Further, a resin film was obtained based on the same manufacturing method as in Example 1 (b) above.
The analysis results based on the above analysis method are shown below.
Amount of remaining solvent: 0.1% by weight or less Acetic anhydride as a raw material and acetic acid as a by-product were not detected, and toluene used for post-reaction treatment was 0.1% by weight or less.
Refractive index: 1.5657
Acetylated product rate: 28.0% (HPLC area %: compound (1) 3.5%, compound (2) 47.4%, compound (3) 46.1%)
Glass transition temperature (Tg) of resin film: The obtained film was brittle and could not be measured.

<Comparative example 2>
A resin film was obtained using 2,2-bis(4-hydroxy-3-allylphenyl)propane (3) based on the same manufacturing method as in Example 1 (b) above.
The analysis results based on the above analysis method are shown below.
Refractive index: 1.5870
Acetylated product rate: 0% (HPLC area %: compound (1) 0%, compound (2) 0%, compound (3) 95.6%)
Glass transition temperature (Tg) of resin film: The obtained film was brittle and could not be measured.

From the analysis results of Examples 1 to 4 and Comparative Examples 1 and 2, it was found that as the content ratio (acetylated product ratio) of compound (1) and compound (2) increases, the refractive index of the resin raw material composition decreases. confirmed.
According to Maxwell's equations, the relationship between the dielectric constant (ε) of the dielectric properties of a substance and the refractive index (n) of the substance is ``ε=n ² '' (this relational expression is, for example, Shogo Saito, Electronic Photography, Vol. 11, No. 1, pp. 26-32, 1972). That is, it can be said that the lower the refractive index of a substance, the lower the dielectric constant of that substance.
That is, compared to the resin raw material composition of Comparative Example 1 and the 2,2-bis(4-hydroxy-3-allylphenyl)propane used in Comparative Example 2, the resin raw material composition of the present invention has a dielectric property. It has been revealed that this material has a low dielectric constant and excellent dielectric properties.

The resin raw material composition of Comparative Example 1 and the cured product of the polyphenylene ether resin using 2,2-bis(4-hydroxy-3-allylphenyl)propane used in Comparative Example 2 only yielded brittle films. The mechanical strength was so insufficient that the glass transition temperature could not be measured by TMA analysis under tensile load.
On the other hand, when the resin raw material composition of the present invention is used, the glass transition temperature can be measured by TMA analysis under tensile load, and it has been revealed that the composition has sufficient mechanical strength.
The relationship between the refractive index of the resin raw material compositions of Examples 1 to 4 and the glass transition temperature of the resin film obtained from them is shown in FIG.
As shown in Figure 1, the resin raw material composition of the present invention having a refractive index in the range of 1.546 or more and 1.551 or less has a glass transition temperature of 160°C or more of the polyphenylene ether resin film obtained using the composition. It became clear that a cured product with excellent heat resistance could be obtained.
It has been revealed that when the composition for resin raw materials of the present invention is used for curing polyphenylene ether resin, a cured product having sufficient mechanical strength and excellent heat resistance can be obtained. It has also been revealed that the curable resin composition of the present invention contains a resin raw material composition with excellent dielectric properties, and can yield a cured product having sufficient mechanical strength and excellent heat resistance. Due to these properties, the curable resin composition using a curing agent containing the resin raw material composition having excellent dielectric properties of the present invention can be used as a substrate material for a printed wiring board, for example, to produce a printed wiring board with excellent electrical properties. You can expect to get.

Claims (12)

Contains 2,2-bis(4-acetoxy-3-allylphenyl)propane (compound (1)), has a solvent content of 5% by weight or less, and has a refractive index of 1.546 or more at 25°C. .551 or less, a composition for resin raw materials. 2-(4-hydroxy-3-allylphenyl)-2-(4-acetoxy-3-allylphenyl)propane (compound (2)) and 2,2-bis(4-hydroxy-3-allylphenyl)propane The composition for resin raw material according to claim 1, which contains (compound (3)). Based on the area percentage of each peak of the compound (1), compound (2), and compound (3) detected by analyzing the composition for resin raw material by high performance liquid chromatography, according to the following [calculation formula] The resin raw material composition according to claim 2, wherein the calculated acetylation rate is in the range of 60% to 99%.
[a formula]
Acetylation rate = [(a×2+b)×100×0.5]÷(a+b+c)
a: Area% of compound (1)
b: Area% of compound (2)
c: Area% of compound (3) The total amount of the compounds (1), (2) and (3) contained in the resin raw material composition is relative to the total area of the peaks of all components detected when analyzed by high performance liquid chromatography. 4. The resin raw material composition according to claim 3, wherein the ratio of the total area of peaks in which compounds (1), (2), and (3) are detected is 75 area % or more. An organic solvent solution of the resin raw material composition according to any one of claims 1 to 4. A curable resin composition containing component (A) and component (B).
(A): Polyphenylene ether resin (B): Curing agent containing at least the composition for resin raw material according to any one of claims 1 to 4. The curable resin composition according to claim 6, containing component (C).
(C): Reaction initiator The curable resin composition according to claim 7, further comprising component (D).
(D): Filler A varnish containing the curable resin composition according to claim 6 and component (E).
(E): Solvent A prepreg containing the curable resin composition according to claim 6 and component (F).
(F): Reinforced fiber A cured product obtained by curing the curable resin composition according to claim 6. A cured product obtained by curing the prepreg according to claim 10.