WO2022034753A1 - Manufacturing method for resin having vinyl group, resin having vinyl group, curable resin composition, and cured product - Google Patents

Manufacturing method for resin having vinyl group, resin having vinyl group, curable resin composition, and cured product Download PDF

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Publication number
WO2022034753A1
WO2022034753A1 PCT/JP2021/025106 JP2021025106W WO2022034753A1 WO 2022034753 A1 WO2022034753 A1 WO 2022034753A1 JP 2021025106 W JP2021025106 W JP 2021025106W WO 2022034753 A1 WO2022034753 A1 WO 2022034753A1
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Prior art keywords
resin
vinyl group
group
equivalent
styrene
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PCT/JP2021/025106
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French (fr)
Japanese (ja)
Inventor
与一 ▲高▼野
拓矢 魚谷
祥一 伊藤
享 印南
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三菱瓦斯化学株式会社
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Publication of WO2022034753A1 publication Critical patent/WO2022034753A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes

Definitions

  • the present invention relates to a method for producing a resin having a vinyl group, a resin having a vinyl group, a curable resin composition, and a cured product.
  • Resins having a vinyl group such as vinylbenzyl ether compounds are excellent in dielectric properties, heat resistance, and low hygroscopicity, and are therefore used as materials for electronic devices that handle high-frequency signals.
  • a vinylbenzyl ether compound and a method for producing the same for example, those disclosed in Patent Document 1 and Patent Document 2 are known.
  • JP-A-2019-157015 Japanese Unexamined Patent Publication No. 8-120039
  • An object of the present invention is to solve such a problem, a method for producing a resin having a novel vinyl group having excellent heat resistance and excellent dielectric properties, a resin having a novel vinyl group, and a resin having a novel vinyl group.
  • a method for producing a resin having a vinyl group which comprises reacting a terpenphenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group in the presence of a basic compound.
  • ⁇ 2> The method for producing a resin having a vinyl group according to ⁇ 1>, wherein the basic compound contains at least one of an alkali metal alkoxide and an alkali metal hydroxide.
  • ⁇ 3> The method for producing a resin having a vinyl group according to ⁇ 1> or ⁇ 2>, wherein the styrene having a methyl halide group contains a compound represented by the formula (1).
  • Equation (1) (In formula (1), X represents chlorine or bromine.)
  • ⁇ 4> The method for producing a resin having a vinyl group according to any one of ⁇ 1> to ⁇ 3>, wherein the styrene having a methyl halide group contains metachloromethylstyrene and / or parachloromethylstyrene. .. ⁇ 5>
  • Mn number average molecular weight
  • a method for producing a resin having a vinyl group One of ⁇ 1> to ⁇ 5>, wherein the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq has a styrene-equivalent weight average molecular weight (Mw) of 650 or more and 1,200 or less.
  • Mw styrene-equivalent weight average molecular weight
  • Equation (2) (In formula (2), * indicates a binding site with another structural unit or end group.)
  • Equation (3) (In formula (3), * indicates a binding site with another structural unit or terminal group.
  • m, n and o independently represent the molar ratio of the structural unit, and m is a number of 1 or more.
  • N is a number of 1 or more, and o represents a number of 0 or more.
  • Mn number average molecular weight
  • Mw styrene-equivalent weight average molecular weight
  • thermosetting compound is selected from compounds other than the resin having a vinyl group according to any one of ⁇ 7> to ⁇ 11> and having a carbon-carbon unsaturated bond group and an epoxy resin.
  • the curable resin composition according to ⁇ 13> which comprises at least one thereof.
  • ⁇ 15> The cured product of the curable resin composition according to any one of ⁇ 12> to ⁇ 14>.
  • a method for producing a resin having a novel vinyl group having excellent heat resistance and excellent dielectric properties, a resin having a novel vinyl group, and a curable resin composition using the resin having the vinyl group It has become possible to provide products and cured products.
  • the present embodiment will be described in detail.
  • the following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
  • "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
  • various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
  • the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the notation that does not describe substitution and non-substitution is preferably non-substitution.
  • the method for producing a resin having a vinyl group according to the present embodiment includes reacting a terpenephenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group in the presence of a basic compound. It is characterized by that. With such a configuration, a resin having a vinyl group having excellent heat resistance and excellent dielectric properties can be obtained.
  • a terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is used.
  • the reaction with styrene having a methyl halide group can be effectively promoted, and the vinyl group can be effectively introduced into the terpene phenol resin.
  • the amount of hydroxyl groups remaining in the obtained resin having a vinyl group can be reduced, and the dielectric properties can be further improved.
  • the hydroxyl group equivalent to 580 g / eq or less, a resin having better heat resistance can be obtained.
  • the effects of low dielectric property and high heat resistance derived from the alicyclic structure can be more effectively achieved.
  • the hydroxyl group equivalent of the terpene phenol resin is 260 g / eq or more, preferably 270 g / eq or more, and more preferably 280 g / eq or more.
  • the hydroxyl group equivalent of the terpene phenol resin is 580 g / eq or less, preferably 560 g / eq or less, and more preferably 540 g / eq or less.
  • only one kind of terpene phenol resin may be used, or two or more kinds may be used. When two or more kinds are used, the hydroxyl group equivalent of the mixture is in the above range. The hydroxyl group equivalent is measured according to the description of Examples described later.
  • the terpene phenol resin used in the production method of the present embodiment preferably has a styrene-equivalent number average molecular weight (Mn) of 400 or more, more preferably 500 or more, and further preferably 520 or more.
  • Mn styrene-equivalent number average molecular weight
  • the number average molecular weight (Mn) is preferably 900 or less, more preferably 700 or less, and even more preferably 680 or less.
  • the solvent solubility is improved, the melt viscosity of the resin is lowered, and the handleability of the resin tends to be further improved.
  • the terpene phenol resin used in the production method of the present embodiment preferably has a styrene-equivalent weight average molecular weight (Mw) of 650 or more, and more preferably 760 or more.
  • Mw styrene-equivalent weight average molecular weight
  • the weight average molecular weight (Mw) is preferably 1,200 or less, and more preferably 1,050 or less.
  • the weight average molecular weight and the number average molecular weight of the terpene phenol resin are measured according to the methods described in Examples described later.
  • Examples of the terpene phenol resin used in the production method of the present embodiment include those having a terpene compound-derived structural unit (b1) and a phenol compound-derived structural unit (b2).
  • Examples of the terpene compound include monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (including d-form, l-form and d / l-form (dipentene)).
  • Examples of the phenol compound include phenol, m-cresol, o-cresol, p-cresol, 2,6-xylenol, p-tert-butylphenol and the like.
  • the terpene phenol resin used in the production method of the present embodiment may or may not have a structural unit other than the above-mentioned structural unit (b1) and the structural unit (b2).
  • the constituent unit (b1) and the constituent unit (b2) preferably occupy 90 mol% or more of all the constituent units excluding the terminal group, and 95 to 100 mol%. It is more preferably occupied, more preferably 98 to 100 mol%, and may be 100 mol%.
  • the constituent unit (b1), the constituent unit (b2), and the constituent units other than these may be only one type, or two or more types, respectively. It may be.
  • the structural unit (b1) and the structural unit (b2) may be a random polymer or a block polymer.
  • the terpene phenol resin is preferably a resin containing a structural unit represented by the following formula (TP1). Equation (TP1)
  • R 11 to R 13 represent hydrocarbon groups having 1 to 20 carbon atoms which may independently have substituents
  • R 10 represents a substituent
  • m1 and n1 are molar ratios. Represents an integer of 1 or more independently, and s represents an integer of 0 to 3.
  • R 11 to R 13 represent hydrocarbon groups having 1 to 20 carbon atoms which may independently have substituents. Examples of the substituent contained in the hydrocarbon group represented by R 11 to R 13 include a halogen atom and the like.
  • the hydrocarbon group represented by R 11 to R 13 is preferably an unsubstituted hydrocarbon group. Examples of the hydrocarbon group represented by R 11 to R 13 include an alkyl group and an aryl group, and an alkyl group is preferable.
  • the number of carbon atoms of the hydrocarbon group represented by R 11 to R 13 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and even more preferably 1. It is particularly preferable that R 11 to R 13 are methyl groups.
  • R 10 represents a substituent.
  • substituents include an alkyl group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a halogen atom and the like.
  • m1 and n1 indicate a molar ratio, and each represents an integer of 1 or more.
  • the molar ratio of m1: n1 is preferably 1 to 6: 1, more preferably 2 to 5: 1.
  • the structural unit derived from the terpene compound and the structural unit derived from the phenol compound may be a block polymer or a random polymer.
  • the terminal of the terpene phenol resin represented by the formula (TP1) is preferably a terpene chain or a hydrogen atom.
  • the resin containing the structural unit represented by the formula (TP1) may contain a structural unit other than the structural unit represented by the formula (TP1) as long as it does not deviate from the gist of the present invention.
  • the structural unit represented by the formula (TP1) preferably occupies 90 mol% or more of all the structural units excluding the terminal group, and is 95 to 100 mol%. It is more preferable to occupy 98 to 100 mol%, and it may be 100 mol%.
  • the structural unit represented by the formula (TP1) may be only one kind or two or more kinds.
  • a typical structure of the terpene phenol resin used in this embodiment is represented by the following formula (TP2).
  • Equation (TP2) In the formula (TP2), m2 and n2 represent molar ratios, and each represents an integer of 1 or more. m2: n2 is preferably 1 to 6: 1 and more preferably 2 to 5: 1.
  • the terpene-derived structural unit and the phenol-derived structural unit may be a block polymer or a random polymer.
  • the terminal of the terpene phenol resin represented by the formula (TP2) is preferably a terpene chain or a hydrogen atom.
  • the resin containing the structural unit represented by the formula (TP2) may contain a structural unit other than the structural unit represented by the formula (TP2) as long as it does not deviate from the gist of the present invention.
  • the structural unit represented by the formula (TP2) preferably occupies 90 mol% or more of all the structural units excluding the terminal group, and 95 to 100 mol%. It is more preferably occupied, more preferably 98 to 100 mol%, and may be 100 mol%.
  • the structural unit represented by the formula (TP2) may be only one kind or two or more kinds.
  • styrene having a methyl halide group is used.
  • a resin having a vinyl group can be obtained by reacting with a hydroxyl group having a terpenphenol resin having a hydroxyl group equivalent of 260 to 580 g / eq.
  • the styrene having a methyl halide group contains the compound represented by the formula (1).
  • a resin having a vinyl group having more excellent performance can be obtained.
  • Equation (1) (In formula (1), X represents chlorine or bromine.) In the formula (1), X is preferably chlorine.
  • the styrene having a methyl halide group is preferably metachloromethylstyrene and / or parachloromethylstyrene.
  • the number of moles of styrene having a methyl halide group is preferably 1 to 2 mol with respect to 1 mol of the hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq. More preferably, it is .03 to 1.3 mol.
  • a terpenphenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and styrene having a methyl halide group are reacted in the presence of a basic compound.
  • a basic compound By reacting in the presence of a basic compound, the reaction between the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and the styrene having a methyl halide group proceeds.
  • the basic compound preferably contains at least one of an alkali metal alkoxide and an alkali metal hydroxide, more preferably an alkali metal hydroxide.
  • the alkali metal hydroxide is preferably used as an aqueous solution from the viewpoint of reactivity.
  • the alkali metal include lithium, potassium and sodium, and sodium is preferable.
  • the alkoxide constituting the alkali metal alkoxide include methoxide and ethoxide.
  • the total amount of the alkali metal alkoxide and the alkali metal hydroxide added to the reaction system is 1.5 to 5 with respect to 1 mol of the hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq. It is preferably mol, more preferably 3.5 to 4.7 mol.
  • the basic compound (particularly, the alkali metal alkoxide and the alkali metal hydroxide) may be added to the reaction system at one time, or may be added in two or more times. good.
  • phase transfer catalyst when an alkali metal hydroxide is used, a phase transfer catalyst may be used in combination. Tetrabutylammonium bromide is exemplified as the phase transfer catalyst.
  • the reaction between the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and the styrene having a methyl halide group is preferably carried out at 50 to 80 ° C.
  • a solvent when reacting the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group.
  • the solvent can be appropriately determined depending on the type of the basic compound used.
  • the solvent is exemplified by aromatic hydrocarbons (preferably toluene) and water. More specifically, it is preferable to add an aqueous solution of an aromatic hydrocarbon and an alkali metal hydroxide to the reaction system for use.
  • the solvent is preferably an aprotic polar solvent.
  • the resin obtained after the reaction between the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and styrene having a methyl halide group it is preferable to separate and purify the resin obtained after the reaction between the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and styrene having a methyl halide group. Separation and purification can be performed according to a conventional method.
  • the resin having a vinyl group of the present embodiment is a resin in which at least a part of the phenolic hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is modified with a vinylbenzyl group.
  • a resin having a vinyl group has excellent heat resistance and also excellent dielectric properties.
  • the resin having a vinyl group of the present embodiment is preferably a resin having a structural unit represented by the formula (2).
  • Equation (2) (In formula (2), * indicates a binding site with another structural unit or end group.)
  • the resin having the structural unit represented by the formula (2) usually contains a structural unit (b1) derived from a terpene compound in addition to the above structural unit, and further contains a structural unit (b2) derived from a phenol compound. May be good.
  • the terminal group of the resin having the structural unit represented by the formula (2) is preferably a chain derived from a terpene compound or a hydrogen atom.
  • the resin having a vinyl group of the present embodiment preferably has a structural unit represented by the formula (3).
  • Equation (3) (In formula (3), * indicates a binding site with another structural unit or terminal group.
  • m, n and o independently represent the molar ratio of the structural unit, and m is a number of 1 or more.
  • N is a number of 1 or more, and o represents a number of 0 or more.)
  • m is a number of 1 or more
  • n is a number of 1 or more
  • o is a number of 0 or more.
  • the molar ratio of n: m is preferably 1: 1 to 6, more preferably 1: 2 to 5.
  • o is preferably 0.023 or less, more preferably 0.018 or less.
  • the total of m, n and o is preferably 90 mol or more, more preferably 95 mol or more, and 98 mol or more, when the total constituent unit in the present embodiment is 100 mol. Is more preferable.
  • m, n and o are in a range satisfying the number average molecular weight and the weight average molecular weight in terms of styrene.
  • the terminal group is preferably a chain derived from a terpene compound or a hydrogen atom.
  • each structural unit may be a block polymer or a random polymer.
  • the resin having a vinyl group of the present embodiment may contain a structural unit other than the structural unit represented by the formula (3) as long as it does not deviate from the gist of the present invention.
  • each structural unit in the formula (3) may be only one kind or two or more kinds.
  • the resin having a vinyl group of the present embodiment preferably has a styrene-equivalent number average molecular weight (Mn) of 700 or more, and more preferably 800 or more.
  • Mn styrene-equivalent number average molecular weight
  • the number average molecular weight (Mn) is preferably 1,200 or less, more preferably 1,000 or less.
  • the resin having a vinyl group of the present embodiment preferably has a styrene-equivalent weight average molecular weight (Mw) of 1,000 or more, and more preferably 1,100 or more.
  • Mw styrene-equivalent weight average molecular weight
  • the weight average molecular weight (Mw) is preferably 1,500 or less, and more preferably 1,400 or less.
  • the weight average molecular weight and the number average molecular weight of the resin having a vinyl group of this embodiment are measured according to the methods described in Examples described later.
  • the resin having a vinyl group of the present embodiment preferably has a hydroxyl group equivalent of 15,000 g / eq or more, and more preferably 20,000 g / eq or more.
  • a hydroxyl group equivalent 15,000 g / eq or more, and more preferably 20,000 g / eq or more.
  • the resin having a vinyl group of the present embodiment is a resin obtained by reacting a terpenephenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group in the presence of a basic compound. It is preferable to have. That is, it is preferable that the resin is produced according to the method for producing a resin having a vinyl group according to the present embodiment.
  • the resin having a vinyl group of this embodiment can be used as a curable resin composition.
  • the curable resin composition may consist of only one or more kinds of resins having a vinyl group of the present embodiment, and further, a thermosetting compound other than the resin having a vinyl group of the present embodiment. May include.
  • the thermosetting compound preferably contains at least one compound selected from a compound having a carbon-carbon unsaturated bond group and an epoxy resin, which is a compound other than the resin having a vinyl group of the present embodiment.
  • the curable resin composition may contain one kind or two or more kinds of various additives.
  • Additives include flame retardants, UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoaming agents, and dispersions. Examples thereof include agents, leveling agents, brighteners, polymerization inhibitors and the like.
  • the cured product of the present embodiment is a cured product of the curable resin composition. Since such a cured product has excellent heat resistance and dielectric properties, it can be suitably used as an insulating layer for a printed wiring board and a material for a semiconductor package.
  • ⁇ Measurement of hydroxyl group equivalent of terpene phenol resin was measured according to the following method. Weigh 3 g of terpene phenol resin in an iodine flask (6 g for a resin having a hydroxyl equivalent of 1,000 g / eq or more), and add 15 mL of a separately prepared acetylation reagent (10% by volume acetic anhydride pyridine solution) to dissolve the resin. I let you. An iodine flask with a stopper was immersed in an oil bath at 95 ° C to 100 ° C, and the mixture was heated and stirred for 1 hour.
  • the mixture was air-cooled, the content solution was transferred to a conical beaker having a volume of 300 mL, washed with 5 mL of toluene, 20 mL of pure water, and 40 mL of 2-butanone, and the content solution adhering to the iodine flask was recovered. Twenty mL of a 1 mol / L NaOH aqueous solution was accurately measured, added to a conical beaker and thoroughly mixed, and then titration was performed using a 0.2 mol / L NaOH aqueous solution using a phenolphthalein solution as an indicator.
  • Equation (i) Factor of 0.2 mol / LNaOH The unit of hydroxyl group equivalent is shown in g / eq.
  • the number average molecular weight and the weight average molecular weight of the terpene phenol resin and the vinylbenzyl ether compound were determined by the gel permeation chromatography (GPC) method. Showa Denko Corporation, KF-801, KF-802, KF-803, KF-804 are connected and used for the analysis column, and the differential refractometer RID-20A, manufactured by Shimadzu Corporation, is used for detection. Using.
  • the resin to be measured (terpene phenol resin, vinyl benzyl ether compound) was dissolved in 2 mL of the eluent in tetrahydrofuran, the injection amount into the column was 20 ⁇ L, the eluent flow rate was 1 mL / min, and the analysis was performed at a column temperature of 40 ° C. went.
  • a molecular weight calibration curve was created using the standard polystyrene PStQuick MP-N manufactured by Tosoh Corporation, and the polystyrene-equivalent molecular weight was estimated.
  • Dichloromethane used was an ultra-dehydrated grade manufactured by Wako Pure Chemical Industries, Ltd.
  • the absorbance was measured using FT-IR (Nicolet 6700) manufactured by Thermo Fisher Scientific.
  • ⁇ 1 1 H-NMR analysis> The 1 H-NMR of the resin having a vinyl group was measured in a deuterium-substituted chloroform solvent using a nuclear magnetic resonance apparatus manufactured by BRUKER and AVANCEII 600 MHz as an apparatus.
  • ⁇ (ppm) described later indicates a chemical shift represented by the following equation.
  • ⁇ (ppm) 106 ⁇ ( ⁇ S - ⁇ R ) / ⁇ R ⁇ S : Resonance frequency (Hz) of the sample ⁇ R : Resonance frequency (Hz) of standard substance trimethylsilane (TMS)
  • Example 1 Toluene phenol resin YS Polystar K125 (manufactured by Yasuhara Chemical Industries, Ltd., hydroxyl weight equivalent 311 g / eq, styrene equivalent number average molecular weight 550, styrene equivalent weight average molecular weight 789) in a reaction vessel with a volume of 500 mL equipped with a stirrer, thermometer and perfusion tube.
  • the obtained solution was concentrated with a rotary evaporator, diluted with 319.1 g of 2-butanone (Fuji Film Wako Pure Chemical Industries, Ltd., special grade), and solidified by dropping into methanol.
  • the separated solid was washed with pure water and then with methanol, washed again with pure water and methanol, and dried under reduced pressure to obtain 21.7 g of the target vinyl benzyl ether compound A.
  • novel peaks derived from the vinylbenzyl ether skeleton were observed at 5.02 ppm, 5.25 ppm, 5.74 ppm, 5.78 ppm, and 6.7 to 7.2 ppm.
  • the number average molecular weight of the vinylbenzyl ether compound A was 857, the weight average molecular weight was 1,230, and the hydroxyl group equivalent was 77,000.
  • Example 2 Toluene phenol resin YS Polystar G125 (manufactured by Yasuhara Chemical Co., Ltd., hydroxyl equivalent 476 g / eq, styrene equivalent number average molecular weight 650, styrene equivalent weight average molecular weight 1) in a reaction vessel with a volume of 500 mL equipped with a stirrer, thermometer and perfusion tube. , 029) 33.4 g, toluene 246.6 g, sodium hydroxide aqueous solution 26.8 g, and pure water 28.6 g were charged and heated and stirred at 70 ° C.
  • Styrene equivalent weight average molecular weight 925 49.96 g, N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) 150 g, chloromethylstyrene CMS-P 23.3 g, and the liquid temperature is 50 ° C. The temperature was raised to 1 and the mixture was heated and stirred. While maintaining the liquid temperature at 50 ° C., 29.5 mL of sodium methoxide (28.3% by mass methanol aqueous solution manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 70 minutes.
  • the filtrate was washed with 81.6 g of N, N-dimethylacetamide, and the obtained filtrate was added dropwise to 247.5 g of pure water to solidify the filtrate. After washing with Yakuhin Co., Ltd. (Wako First Class), it was redistributed in 220 g of methanol. The solid was separated by filtration again, washed with methanol and dried under reduced pressure to obtain 55.83 g of a resin having a vinyl group (vinyl benzyl ether compound C).
  • the filtrate was washed with 190 g of N, N-dimethylacetamide, the obtained filtrate was added dropwise to 347 g of pure water to solidify it, and the filtered solid was washed with pure water and then methanol, and then to 309 g of methanol. Redistributed.
  • the solid was separated by filtration again, washed with methanol and dried under reduced pressure to obtain 41.25 g of a resin having a vinyl group (vinyl benzyl ether compound D).
  • the organic phase and the aqueous phase were separated, and the organic phase was washed with a 1.4 mass% sulfuric acid aqueous solution and then a 30 mass% methanol aqueous solution.
  • the obtained solution was concentrated with a rotary evaporator, diluted with 228.5 g of 2-butanone (Fuji Film Wako Pure Chemical Industries, Ltd., special grade), and solidified by dropping into methanol.
  • the separated solid was washed with pure water and then with methanol, washed again with pure water and methanol, and dried under reduced pressure to obtain 32.0 g of a resin (vinyl benzyl ether compound E) having a target vinyl group.
  • Example 3 The vinyl benzyl ether compound A (4.5 g) obtained above was placed in a mold having a length of 100 mm, a width of 30 mm and a thickness of 1 mm, and used at 200 ° C. using a 5-stage press machine VH2-1630 manufactured by Kitagawa Seiki Co., Ltd. , Vacuum press molding was performed for 90 minutes to obtain a cured product A.
  • the evaluation results are shown in Table 2.
  • Example 4 a cured product B was obtained according to Example 3 except that the vinyl benzyl ether compound B was used instead of the vinyl benzyl ether compound A.
  • the evaluation results are shown in Table 2.
  • a cured product D was obtained according to Example 3 except that the vinyl benzyl ether compound D was used instead of the vinyl benzyl ether compound A.
  • the cured product D was extremely fragile, and the characteristics of the cured product, which will be described later, could not be evaluated.
  • a cured product E was obtained according to Example 3 except that the vinyl benzyl ether compound E was used instead of the vinyl benzyl ether compound A.
  • the cured product E was very fragile, and the characteristics of the cured product, which will be described later, could not be evaluated.
  • the characteristics of the cured product were evaluated by the following method. ⁇ Glass transition temperature> The glass transition temperature of the cured product was measured by using DMS6100 manufactured by Seiko Instruments Co., Ltd. for the cured product cut to a length of 50 mm and a width of 5 mm at a vibration frequency of 10 Hz and a heating rate of 2 ° C / min. The temperature was taken as the peak temperature of the obtained loss elastic modulus.
  • the dielectric constant and dielectric loss tangent of the cured product were measured at a frequency of 10 GHz by a cavity resonator perturbation method using an Agilent 8722ES Network Analyzer for the cured product cut to a length of 100 mm and a width of 0.8 mm. ..

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Abstract

Provided are a manufacturing method for a novel resin having a vinyl group, said resin excelling in heat resistance and in a dielectric characteristic, a novel resin having a vinyl group, and a curable resin composition and a cured product using the resin having a vinyl group. The manufacturing method for a resin having a vinyl group includes causing a terpene phenol resin having a hydroxyl equivalent of 260-580 g/eq and a styrene having a halogenated methyl group to react in the presence of a basic compound.

Description

ビニル基を有する樹脂の製造方法、ビニル基を有する樹脂、硬化性樹脂組成物および硬化物A method for producing a resin having a vinyl group, a resin having a vinyl group, a curable resin composition and a cured product.
　本発明は、ビニル基を有する樹脂の製造方法、ビニル基を有する樹脂、硬化性樹脂組成物および硬化物に関する。 The present invention relates to a method for producing a resin having a vinyl group, a resin having a vinyl group, a curable resin composition, and a cured product.
　ビニルベンジルエーテル化合物等のビニル基を有する樹脂は、誘電特性や耐熱性、低吸湿性に優れているため、高周波信号を扱う電子機器の材料として用いられている。このようなビニルベンジルエーテル化合物およびその製造方法については、例えば、特許文献１、特許文献２に開示されているものが知られている。 Resins having a vinyl group such as vinylbenzyl ether compounds are excellent in dielectric properties, heat resistance, and low hygroscopicity, and are therefore used as materials for electronic devices that handle high-frequency signals. As for such a vinylbenzyl ether compound and a method for producing the same, for example, those disclosed in Patent Document 1 and Patent Document 2 are known.
特開２０１９－１５７０１５号公報JP-A-2019-157015 特開平８－１２００３９号公報Japanese Unexamined Patent Publication No. 8-120039
　そして、近年の技術革新に伴い、耐熱性に優れ、かつ、誘電特性に優れた新規なビニル基を有する樹脂およびその製造方法が求められる。
　本発明はかかる課題を解決することを目的とするものであって、耐熱性に優れ、かつ、誘電特性に優れた新規なビニル基を有する樹脂の製造方法、新規なビニル基を有する樹脂、ならびに、前記ビニル基を有する樹脂を用いた硬化性樹脂組成物および硬化物を提供することを目的とする。 With recent technological innovations, there is a demand for a resin having a novel vinyl group having excellent heat resistance and excellent dielectric properties, and a method for producing the same.
An object of the present invention is to solve such a problem, a method for producing a resin having a novel vinyl group having excellent heat resistance and excellent dielectric properties, a resin having a novel vinyl group, and a resin having a novel vinyl group. , It is an object of the present invention to provide a curable resin composition and a cured product using the resin having a vinyl group.
　上記課題のもと、本発明者が検討を行った結果、所定の水酸基当量を有するテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンを用いることにより、上記課題を解決しうることを見出した。
　具体的には、下記手段により、上記課題は解決された。
＜１＞水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンとを、塩基性化合物の存在下で反応させることを含む、ビニル基を有する樹脂の製造方法。
＜２＞前記塩基性化合物が、アルカリ金属アルコキシドおよびアルカリ金属水酸化物の少なくとも１種を含む、＜１＞に記載のビニル基を有する樹脂の製造方法。
＜３＞前記ハロゲン化メチル基を有するスチレンが、式（１）で表される化合物を含む、＜１＞または＜２＞に記載のビニル基を有する樹脂の製造方法。
式（１）
Figure JPOXMLDOC01-appb-C000004
 （式（１）中、Ｘは、塩素または臭素を表す。）
＜４＞前記ハロゲン化メチル基を有するスチレンが、メタクロロメチルスチレンおよび／またはパラクロロメチルスチレンを含む、＜１＞～＜３＞のいずれか１つに記載のビニル基を有する樹脂の製造方法。
＜５＞前記水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂のスチレン換算の数平均分子量（Ｍｎ）が４００以上９００以下である、＜１＞～＜４＞のいずれか１つに記載のビニル基を有する樹脂の製造方法。
＜６＞前記水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂のスチレン換算の重量平均分子量（Ｍｗ）が６５０以上１，２００以下である、＜１＞～＜５＞のいずれか１つに記載のビニル基を有する樹脂の製造方法。
＜７＞水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂のフェノール性水酸基の少なくとも一部がビニルベンジル基で変性された、ビニル基を有する樹脂。
＜８＞式（２）で表される構成単位を有する、＜７＞に記載のビニル基を有する樹脂。
式（２）
Figure JPOXMLDOC01-appb-C000005
 （式（２）中、＊は他の構成単位または末端基との結合部位を示す。）
＜９＞式（３）で表される構成単位を有する、＜７＞に記載のビニル基を有する樹脂。
式（３）
Figure JPOXMLDOC01-appb-C000006
 （式（３）中、＊は他の構成単位または末端基との結合部位を示す。ｍ、ｎおよびｏは、それぞれ独立に、構成単位のモル比率を表し、ｍは１以上の数であり、ｎは１以上の数であり、ｏは０以上の数を表す。）
＜１０＞スチレン換算数平均分子量（Ｍｎ）が７００以上１,２００以下である、＜７＞～＜９＞のいずれか１つに記載のビニル基を有する樹脂。
＜１１＞スチレン換算重量平均分子量（Ｍｗ）が１,０００以上１,５００以下である、＜７＞～＜１０＞のいずれか１つに記載のビニル基を有する樹脂。
＜１２＞＜７＞～＜１１＞のいずれか１つに記載のビニル基を有する樹脂を含む、硬化性樹脂組成物。
＜１３＞さらに、＜７＞～＜１１＞のいずれか１つに記載のビニル基を有する樹脂以外の熱硬化性化合物を含む、＜１２＞に記載の硬化性樹脂組成物。
＜１４＞前記熱硬化性化合物が、＜７＞～＜１１＞のいずれか１つに記載のビニル基を有する樹脂以外の化合物であって炭素炭素不飽和結合基を有する化合物およびエポキシ樹脂から選択される少なくとも１種を含む、＜１３＞に記載の硬化性樹脂組成物。
＜１５＞＜１２＞～＜１４＞のいずれか１つに記載の硬化性樹脂組成物の硬化物。 As a result of studies by the present inventor based on the above problems, it has been found that the above problems can be solved by using a terpene phenol resin having a predetermined hydroxyl group equivalent and styrene having a methyl halide group.
Specifically, the above problem was solved by the following means.
<1> A method for producing a resin having a vinyl group, which comprises reacting a terpenphenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group in the presence of a basic compound.
<2> The method for producing a resin having a vinyl group according to <1>, wherein the basic compound contains at least one of an alkali metal alkoxide and an alkali metal hydroxide.
<3> The method for producing a resin having a vinyl group according to <1> or <2>, wherein the styrene having a methyl halide group contains a compound represented by the formula (1).
Equation (1)
Figure JPOXMLDOC01-appb-C000004
 (In formula (1), X represents chlorine or bromine.)
<4> The method for producing a resin having a vinyl group according to any one of <1> to <3>, wherein the styrene having a methyl halide group contains metachloromethylstyrene and / or parachloromethylstyrene. ..
<5> The above-mentioned one of <1> to <4>, wherein the styrene-equivalent number average molecular weight (Mn) of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is 400 or more and 900 or less. A method for producing a resin having a vinyl group.
<6> One of <1> to <5>, wherein the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq has a styrene-equivalent weight average molecular weight (Mw) of 650 or more and 1,200 or less. The method for producing a resin having a vinyl group according to the above.
<7> A resin having a vinyl group in which at least a part of the phenolic hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is modified with a vinylbenzyl group.
<8> The resin having a vinyl group according to <7>, which has a structural unit represented by the formula (2).
Equation (2)
Figure JPOXMLDOC01-appb-C000005
 (In formula (2), * indicates a binding site with another structural unit or end group.)
<9> The resin having a vinyl group according to <7>, which has a structural unit represented by the formula (3).
Equation (3)
Figure JPOXMLDOC01-appb-C000006
 (In formula (3), * indicates a binding site with another structural unit or terminal group. m, n and o independently represent the molar ratio of the structural unit, and m is a number of 1 or more. , N is a number of 1 or more, and o represents a number of 0 or more.)
<10> The resin having a vinyl group according to any one of <7> to <9>, which has a styrene-equivalent number average molecular weight (Mn) of 700 or more and 1,200 or less.
<11> The resin having a vinyl group according to any one of <7> to <10>, which has a styrene-equivalent weight average molecular weight (Mw) of 1,000 or more and 1,500 or less.
<12> A curable resin composition containing the resin having a vinyl group according to any one of <7> to <11>.
<13> The curable resin composition according to <12>, further comprising a thermosetting compound other than the resin having a vinyl group according to any one of <7> to <11>.
<14> The thermosetting compound is selected from compounds other than the resin having a vinyl group according to any one of <7> to <11> and having a carbon-carbon unsaturated bond group and an epoxy resin. The curable resin composition according to <13>, which comprises at least one thereof.
<15> The cured product of the curable resin composition according to any one of <12> to <14>.
　本発明により、耐熱性に優れ、かつ、誘電特性に優れた新規なビニル基を有する樹脂の製造方法、新規なビニル基を有する樹脂、ならびに、前記ビニル基を有する樹脂を用いた硬化性樹脂組成物および硬化物を提供可能になった。 According to the present invention, a method for producing a resin having a novel vinyl group having excellent heat resistance and excellent dielectric properties, a resin having a novel vinyl group, and a curable resin composition using the resin having the vinyl group. It has become possible to provide products and cured products.
　以下、本発明を実施するための形態（以下、単に「本実施形態」という）について詳細に説明する。なお、以下の本実施形態は、本発明を説明するための例示であり、本発明は本実施形態のみに限定されない。
　なお、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書において、各種物性値および特性値は、特に述べない限り、２３℃におけるものとする。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。本明細書では、置換および無置換を記していない表記は、無置換の方が好ましい。 Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
In addition, in this specification, "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
In the present specification, various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the notation that does not describe substitution and non-substitution is preferably non-substitution.
　本実施形態のビニル基を有する樹脂の製造方法は、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンとを、塩基性化合物の存在下で反応させることを含むことを特徴とする。このような構成とすることにより、耐熱性に優れ、かつ、誘電特性に優れたビニル基を有する樹脂が得られる。 The method for producing a resin having a vinyl group according to the present embodiment includes reacting a terpenephenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group in the presence of a basic compound. It is characterized by that. With such a configuration, a resin having a vinyl group having excellent heat resistance and excellent dielectric properties can be obtained.
　本実施形態の製造方法では、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂を用いる。テルペンフェノール樹脂の水酸基当量を２６０ｇ／ｅｑ以上とすることにより、ハロゲン化メチル基を有するスチレンとの反応を効果的に進行させることができ、ビニル基をテルペンフェノール樹脂に効果的に導入することができ、得られるビニル基を有する樹脂に残存する水酸基の量を減らすことができ、さらに、誘電特性を向上させることができる。また、水酸基当量を５８０ｇ／ｅｑ以下とすることにより、耐熱性により優れた樹脂が得られる。また、テルペンフェノール樹脂を用いることにより、脂環構造に由来する低誘電特性および高耐熱性という効果がより効果的に達成される。 In the production method of this embodiment, a terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is used. By setting the hydroxyl group equivalent of the terpene phenol resin to 260 g / eq or more, the reaction with styrene having a methyl halide group can be effectively promoted, and the vinyl group can be effectively introduced into the terpene phenol resin. The amount of hydroxyl groups remaining in the obtained resin having a vinyl group can be reduced, and the dielectric properties can be further improved. Further, by setting the hydroxyl group equivalent to 580 g / eq or less, a resin having better heat resistance can be obtained. Further, by using the terpene phenol resin, the effects of low dielectric property and high heat resistance derived from the alicyclic structure can be more effectively achieved.
　前記テルペンフェノール樹脂の水酸基当量は、２６０ｇ／ｅｑ以上であり、２７０ｇ／ｅｑ以上であることが好ましく、２８０ｇ／ｅｑ以上であることがより好ましい。また、前記テルペンフェノール樹脂の水酸基当量は、５８０ｇ／ｅｑ以下であり、５６０ｇ／ｅｑ以下であることが好ましく、５４０ｇ／ｅｑ以下であることがより好ましい。
　本実施形態の製造方法では、テルペンフェノール樹脂を１種のみ用いてもよいし、２種以上用いてもよい。２種以上用いる場合、混合物の水酸基当量が上記範囲となる。
　水酸基当量は、後述する実施例の記載に従って測定される。 The hydroxyl group equivalent of the terpene phenol resin is 260 g / eq or more, preferably 270 g / eq or more, and more preferably 280 g / eq or more. The hydroxyl group equivalent of the terpene phenol resin is 580 g / eq or less, preferably 560 g / eq or less, and more preferably 540 g / eq or less.
In the production method of this embodiment, only one kind of terpene phenol resin may be used, or two or more kinds may be used. When two or more kinds are used, the hydroxyl group equivalent of the mixture is in the above range.
The hydroxyl group equivalent is measured according to the description of Examples described later.
　本実施形態の製造方法で用いるテルペンフェノール樹脂は、スチレン換算の数平均分子量（Ｍｎ）が４００以上であることが好ましく、５００以上であることがより好ましく、５２０以上であることがさらに好ましい。前記下限値以上とすることにより、靭性や柔軟性が向上する傾向にあり、また、成形時の割れやクラックの発生がより効果的に抑制される傾向にある。また、前記数平均分子量（Ｍｎ）は、９００以下であることが好ましく、７００以下であることがより好ましく、６８０以下であることがさらに好ましい。前記上限値以下とすることにより、溶剤溶解性が向上し樹脂の溶融粘度が低下し、樹脂のハンドリング性がより向上する傾向にある。 The terpene phenol resin used in the production method of the present embodiment preferably has a styrene-equivalent number average molecular weight (Mn) of 400 or more, more preferably 500 or more, and further preferably 520 or more. By setting the value to the lower limit or more, the toughness and flexibility tend to be improved, and cracks and cracks during molding tend to be more effectively suppressed. The number average molecular weight (Mn) is preferably 900 or less, more preferably 700 or less, and even more preferably 680 or less. By setting the value to the upper limit or less, the solvent solubility is improved, the melt viscosity of the resin is lowered, and the handleability of the resin tends to be further improved.
　本実施形態の製造方法で用いるテルペンフェノール樹脂は、スチレン換算の重量平均分子量（Ｍｗ）が６５０以上であることが好ましく、７６０以上であることがより好ましい。前記下限値以上とすることにより、靭性や柔軟性が向上する傾向にあり、また、成形時の割れやクラックの発生がより効果的に抑制される傾向にある。また、前記重量平均分子量（Ｍｗ）は、１，２００以下であることが好ましく、１，０５０以下であることがより好ましい。前記上限値以下とすることにより、溶剤溶解性が向上し樹脂の溶融粘度が低下し、樹脂のハンドリング性がより向上する傾向にある。
　テルペンフェノール樹脂の重量平均分子量および数平均分子量は、後述する実施例に記載の方法に従って測定される。 The terpene phenol resin used in the production method of the present embodiment preferably has a styrene-equivalent weight average molecular weight (Mw) of 650 or more, and more preferably 760 or more. By setting the value to the lower limit or more, the toughness and flexibility tend to be improved, and cracks and cracks during molding tend to be more effectively suppressed. The weight average molecular weight (Mw) is preferably 1,200 or less, and more preferably 1,050 or less. By setting the value to the upper limit or less, the solvent solubility is improved, the melt viscosity of the resin is lowered, and the handleability of the resin tends to be further improved.
The weight average molecular weight and the number average molecular weight of the terpene phenol resin are measured according to the methods described in Examples described later.
　本実施形態の製造方法で用いるテルペンフェノール樹脂は、テルペン化合物由来の構成単位（ｂ１）とフェノール化合物由来の構成単位（ｂ２）とを有するものが例示される。テルペン化合物としては、α－ピネン、β－ピネン、リモネン（ｄ体、ｌ体およびｄ／ｌ体（ジペンテン）を包含する）等のモノテルペン類が挙げられる。フェノール化合物としては、フェノール、ｍ－クレゾール、ｏ－クレゾール、ｐ－クレゾール、２，６－キシレノール、ｐ－ｔｅｒｔ－ブチルフェノール等が挙げられる。
　本実施形態の製造方法で用いるテルペンフェノール樹脂は、上記構成単位（ｂ１）と構成単位（ｂ２）以外の構成単位を有していてもよいし、有していなくてもよい。本実施形態の製造方法においては、テルペンフェノール樹脂は、構成単位（ｂ１）および構成単位（ｂ２）が末端基を除く全構成単位の９０モル％以上を占めることが好ましく、９５～１００モル％を占めることがより好ましく、９８～１００モル％を占めることがさらに好ましく、１００モル％であってもよい。
　本実施形態の製造方法で用いるテルペンフェノール樹脂において、構成単位（ｂ１）、構成単位（ｂ２）、これら以外の構成単位は、ぞれぞれ、１種のみであってもよいし、２種以上であってもよい。
　また、本実施形態の製造方法で用いるテルペンフェノール樹脂において、構成単位（ｂ１）、構成単位（ｂ２）は、ランダム重合体であっても、ブロック重合体であってもよい。 Examples of the terpene phenol resin used in the production method of the present embodiment include those having a terpene compound-derived structural unit (b1) and a phenol compound-derived structural unit (b2). Examples of the terpene compound include monoterpenes such as α-pinene, β-pinene, and limonene (including d-form, l-form and d / l-form (dipentene)). Examples of the phenol compound include phenol, m-cresol, o-cresol, p-cresol, 2,6-xylenol, p-tert-butylphenol and the like.
The terpene phenol resin used in the production method of the present embodiment may or may not have a structural unit other than the above-mentioned structural unit (b1) and the structural unit (b2). In the production method of the present embodiment, in the terpene phenol resin, the constituent unit (b1) and the constituent unit (b2) preferably occupy 90 mol% or more of all the constituent units excluding the terminal group, and 95 to 100 mol%. It is more preferably occupied, more preferably 98 to 100 mol%, and may be 100 mol%.
In the terpene phenol resin used in the production method of the present embodiment, the constituent unit (b1), the constituent unit (b2), and the constituent units other than these may be only one type, or two or more types, respectively. It may be.
Further, in the terpene phenol resin used in the production method of the present embodiment, the structural unit (b1) and the structural unit (b2) may be a random polymer or a block polymer.
　本実施形態において、テルペンフェノール樹脂は、下記式（ＴＰ１）で表される構成単位を含む樹脂であることが好ましい。
式（ＴＰ１）
Figure JPOXMLDOC01-appb-C000007
 　上記式中、Ｒ１１～Ｒ１３は、それぞれ独立して置換基を有してもよい炭素数１～２０の炭化水素基を表し、Ｒ１０は置換基を表し、ｍ１およびｎ１は、モル比率を示し、それぞれ独立に、１以上の整数を表し、ｓは０～３の整数を表す。 In the present embodiment, the terpene phenol resin is preferably a resin containing a structural unit represented by the following formula (TP1).
Equation (TP1)
Figure JPOXMLDOC01-appb-C000007
 In the above formula, R 11 to R 13 represent hydrocarbon groups having 1 to 20 carbon atoms which may independently have substituents, R 10 represents a substituent, and m1 and n1 are molar ratios. Represents an integer of 1 or more independently, and s represents an integer of 0 to 3.
　式（ＴＰ１）中、Ｒ１１～Ｒ１３は、それぞれ独立して置換基を有してもよい炭素数１～２０の炭化水素基を表す。Ｒ１１～Ｒ１３が表す炭化水素基が有する置換基としては、ハロゲン原子等が挙げられる。Ｒ１１～Ｒ１３が表す炭化水素基は無置換の炭化水素基であることが好ましい。また、Ｒ１１～Ｒ１３が表す炭化水素基としては、アルキル基、およびアリール基が挙げられ、アルキル基であることが好ましい。Ｒ１１～Ｒ１３が表す炭化水素基の炭素数は、１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、１がより好ましい。Ｒ１１～Ｒ１３はメチル基であることが特に好ましい。 In the formula (TP1), R 11 to R 13 represent hydrocarbon groups having 1 to 20 carbon atoms which may independently have substituents. Examples of the substituent contained in the hydrocarbon group represented by R 11 to R 13 include a halogen atom and the like. The hydrocarbon group represented by R 11 to R 13 is preferably an unsubstituted hydrocarbon group. Examples of the hydrocarbon group represented by R 11 to R 13 include an alkyl group and an aryl group, and an alkyl group is preferable. The number of carbon atoms of the hydrocarbon group represented by R 11 to R 13 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and even more preferably 1. It is particularly preferable that R 11 to R 13 are methyl groups.
　式（ＴＰ１）中、Ｒ１０は置換基を表す。置換基としては、アルキル基、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、ハロゲン原子等が挙げられる。 In formula (TP1), R 10 represents a substituent. Examples of the substituent include an alkyl group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a halogen atom and the like.
　式（ＴＰ１）中、ｍ１およびｎ１は、モル比率を示し、それぞれ１以上の整数を表す。ｍ１：ｎ１は、モル比率で、１～６：１であることが好ましく、２～５：１であることがさらに好ましい。 In the formula (TP1), m1 and n1 indicate a molar ratio, and each represents an integer of 1 or more. The molar ratio of m1: n1 is preferably 1 to 6: 1, more preferably 2 to 5: 1.
　式（ＴＰ１）において、テルペン化合物由来の構成単位とフェノール化合物由来の構成単位は、ブロック重合体であっても、ランダム重合体であってもよい。
　式（ＴＰ１）で表されるテルペンフェノール樹脂の末端は、テルペン鎖または水素原子であることが好ましい。
　式（ＴＰ１）で表される構成単位を含む樹脂は、本発明の趣旨を逸脱しない範囲で、式（ＴＰ１）で表される構成単位以外の構成単位を含んでいてもよい。式（ＴＰ１）で表される構成単位を含む樹脂においては、式（ＴＰ１）で表される構成単位が末端基を除く全構成単位の９０モル％以上を占めることが好ましく、９５～１００モル％を占めることがより好ましく、９８～１００モル％を占めることがさらに好ましく、１００モル％であってもよい。
　式（ＴＰ１）で表される構成単位を含む樹脂において、式（ＴＰ１）で表される構成単位は、１種のみであってもよいし、２種以上であってもよい。 In the formula (TP1), the structural unit derived from the terpene compound and the structural unit derived from the phenol compound may be a block polymer or a random polymer.
The terminal of the terpene phenol resin represented by the formula (TP1) is preferably a terpene chain or a hydrogen atom.
The resin containing the structural unit represented by the formula (TP1) may contain a structural unit other than the structural unit represented by the formula (TP1) as long as it does not deviate from the gist of the present invention. In the resin containing the structural unit represented by the formula (TP1), the structural unit represented by the formula (TP1) preferably occupies 90 mol% or more of all the structural units excluding the terminal group, and is 95 to 100 mol%. It is more preferable to occupy 98 to 100 mol%, and it may be 100 mol%.
In the resin containing the structural unit represented by the formula (TP1), the structural unit represented by the formula (TP1) may be only one kind or two or more kinds.
　本実施形態で用いるテルペンフェノール樹脂の代表的な構造は、下記式（ＴＰ２）で表されるものである。
式（ＴＰ２）
Figure JPOXMLDOC01-appb-C000008
 　式（ＴＰ２）において、ｍ２およびｎ２は、モル比率を示し、それぞれ１以上の整数を表す。ｍ２：ｎ２は、１～６：１であることが好ましく、２～５：１であることがさらに好ましい。
　式（ＴＰ２）において、テルペン由来の構成単位とフェノール由来の構成単位は、ブロック重合体であっても、ランダム重合体であってもよい。
　式（ＴＰ２）で表されるテルペンフェノール樹脂の末端は、テルペン鎖または水素原子であることが好ましい。
　式（ＴＰ２）で表される構成単位を含む樹脂は、本発明の趣旨を逸脱しない範囲で、式（ＴＰ２）で表される構成単位以外の構成単位を含んでいてもよい。式（ＴＰ２）で表される構成単位を含む樹脂は、式（ＴＰ２）で表される構成単位が末端基を除く全構成単位の９０モル％以上を占めることが好ましく、９５～１００モル％を占めることがより好ましく、９８～１００モル％を占めることがさらに好ましく、１００モル％であってもよい。
　式（ＴＰ２）で表される構成単位を含む樹脂において、式（ＴＰ２）で表される構成単位は、１種のみであってもよいし、２種以上であってもよい。 A typical structure of the terpene phenol resin used in this embodiment is represented by the following formula (TP2).
Equation (TP2)
Figure JPOXMLDOC01-appb-C000008
 In the formula (TP2), m2 and n2 represent molar ratios, and each represents an integer of 1 or more. m2: n2 is preferably 1 to 6: 1 and more preferably 2 to 5: 1.
In the formula (TP2), the terpene-derived structural unit and the phenol-derived structural unit may be a block polymer or a random polymer.
The terminal of the terpene phenol resin represented by the formula (TP2) is preferably a terpene chain or a hydrogen atom.
The resin containing the structural unit represented by the formula (TP2) may contain a structural unit other than the structural unit represented by the formula (TP2) as long as it does not deviate from the gist of the present invention. In the resin containing the structural unit represented by the formula (TP2), the structural unit represented by the formula (TP2) preferably occupies 90 mol% or more of all the structural units excluding the terminal group, and 95 to 100 mol%. It is more preferably occupied, more preferably 98 to 100 mol%, and may be 100 mol%.
In the resin containing the structural unit represented by the formula (TP2), the structural unit represented by the formula (TP2) may be only one kind or two or more kinds.
　本実施形態の製造方法では、ハロゲン化メチル基を有するスチレンを用いる。ハロゲン化メチル基を有するスチレンを用いることにより、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂が有する水酸基と反応し、ビニル基を有する樹脂が得られる。 In the production method of this embodiment, styrene having a methyl halide group is used. By using styrene having a methyl halide group, a resin having a vinyl group can be obtained by reacting with a hydroxyl group having a terpenphenol resin having a hydroxyl group equivalent of 260 to 580 g / eq.
　前記ハロゲン化メチル基を有するスチレンが、式（１）で表される化合物を含むことが好ましい。このような構造の化合物を用いることにより、より各種性能に優れたビニル基を有する樹脂が得られる。
式（１）
Figure JPOXMLDOC01-appb-C000009
 （式（１）中、Ｘは、塩素または臭素を表す。）
　式（１）において、Ｘは、塩素が好ましい。
　前記ハロゲン化メチル基を有するスチレンは、メタクロロメチルスチレンおよび／またはパラクロロメチルスチレンが好ましい。 It is preferable that the styrene having a methyl halide group contains the compound represented by the formula (1). By using a compound having such a structure, a resin having a vinyl group having more excellent performance can be obtained.
Equation (1)
Figure JPOXMLDOC01-appb-C000009
 (In formula (1), X represents chlorine or bromine.)
In the formula (1), X is preferably chlorine.
The styrene having a methyl halide group is preferably metachloromethylstyrene and / or parachloromethylstyrene.
　本実施形態の製造方法においては、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂が有する水酸基１モルに対するハロゲン化メチル基を有するスチレンのモル数が１～２モルであることが好ましく、１.０３～１．３モルであることがより好ましい。 In the production method of the present embodiment, the number of moles of styrene having a methyl halide group is preferably 1 to 2 mol with respect to 1 mol of the hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq. More preferably, it is .03 to 1.3 mol.
　本実施形態の製造方法によれば、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンとを、塩基性化合物の存在下で反応させる。塩基性化合物の存在下で反応させることにより、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンとの反応が進行する。
　塩基性化合物は、アルカリ金属アルコキシドおよびアルカリ金属水酸化物の少なくとも１種を含むことが好ましく、アルカリ金属水酸化物がより好ましい。アルカリ金属水酸化物は反応性の観点から水溶液として使用することが好ましい。アルカリ金属としては、リチウム、カリウム、ナトリウムが例示され、ナトリウムが好ましい。また、アルカリ金属アルコキシドを構成するアルコキシドとしては、メトキシド、エトキシドが例示される。
　本実施形態においては、反応系に添加するアルカリ金属アルコキシドおよびアルカリ金属水酸化物の総量が、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂が有する水酸基１モルに対し、１．５～５モルであることが好ましく、３．５～４．７モルであることがより好ましい。 According to the production method of the present embodiment, a terpenphenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and styrene having a methyl halide group are reacted in the presence of a basic compound. By reacting in the presence of a basic compound, the reaction between the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and the styrene having a methyl halide group proceeds.
The basic compound preferably contains at least one of an alkali metal alkoxide and an alkali metal hydroxide, more preferably an alkali metal hydroxide. The alkali metal hydroxide is preferably used as an aqueous solution from the viewpoint of reactivity. Examples of the alkali metal include lithium, potassium and sodium, and sodium is preferable. Examples of the alkoxide constituting the alkali metal alkoxide include methoxide and ethoxide.
In the present embodiment, the total amount of the alkali metal alkoxide and the alkali metal hydroxide added to the reaction system is 1.5 to 5 with respect to 1 mol of the hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq. It is preferably mol, more preferably 3.5 to 4.7 mol.
　本実施形態の製造方法においては、塩基性化合物（特に、アルカリ金属アルコキシドおよびアルカリ金属水酸化物）は、反応系に１回に投入してもよいし、２回以上に分けて投入してもよい。 In the production method of the present embodiment, the basic compound (particularly, the alkali metal alkoxide and the alkali metal hydroxide) may be added to the reaction system at one time, or may be added in two or more times. good.
　本実施形態の製造方法では、アルカリ金属水酸化物を使用する場合、相関移動触媒を併用してもよい。相関移動触媒としては、テトラブチルアンモニウムブロマイドが例示される。 In the production method of this embodiment, when an alkali metal hydroxide is used, a phase transfer catalyst may be used in combination. Tetrabutylammonium bromide is exemplified as the phase transfer catalyst.
　本実施形態の製造方法においては、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンの反応は、５０～８０℃で行うことが好ましい。 In the production method of the present embodiment, the reaction between the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and the styrene having a methyl halide group is preferably carried out at 50 to 80 ° C.
　本実施形態の製造方法では、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンとを反応させる際に、溶媒を用いることが好ましい。
　溶媒は、用いる塩基性化合物の種類に応じて、適宜定めることができる。
　塩基性化合物として、アルカリ金属水酸化物を用いる場合、溶媒は、芳香族炭化水素（好ましくはトルエン）および水が例示される。より具体的には、反応系に芳香族炭化水素とアルカリ金属水酸化物の水溶液を添加して用いることが好ましい。
　塩基性化合物として、アルカリ金属アルコキシドを用いる場合、溶媒は非プロトン性極性溶媒が好ましい。 In the production method of the present embodiment, it is preferable to use a solvent when reacting the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group.
The solvent can be appropriately determined depending on the type of the basic compound used.
When an alkali metal hydroxide is used as the basic compound, the solvent is exemplified by aromatic hydrocarbons (preferably toluene) and water. More specifically, it is preferable to add an aqueous solution of an aromatic hydrocarbon and an alkali metal hydroxide to the reaction system for use.
When an alkali metal alkoxide is used as the basic compound, the solvent is preferably an aprotic polar solvent.
　本実施形態の製造方法においては、上記水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンの反応後に得られる樹脂を分離精製することが好ましい。分離精製は常法に従って行うことができる。 In the production method of the present embodiment, it is preferable to separate and purify the resin obtained after the reaction between the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq and styrene having a methyl halide group. Separation and purification can be performed according to a conventional method.
　次に、本実施形態のビニル基を有する樹脂について説明する。
　本実施形態のビニル基を有する樹脂は、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂のフェノール性水酸基の少なくとも一部がビニルベンジル基で変性された樹脂である。このようなビニル基を有する樹脂は、耐熱性に優れ、かつ、誘電特性にも優れている。 Next, the resin having a vinyl group of this embodiment will be described.
The resin having a vinyl group of the present embodiment is a resin in which at least a part of the phenolic hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is modified with a vinylbenzyl group. Such a resin having a vinyl group has excellent heat resistance and also excellent dielectric properties.
　より具体的には、本実施形態のビニル基を有する樹脂は、式（２）で表される構成単位を有する樹脂であることが好ましい。
式（２）
Figure JPOXMLDOC01-appb-C000010
 （式（２）中、＊は他の構成単位または末端基との結合部位を示す。）
　式（２）で表される構成単位を有する樹脂は、通常、上記構成単位に加え、テルペン化合物由来の構成単位（ｂ１）を含み、さらに、フェノール化合物由来の構成単位（ｂ２）を含んでいてもよい。
　また、式（２）で表される構成単位を有する樹脂の末端基は、テルペン化合物由来の鎖または水素原子であることが好ましい。 More specifically, the resin having a vinyl group of the present embodiment is preferably a resin having a structural unit represented by the formula (2).
Equation (2)
Figure JPOXMLDOC01-appb-C000010
 (In formula (2), * indicates a binding site with another structural unit or end group.)
The resin having the structural unit represented by the formula (2) usually contains a structural unit (b1) derived from a terpene compound in addition to the above structural unit, and further contains a structural unit (b2) derived from a phenol compound. May be good.
Further, the terminal group of the resin having the structural unit represented by the formula (2) is preferably a chain derived from a terpene compound or a hydrogen atom.
　本実施形態のビニル基を有する樹脂は、好ましくは、式（３）で表される構成単位を有する。
式（３）
Figure JPOXMLDOC01-appb-C000011
 （式（３）中、＊は他の構成単位または末端基との結合部位を示す。ｍ、ｎおよびｏは、それぞれ独立に、構成単位のモル比率を表し、ｍは１以上の数であり、ｎは１以上の数であり、ｏは０以上の数を表す。） The resin having a vinyl group of the present embodiment preferably has a structural unit represented by the formula (3).
Equation (3)
Figure JPOXMLDOC01-appb-C000011
 (In formula (3), * indicates a binding site with another structural unit or terminal group. m, n and o independently represent the molar ratio of the structural unit, and m is a number of 1 or more. , N is a number of 1 or more, and o represents a number of 0 or more.)
　ｍは、１以上の数であり、ｎは、１以上の数であり、ｏは、０以上の数である。ｎ：ｍのモル比率は、１：１～６であることが好ましく、１：２～５であることがより好ましい。
　ｏは、０．０２３以下が好ましく、０．０１８以下がより好ましい。前記上限値以下とすることにより、誘電率および誘電正接が低くなり、また、架橋密度が高くなる傾向にあり好ましい。
　ｍ、ｎおよびｏの合計は、本実施形態における全構成単位を１００モルとしたときに、モル比率が、９０モル以上であることが好ましく、９５モル以上であることがより好ましく、９８モル以上であることがさらに好ましい。
　ｍ、ｎおよびｏは、上記スチレン換算の数平均分子量および重量平均分子量を満たす範囲であることが好ましい。
　上記式（３）において、末端基は、テルペン化合物由来の鎖または水素原子であることが好ましい。
　式（３）において、各構成単位は、ブロック重合体であっても、ランダム重合体であってもよい。 m is a number of 1 or more, n is a number of 1 or more, and o is a number of 0 or more. The molar ratio of n: m is preferably 1: 1 to 6, more preferably 1: 2 to 5.
o is preferably 0.023 or less, more preferably 0.018 or less. By setting the value to the upper limit or less, the dielectric constant and the dielectric loss tangent tend to be low, and the crosslink density tends to be high, which is preferable.
The total of m, n and o is preferably 90 mol or more, more preferably 95 mol or more, and 98 mol or more, when the total constituent unit in the present embodiment is 100 mol. Is more preferable.
It is preferable that m, n and o are in a range satisfying the number average molecular weight and the weight average molecular weight in terms of styrene.
In the above formula (3), the terminal group is preferably a chain derived from a terpene compound or a hydrogen atom.
In the formula (3), each structural unit may be a block polymer or a random polymer.
　本実施形態のビニル基を有する樹脂は、本発明の趣旨を逸脱しない範囲で、式（３）で表される構成単位以外の構成単位を含んでいてもよい。
　本実施形態のビニル基を有する樹脂において、式（３）における各構成単位は、それぞれ、１種のみであってもよいし、２種以上であってもよい。 The resin having a vinyl group of the present embodiment may contain a structural unit other than the structural unit represented by the formula (3) as long as it does not deviate from the gist of the present invention.
In the resin having a vinyl group of the present embodiment, each structural unit in the formula (3) may be only one kind or two or more kinds.
　本実施形態のビニル基を有する樹脂は、スチレン換算数平均分子量（Ｍｎ）が７００以上であることが好ましく、８００以上であることがより好ましい。前記下限値以上とすることにより、靭性や柔軟性が向上する傾向にあり、また、成形時の割れやクラックの発生がより効果的に抑制される傾向にある。また、前記数平均分子量（Ｍｎ）は、１,２００以下であることが好ましく、１，０００以下であることがより好ましい。前記上限値以下とすることにより、溶剤溶解性が向上し樹脂の溶融粘度が低下し、樹脂のハンドリング性がより向上する傾向にある。 The resin having a vinyl group of the present embodiment preferably has a styrene-equivalent number average molecular weight (Mn) of 700 or more, and more preferably 800 or more. By setting the value to the lower limit or more, the toughness and flexibility tend to be improved, and cracks and cracks during molding tend to be more effectively suppressed. The number average molecular weight (Mn) is preferably 1,200 or less, more preferably 1,000 or less. By setting the value to the upper limit or less, the solvent solubility is improved, the melt viscosity of the resin is lowered, and the handleability of the resin tends to be further improved.
　本実施形態のビニル基を有する樹脂は、スチレン換算重量平均分子量（Ｍｗ）が１,０００以上であることが好ましく、１，１００以上であることがより好ましい。前記下限値以上とすることにより、靭性や柔軟性が向上する傾向にあり、また、成形時の割れやクラックの発生がより効果的に抑制される傾向にある。また、前記重量平均分子量（Ｍｗ）は、１,５００以下であることが好ましく、１，４００以下であることがより好ましい。前記上限値以下とすることにより、溶剤溶解性が向上し樹脂の溶融粘度が低下し、樹脂のハンドリング性がより向上する傾向にある。
　本実施形態のビニル基を有する樹脂の重量平均分子量および数平均分子量は、後述する実施例に記載の方法に従って測定される。 The resin having a vinyl group of the present embodiment preferably has a styrene-equivalent weight average molecular weight (Mw) of 1,000 or more, and more preferably 1,100 or more. By setting the value to the lower limit or more, the toughness and flexibility tend to be improved, and cracks and cracks during molding tend to be more effectively suppressed. The weight average molecular weight (Mw) is preferably 1,500 or less, and more preferably 1,400 or less. By setting the value to the upper limit or less, the solvent solubility is improved, the melt viscosity of the resin is lowered, and the handleability of the resin tends to be further improved.
The weight average molecular weight and the number average molecular weight of the resin having a vinyl group of this embodiment are measured according to the methods described in Examples described later.
　本実施形態のビニル基を有する樹脂は、水酸基当量が１５，０００ｇ／ｅｑ以上であることが好ましく、２０，０００ｇ／ｅｑ以上であることがより好ましい。前記下限値以上とすることにより、誘電率および誘電正接をより低くできる傾向にある。前記水酸基当量の上限値は、高ければ高い方がよいが、１００，０００ｇ／ｅｑ以下が実際的である。
　水酸基当量は、後述する実施例の記載に従って測定される。 The resin having a vinyl group of the present embodiment preferably has a hydroxyl group equivalent of 15,000 g / eq or more, and more preferably 20,000 g / eq or more. By setting the value to the lower limit or higher, the permittivity and the dielectric loss tangent tend to be lower. The higher the upper limit of the hydroxyl group equivalent, the better, but it is practically 100,000 g / eq or less.
The hydroxyl group equivalent is measured according to the description of Examples described later.
　本実施形態のビニル基を有する樹脂は、水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンとを、塩基性化合物の存在下で反応させることによって得られる樹脂であることが好ましい。すなわち、本実施形態のビニル基を有する樹脂の製造方法に従って製造される樹脂であることが好ましい。 The resin having a vinyl group of the present embodiment is a resin obtained by reacting a terpenephenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group in the presence of a basic compound. It is preferable to have. That is, it is preferable that the resin is produced according to the method for producing a resin having a vinyl group according to the present embodiment.
＜用途＞
　本実施形態のビニル基を有する樹脂は、硬化性樹脂組成物として用いることができる。前記硬化性樹脂組成物は、１種または２種以上の本実施形態のビニル基を有する樹脂のみからなっていてもよいし、さらに、本実施形態のビニル基を有する樹脂以外の熱硬化性化合物を含んでいてもよい。前記熱硬化性化合物は、本実施形態のビニル基を有する樹脂以外の化合物であって炭素炭素不飽和結合基を有する化合物およびエポキシ樹脂から選択される少なくとも１種を含むことが好ましい。
　さらに、前記硬化性樹脂組成物は、１種または２種以上の各種添加剤を含有してもよい。添加剤としては、難燃剤、紫外線吸収剤、酸化防止剤、光重合開始剤、蛍光増白剤、光増感剤、染料、顔料、増粘剤、流動調整剤、滑剤、消泡剤、分散剤、レベリング剤、光沢剤、重合禁止剤等が挙げられる。
　本実施形態の硬化物は、前記硬化性樹脂組成物を硬化したものである。この様な硬化物は、耐熱性に優れ、かつ、誘電特性に優れることから、プリント配線板の絶縁層、半導体パッケージ用材料として好適に用いることができる。 <Use>
The resin having a vinyl group of this embodiment can be used as a curable resin composition. The curable resin composition may consist of only one or more kinds of resins having a vinyl group of the present embodiment, and further, a thermosetting compound other than the resin having a vinyl group of the present embodiment. May include. The thermosetting compound preferably contains at least one compound selected from a compound having a carbon-carbon unsaturated bond group and an epoxy resin, which is a compound other than the resin having a vinyl group of the present embodiment.
Further, the curable resin composition may contain one kind or two or more kinds of various additives. Additives include flame retardants, UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoaming agents, and dispersions. Examples thereof include agents, leveling agents, brighteners, polymerization inhibitors and the like.
The cured product of the present embodiment is a cured product of the curable resin composition. Since such a cured product has excellent heat resistance and dielectric properties, it can be suitably used as an insulating layer for a printed wiring board and a material for a semiconductor package.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。
　実施例で用いた測定機器等が廃番等により入手困難な場合、他の同等の性能を有する機器を用いて測定することができる。 Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
If the measuring device or the like used in the examples is difficult to obtain due to a discontinued number or the like, measurement can be performed using another device having the same performance.
＜テルペンフェノール樹脂の水酸基当量の測定＞
　テルペンフェノール樹脂の水酸基当量は、以下の方法に従って測定した。
　テルペンフェノール樹脂をヨウ素フラスコに３ｇ（水酸基当量が１，０００ｇ／ｅｑ以上の樹脂では６ｇ）秤量し、別途調製したアセチル化試薬（１０体積％の無水酢酸ピリジン溶液）を１５ｍＬ加えて、樹脂を溶解させた。９５℃～１００℃のオイルバスに栓をしたヨウ素フラスコを浸け、１時間加熱撹拌した。加熱撹拌後、空冷し、３００ｍＬの容積のコニカルビーカーへ内容液を移し替え、トルエン５ｍＬ、純水２０ｍＬ、２－ブタノン４０ｍＬで洗浄し、ヨウ素フラスコに付着した内容液を回収した。１ｍｏｌ／ＬのＮａＯＨ水溶液２０ｍＬを正確に測り取り、コニカルビーカーに加えて十分に混合した後に、０．２ｍｏｌ／ＬのＮａＯＨ水溶液を用いて、フェノールフタレイン溶液を指示薬とした滴定を行った。テルペンフェノール樹脂試料を用いないブランクサンプルについても同様に滴定を実施し、各滴定結果から下記式（ｉ）を用いて、水酸基当量を算出した。
式（ｉ）
Figure JPOXMLDOC01-appb-M000012
 Ｆ：０．２ｍｏｌ／ＬＮａＯＨのファクター
　水酸基当量の単位は、ｇ／ｅｑで示した。 <Measurement of hydroxyl group equivalent of terpene phenol resin>
The hydroxyl group equivalent of the terpene phenol resin was measured according to the following method.
Weigh 3 g of terpene phenol resin in an iodine flask (6 g for a resin having a hydroxyl equivalent of 1,000 g / eq or more), and add 15 mL of a separately prepared acetylation reagent (10% by volume acetic anhydride pyridine solution) to dissolve the resin. I let you. An iodine flask with a stopper was immersed in an oil bath at 95 ° C to 100 ° C, and the mixture was heated and stirred for 1 hour. After heating and stirring, the mixture was air-cooled, the content solution was transferred to a conical beaker having a volume of 300 mL, washed with 5 mL of toluene, 20 mL of pure water, and 40 mL of 2-butanone, and the content solution adhering to the iodine flask was recovered. Twenty mL of a 1 mol / L NaOH aqueous solution was accurately measured, added to a conical beaker and thoroughly mixed, and then titration was performed using a 0.2 mol / L NaOH aqueous solution using a phenolphthalein solution as an indicator. Titration was also carried out in the same manner for the blank sample not using the terpene phenol resin sample, and the hydroxyl group equivalent was calculated from each titration result using the following formula (i).
Equation (i)
Figure JPOXMLDOC01-appb-M000012
 F: Factor of 0.2 mol / LNaOH The unit of hydroxyl group equivalent is shown in g / eq.
＜数平均分子量、重量平均分子量の測定＞
　テルペンフェノール樹脂およびビニルベンジルエーテル化合物の数平均分子量および重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により求めた。
　分析カラムには昭和電工（株）製、ＫＦ－８０１、ＫＦ－８０２、ＫＦ－８０３、ＫＦ－８０４を連結して用い、検出には（株）島津製作所製、示差屈折検出器ＲＩＤ－２０Ａを用いた。溶離液であるテトラヒドロフラン２ｍＬに測定対象となる樹脂（テルペンフェノール樹脂、ビニルベンジルエーテル化合物）を８０ｍｇ溶解し、カラムへの注入量を２０μＬとし、溶離液流量１ｍＬ/ｍｉｎ、カラム温度４０℃で分析を行った。東ソー（株）製標準ポリスチレンＰＳｔＱｕｉｃｋ ＭＰ-Ｎにより分子量校正曲線を作成し、ポリスチレン換算分子量を見積もった。 <Measurement of number average molecular weight and weight average molecular weight>
The number average molecular weight and the weight average molecular weight of the terpene phenol resin and the vinylbenzyl ether compound were determined by the gel permeation chromatography (GPC) method.
Showa Denko Corporation, KF-801, KF-802, KF-803, KF-804 are connected and used for the analysis column, and the differential refractometer RID-20A, manufactured by Shimadzu Corporation, is used for detection. Using. 80 mg of the resin to be measured (terpene phenol resin, vinyl benzyl ether compound) was dissolved in 2 mL of the eluent in tetrahydrofuran, the injection amount into the column was 20 μL, the eluent flow rate was 1 mL / min, and the analysis was performed at a column temperature of 40 ° C. went. A molecular weight calibration curve was created using the standard polystyrene PStQuick MP-N manufactured by Tosoh Corporation, and the polystyrene-equivalent molecular weight was estimated.
＜ビニルベンジルエーテル化合物の水酸基当量の測定＞
　ビニルベンジルエーテル化合物の水酸基当量は、ジクロロメタン０．０８ｇ／ｍＬ溶液を、液セル法（ＫＢｒ窓材、光路長＝１ｍｍ）にて吸光度を測定し、フェノールを標準物質として作成した検量線より求めた。水酸基当量の単位は、ｇ／ｅｑで示した。
　ジクロロメタンは、富士フイルム和光純薬（株）製、超脱水グレードを用いた。吸光度の測定は、サーモフィッシャーサイエンティフィック製ＦＴ-ＩＲ（Ｎｉｃｏｌｅｔ ６７００）を用いて行った。 <Measurement of hydroxyl group equivalent of vinyl benzyl ether compound>
The hydroxyl group equivalent of the vinylbenzyl ether compound was determined from the calibration curve prepared by measuring the absorbance of a 0.08 g / mL solution of dichloromethane by the liquid cell method (KBr window material, optical path length = 1 mm) and using phenol as a standard substance. .. The unit of hydroxyl group equivalent is expressed in g / eq.
Dichloromethane used was an ultra-dehydrated grade manufactured by Wako Pure Chemical Industries, Ltd. The absorbance was measured using FT-IR (Nicolet 6700) manufactured by Thermo Fisher Scientific.
＜１Ｈ－ＮＭＲの分析＞
　ビニル基を有する樹脂の１Ｈ－ＮＭＲは、装置として、ＢＲＵＫＥＲ製、核磁気共鳴装置、ＡＶＡＮＣＥＩＩ６００ＭＨｚを用い、重水素置換クロロホルム溶剤中で測定を行った。尚、後述のδ（ｐｐｍ）は次式で表される化学シフトを示す。
δ（ｐｐｍ）＝１０６×（νＳ－νＲ）／νＲ
νＳ：試料の共鳴周波数（Ｈｚ）
νＲ：標準物質のトリメチルシラン（ＴＭＳ）の共鳴周波数（Ｈｚ） < 1 1 H-NMR analysis>
The 1 H-NMR of the resin having a vinyl group was measured in a deuterium-substituted chloroform solvent using a nuclear magnetic resonance apparatus manufactured by BRUKER and AVANCEII 600 MHz as an apparatus. In addition, δ (ppm) described later indicates a chemical shift represented by the following equation.
δ (ppm) = 106 × (ν S -ν R ) / ν R
ν S : Resonance frequency (Hz) of the sample
ν R : Resonance frequency (Hz) of standard substance trimethylsilane (TMS)
＜実施例１＞
　撹拌装置、温度計および還流管を備えた５００ｍＬの容積の反応容器にテルペンフェノール樹脂ＹＳポリスターＫ１２５（ヤスハラケミカル（株）製、水酸基当量３１１ｇ／ｅｑ、スチレン換算数平均分子量５５０、スチレン換算重量平均分子量７８９）２９．６ｇ、トルエン（富士フイルム和光純薬（株）製）２２０ｇおよび水酸化ナトリウム水溶液（関東化学（株）製、濃度：４８質量％）３６．１ｇ、純水４３．３ｇを仕込み、７０℃に加熱撹拌した。反応温度を７０℃に保ちながらテトラブチルアンモニウムブロマイド（東京化成工業（株）製）の７０質量％水溶液１０．９ｇおよびクロロメチルスチレンＣＭＳ－Ｐ（メタクロロメチルスチレンとパラクロロメチルスチレンの混合物、ＡＧＣセイミケミカル（株）製）１９．５ｇを加え、１７０分撹拌した。有機相と水相を分液し、有機層を１．４質量％硫酸水溶液、次いで３０質量％メタノール水溶液で洗浄した。得られた溶液をロータリーエバポレーターで濃縮した後、２－ブタノン（富士フイルム和光純薬（株）、特級）３１９．１ｇで希釈し、メタノール中に滴下することで固形化した。ろ別した固体を純水、次いでメタノールで洗浄した後、再度純水、メタノールで洗浄し、減圧乾燥して目的とするビニルベンジルエーテル化合物Ａ　２１．７ｇを得た。
　１Ｈ-ＮＭＲ分析の結果ビニルベンジルエーテル骨格に由来する新規ピークが、５．０２ｐｐｍ、５．２５ｐｐｍ、５．７４ｐｐｍ、５．７８ｐｐｍ、６．７～７．２ｐｐｍに観測された。ビニルベンジルエーテル化合物Ａの数平均分子量は８５７、重量平均分子量は１，２３０、水酸基当量は７７，０００であった。 <Example 1>
Toluene phenol resin YS Polystar K125 (manufactured by Yasuhara Chemical Industries, Ltd., hydroxyl weight equivalent 311 g / eq, styrene equivalent number average molecular weight 550, styrene equivalent weight average molecular weight 789) in a reaction vessel with a volume of 500 mL equipped with a stirrer, thermometer and perfusion tube. ) 29.6 g, toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 220 g, aqueous sodium hydroxide solution (manufactured by Kanto Chemical Industries, Ltd., concentration: 48% by mass) 36.1 g, pure water 43.3 g, 70 The mixture was heated and stirred at ° C. While maintaining the reaction temperature at 70 ° C, 10.9 g of a 70 mass% aqueous solution of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and chloromethylstyrene CMS-P (mixture of metachloromethylstyrene and parachloromethylstyrene, AGC) 19.5 g (manufactured by Seimi Chemical Co., Ltd.) was added, and the mixture was stirred for 170 minutes. The organic phase and the aqueous phase were separated, and the organic layer was washed with a 1.4 mass% sulfuric acid aqueous solution and then a 30 mass% methanol aqueous solution. The obtained solution was concentrated with a rotary evaporator, diluted with 319.1 g of 2-butanone (Fuji Film Wako Pure Chemical Industries, Ltd., special grade), and solidified by dropping into methanol. The separated solid was washed with pure water and then with methanol, washed again with pure water and methanol, and dried under reduced pressure to obtain 21.7 g of the target vinyl benzyl ether compound A.
1 As a result of 1 H-NMR analysis, novel peaks derived from the vinylbenzyl ether skeleton were observed at 5.02 ppm, 5.25 ppm, 5.74 ppm, 5.78 ppm, and 6.7 to 7.2 ppm. The number average molecular weight of the vinylbenzyl ether compound A was 857, the weight average molecular weight was 1,230, and the hydroxyl group equivalent was 77,000.
＜実施例２＞
　撹拌装置、温度計および還流管を備えた５００ｍＬの容積の反応容器にテルペンフェノール樹脂　ＹＳポリスターＧ１２５（ヤスハラケミカル（株）製、水酸基当量４７６ｇ／ｅｑ、スチレン換算数平均分子量６５０、スチレン換算重量平均分子量１，０２９）３３．４ｇ、トルエン２４６．６ｇおよび水酸化ナトリウム水溶液２６．８ｇ、純水２８．６ｇを仕込み、７０℃に加熱撹拌した。反応温度を７０℃に保ちながらテトラブチルアンモニウムブロマイドの７０質量％水溶液８．１ｇおよびクロロメチルスチレンＣＭＳ－Ｐ　１４．５ｇを加え、１７０分撹拌した。有機相と水相を分液し、有機相を１．４質量％硫酸水溶液、次いで３０質量％メタノール水溶液で洗浄した。得られた溶液をロータリーエバポレーターで濃縮した後、２－ブタノン２６７．２ｇで希釈し、メタノール中に滴下することで固形化した。ろ別した固体を純水、次いでメタノールで洗浄した後、再度純水、メタノールで洗浄し、減圧乾燥して目的とするビニル基を有する樹脂（ビニルベンジルエーテル化合物Ｂ）２４．４ｇを得た。
　１Ｈ-ＮＭＲ分析の結果ビニルベンジルエーテル骨格に由来する新規ピークが、５．０２ｐｐｍ、５．２５ｐｐｍ、５．７４ｐｐｍ、５．７８ｐｐｍ、６．７～７．２ｐｐｍに観測された。ビニルベンジルエーテル化合物Ｂの数平均分子量は９９２、重量平均分子量は１，３９６、水酸基当量は２４，２４１ｇ／ｅｑであった。 <Example 2>
Toluene phenol resin YS Polystar G125 (manufactured by Yasuhara Chemical Co., Ltd., hydroxyl equivalent 476 g / eq, styrene equivalent number average molecular weight 650, styrene equivalent weight average molecular weight 1) in a reaction vessel with a volume of 500 mL equipped with a stirrer, thermometer and perfusion tube. , 029) 33.4 g, toluene 246.6 g, sodium hydroxide aqueous solution 26.8 g, and pure water 28.6 g were charged and heated and stirred at 70 ° C. While maintaining the reaction temperature at 70 ° C., 8.1 g of a 70 mass% aqueous solution of tetrabutylammonium bromide and 14.5 g of chloromethylstyrene CMS-P were added, and the mixture was stirred for 170 minutes. The organic phase and the aqueous phase were separated, and the organic phase was washed with a 1.4 mass% sulfuric acid aqueous solution and then a 30 mass% methanol aqueous solution. The obtained solution was concentrated by a rotary evaporator, diluted with 267.2 g of 2-butanone, and solidified by dropping into methanol. The separated solid was washed with pure water and then with methanol, washed again with pure water and methanol, and dried under reduced pressure to obtain 24.4 g of a resin (vinyl benzyl ether compound B) having a target vinyl group.
1 As a result of 1 H-NMR analysis, novel peaks derived from the vinylbenzyl ether skeleton were observed at 5.02 ppm, 5.25 ppm, 5.74 ppm, 5.78 ppm, and 6.7 to 7.2 ppm. The number average molecular weight of the vinylbenzyl ether compound B was 992, the weight average molecular weight was 1,396, and the hydroxyl group equivalent was 24,241 g / eq.
＜比較例１＞
　撹拌装置、温度計および還流管を備えた５００ｍＬの容積の反応容器に窒素雰囲気下で、テルペンフェノール樹脂　ＹＳポリスターＳ１４５（ヤスハラケミカル（株）製、水酸基当量が６４１ｇ／ｅｑ、スチレン換算数平均分子量６１２、スチレン換算重量平均分子量９２５）４９．９６ｇ、Ｎ，Ｎ－ジメチルアセトアミド（富士フイルム和光純薬（株）製、和光特級）１５０ｇ、クロロメチルスチレンＣＭＳ－Ｐ　２３．３ｇを仕込み、液温を５０℃に昇温させ加熱撹拌した。液温を５０℃に保ちながらナトリウムメトキシド（東京化成工業（株）製、２８．３質量％メタノール水溶液）２９．５ｍＬを滴下し、７０分撹拌した。さらにナトリウムメトキシド２ｍＬを滴下し、７０℃に昇温させ、６０分撹拌した。次に、リン酸（富士フイルム和光純薬（株）製、８５．６％）１．３６ｇ、Ｎ，Ｎ－ジメチルアセトアミド２．５２ｇを混合した溶液を添加して反応を停止した。反応停止から７０分経過後に濾紙Ｎｏ．５Ａ（桐山製作所社製）および桐山漏斗ＳＢ－６０（桐山製作所社製、直径６０ｍｍ）を用いて吸引ろ過した。濾物をＮ，Ｎ－ジメチルアセトアミド８１．６ｇで洗浄し、得られたろ液を２４７．５ｇの純水に滴下することで固形化し、ろ別した固体を純水、次いでメタノール（富士フイルム和光純薬（株）製、和光一級）で洗浄した後、２２０ｇのメタノールに再分散させた。再度固体をろ別し、メタノールで洗浄後減圧乾燥することで、ビニル基を有する樹脂（ビニルベンジルエーテル化合物Ｃ）を５５．８３ｇ得た。
　１Ｈ-ＮＭＲ分析の結果ビニルベンジルエーテル骨格に由来する新規ピークが、５．０２ｐｐｍ、５．２４ｐｐｍ、５．２６ｐｐｍ、５．７５ｐｐｍ、５．７８ｐｐｍ、６．７～７．２ｐｐｍに観測された。ビニルベンジルエーテル化合物Ｃの数平均分子量は６９８、重量平均分子量は１，０７２、水酸基当量は２４，５１５ｇ／ｅｑであった。 <Comparative Example 1>
Terpenphenol resin YS Polystar S145 (manufactured by Yasuhara Chemical Industries, Ltd., hydroxyl group equivalent 641 g / eq, styrene equivalent number average molecular weight 612, styrene equivalent number average molecular weight 612, under nitrogen atmosphere in a reaction vessel with a volume of 500 mL equipped with a stirrer, thermometer and perfusion tube. Styrene equivalent weight average molecular weight 925) 49.96 g, N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd., Wako Special Grade) 150 g, chloromethylstyrene CMS-P 23.3 g, and the liquid temperature is 50 ° C. The temperature was raised to 1 and the mixture was heated and stirred. While maintaining the liquid temperature at 50 ° C., 29.5 mL of sodium methoxide (28.3% by mass methanol aqueous solution manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 70 minutes. Further, 2 mL of sodium methoxide was added dropwise, the temperature was raised to 70 ° C., and the mixture was stirred for 60 minutes. Next, a solution containing 1.36 g of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., 85.6%) and 2.52 g of N, N-dimethylacetamide was added to terminate the reaction. 70 minutes after the reaction was stopped, the filter paper No. Suction filtration was performed using 5A (manufactured by Kiriyama Glass Co., Ltd.) and Kiriyama Funnel SB-60 (manufactured by Kiriyama Glass Co., Ltd., diameter 60 mm). The filtrate was washed with 81.6 g of N, N-dimethylacetamide, and the obtained filtrate was added dropwise to 247.5 g of pure water to solidify the filtrate. After washing with Yakuhin Co., Ltd. (Wako First Class), it was redistributed in 220 g of methanol. The solid was separated by filtration again, washed with methanol and dried under reduced pressure to obtain 55.83 g of a resin having a vinyl group (vinyl benzyl ether compound C).
1 As a result of 1 H-NMR analysis, novel peaks derived from the vinylbenzyl ether skeleton were observed at 5.02 ppm, 5.24 ppm, 5.26 ppm, 5.75 ppm, 5.78 ppm, and 6.7 to 7.2 ppm. The number average molecular weight of the vinylbenzyl ether compound C was 698, the weight average molecular weight was 1,072, and the hydroxyl group equivalent was 24,515 g / eq.
＜比較例２＞
　撹拌装置、温度計および還流管を備えた５００ｍＬの容積の反応容器に窒素雰囲気下で、テルペンフェノール樹脂　ＹＳポリスターＵ１１５（ヤスハラケミカル（株）製、水酸基当量が３，０４２ｇ／ｅｑ、スチレン換算数平均分子量５３３、スチレン換算重量平均分子量９８２）７５ｇ、Ｎ，Ｎ－ジメチルアセトアミド３００ｇ、クロロメチルスチレンＣＭＳ－Ｐ７．３ｇを仕込み、液温を５０℃に昇温させ加熱撹拌した。液温を５０℃に保ちながらナトリウムメトキシド９．３ｍＬを滴下し、７０分撹拌した。さらにナトリウムメトキシド０．６ｍＬを滴下し、７０℃に昇温させ、６０分撹拌した。次に、リン酸０．４５ｇ、Ｎ，Ｎ－ジメチルアセトアミド１．７ｇを混合した溶液を添加して反応を停止した。反応停止から７０分経過後にろ紙Ｎｏ．５Ａ（桐山製作所社製）および桐山漏斗ＳＢ－６０（桐山製作所社製、直径６０ｍｍ）を用いて吸引ろ過した。ろ物をＮ，Ｎ－ジメチルアセトアミド１９０ｇで洗浄し、得られたろ液を３４７ｇの純水に滴下することで固形化し、ろ別した固体を純水、次いでメタノールで洗浄した後、３０９ｇのメタノールに再分散させた。再度固体をろ別し、メタノールで洗浄後減圧乾燥することで、ビニル基を有する樹脂（ビニルベンジルエーテル化合物Ｄ）を４１．２５ｇ得た。
　１Ｈ-ＮＭＲ分析の結果ビニルベンジルエーテル骨格に由来する新規ピークが、４．７８ｐｐｍ、５．２４ｐｐｍ、５．２６ｐｐｍ、５．７５ｐｐｍ、５．７９ｐｐｍ、６．４～７．２ｐｐｍに観測された。ビニルベンジルエーテル化合物Ｄの数平均分子量は６５８、重量平均分子量は１，０９９、水酸基当量は１２，９１９ｇ／ｅｑであった。 <Comparative Example 2>
Terpenphenol resin YS Polystar U115 (manufactured by Yasuhara Chemical Co., Ltd., hydroxyl group equivalent of 3,042 g / eq, styrene equivalent number average molecular weight) in a reaction vessel with a volume of 500 mL equipped with a stirrer, thermometer and perfusion tube under a nitrogen atmosphere. 533, styrene equivalent weight average molecular weight 982) 75 g, N, N-dimethylacetamide 300 g, and chloromethylstyrene CMS-P7.3 g were charged, the liquid temperature was raised to 50 ° C., and the mixture was heated and stirred. 9.3 mL of sodium methoxide was added dropwise while keeping the liquid temperature at 50 ° C., and the mixture was stirred for 70 minutes. Further, 0.6 mL of sodium methoxide was added dropwise, the temperature was raised to 70 ° C., and the mixture was stirred for 60 minutes. Next, a mixed solution of 0.45 g of phosphoric acid and 1.7 g of N, N-dimethylacetamide was added to terminate the reaction. 70 minutes after the reaction was stopped, the filter paper No. Suction filtration was performed using 5A (manufactured by Kiriyama Glass Co., Ltd.) and Kiriyama Funnel SB-60 (manufactured by Kiriyama Glass Co., Ltd., diameter 60 mm). The filtrate was washed with 190 g of N, N-dimethylacetamide, the obtained filtrate was added dropwise to 347 g of pure water to solidify it, and the filtered solid was washed with pure water and then methanol, and then to 309 g of methanol. Redistributed. The solid was separated by filtration again, washed with methanol and dried under reduced pressure to obtain 41.25 g of a resin having a vinyl group (vinyl benzyl ether compound D).
1 As a result of 1 H-NMR analysis, new peaks derived from the vinylbenzyl ether skeleton were observed at 4.78 ppm, 5.24 ppm, 5.26 ppm, 5.75 ppm, 5.79 ppm, and 6.4 to 7.2 ppm. The number average molecular weight of the vinylbenzyl ether compound D was 658, the weight average molecular weight was 1,099, and the hydroxyl group equivalent was 12,919 g / eq.
＜比較例３＞
　撹拌装置、温度計および還流管を備えた５００ｍＬの容積の反応容器にテルペンフェノール樹脂　ＹＳポリスターＵＨ１１５（ヤスハラケミカル（株）製、水酸基当量３，５９６ｇ／ｅｑ、スチレン換算数平均分子量５８２、スチレン換算重量平均分子量９５９）３５．３ｇ、トルエン（富士フイルム和光純薬（株）製）２６０ｇおよび水酸化ナトリウム水溶液（関東化学（株）製、濃度：４８質量％）２７．０ｇ、純水３０．６ｇを仕込み、７０℃に加熱撹拌した。反応温度を７０℃に保ちながらテトラブチルアンモニウムブロマイド（東京化成工業（株）製）の７０質量％水溶液１．５ｇおよびクロロメチルスチレンＣＭＳ－Ｐ（ＡＧＣセイミケミカル（株）製）２．９ｇを加え、１７０分撹拌した。有機相と水相を分液し、有機相を１．４質量％硫酸水溶液、次いで３０質量％メタノール水溶液で洗浄した。得られた溶液をロータリーエバポレーターで濃縮した後、２－ブタノン（富士フイルム和光純薬（株）、特級）２２８．５ｇで希釈し、メタノール中に滴下することで固形化した。ろ別した固体を純水、次いでメタノールで洗浄した後、再度純水、メタノールで洗浄し、減圧乾燥して目的とするビニル基を有する樹脂（ビニルベンジルエーテル化合物Ｅ）３２．０ｇを得た。
　１Ｈ－ＮＭＲ分析の結果ビニルベンジルエーテル骨格に由来する新規ピークが、４．４６ｐｐｍ、５．２５ｐｐｍ、５．２７ｐｐｍ、５．７６ｐｐｍ、５．７９ｐｐｍ、６．４～７．２ｐｐｍに観測された。観測された。ビニルベンジルエーテル化合物Ｅの数平均分子量は７７８、重量平均分子量は１，２０９、水酸基当量は８，８６６ｇ／ｅｑであった。 <Comparative Example 3>
Toluene phenol resin YS Polystar UH115 (manufactured by Yasuhara Chemical Industries, Ltd., hydroxyl equivalent 3,596 g / eq, styrene equivalent number average molecular weight 582, styrene equivalent weight average) in a reaction vessel with a volume of 500 mL equipped with a stirrer, thermometer and perfusion tube. Molecular weight 959) 35.3 g, toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 260 g, sodium hydroxide aqueous solution (manufactured by Kanto Chemical Industries, Ltd., concentration: 48% by mass) 27.0 g, pure water 30.6 g , 70 ° C. with heating and stirring. While maintaining the reaction temperature at 70 ° C., add 1.5 g of a 70 mass% aqueous solution of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.9 g of chloromethylstyrene CMS-P (manufactured by AGC Seimi Chemical Co., Ltd.). , 170 minutes stirring. The organic phase and the aqueous phase were separated, and the organic phase was washed with a 1.4 mass% sulfuric acid aqueous solution and then a 30 mass% methanol aqueous solution. The obtained solution was concentrated with a rotary evaporator, diluted with 228.5 g of 2-butanone (Fuji Film Wako Pure Chemical Industries, Ltd., special grade), and solidified by dropping into methanol. The separated solid was washed with pure water and then with methanol, washed again with pure water and methanol, and dried under reduced pressure to obtain 32.0 g of a resin (vinyl benzyl ether compound E) having a target vinyl group.
1 As a result of 1 H-NMR analysis, new peaks derived from the vinylbenzyl ether skeleton were observed at 4.46 ppm, 5.25 ppm, 5.27 ppm, 5.76 ppm, 5.79 ppm, and 6.4 to 7.2 ppm. It was observed. The number average molecular weight of the vinylbenzyl ether compound E was 778, the weight average molecular weight was 1,209, and the hydroxyl group equivalent was 8,866 g / eq.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
＜実施例３＞
　上記で得られたビニルベンジルエーテル化合物Ａ（４．５ｇ）を長さ１００ｍｍ、幅３０ｍｍ、厚み１ｍｍの金型に入れ、北川精機（株）製５段プレス機ＶＨ２－１６３０を用いて、２００℃、９０分間真空プレス成形行い、硬化物Ａを得た。評価結果を表２に示す。 <Example 3>
The vinyl benzyl ether compound A (4.5 g) obtained above was placed in a mold having a length of 100 mm, a width of 30 mm and a thickness of 1 mm, and used at 200 ° C. using a 5-stage press machine VH2-1630 manufactured by Kitagawa Seiki Co., Ltd. , Vacuum press molding was performed for 90 minutes to obtain a cured product A. The evaluation results are shown in Table 2.
＜実施例４＞
　実施例３において、ビニルベンジルエーテル化合物Ａに代えてビニルベンジルエーテル化合物Ｂを用いた以外は実施例３に準拠し硬化物Ｂを得た。評価結果を表２に示す。 <Example 4>
In Example 3, a cured product B was obtained according to Example 3 except that the vinyl benzyl ether compound B was used instead of the vinyl benzyl ether compound A. The evaluation results are shown in Table 2.
＜比較例４＞
　ビニルベンジルエーテル化合物Ａに代えてビニルベンジルエーテル化合物Ｃを用いた以外は実施例３に準拠し硬化物Ｃを得た。評価結果を表２に示す。 <Comparative Example 4>
A cured product C was obtained according to Example 3 except that the vinyl benzyl ether compound C was used instead of the vinyl benzyl ether compound A. The evaluation results are shown in Table 2.
＜比較例５＞
　ビニルベンジルエーテル化合物Ａに代えてビニルベンジルエーテル化合物Ｄを用いた以外は実施例３に準拠し硬化物Ｄを得た。硬化物Ｄは非常に割れやすく、後述する硬化物の特性評価は実施できなかった。 <Comparative Example 5>
A cured product D was obtained according to Example 3 except that the vinyl benzyl ether compound D was used instead of the vinyl benzyl ether compound A. The cured product D was extremely fragile, and the characteristics of the cured product, which will be described later, could not be evaluated.
＜比較例６＞
　ビニルベンジルエーテル化合物Ａに代えてビニルベンジルエーテル化合物Ｅを用いた以外は実施例３に準拠し硬化物Ｅを得た。硬化物Ｅは非常に割れやすく、後述する硬化物の特性評価は実施できなかった。 <Comparative Example 6>
A cured product E was obtained according to Example 3 except that the vinyl benzyl ether compound E was used instead of the vinyl benzyl ether compound A. The cured product E was very fragile, and the characteristics of the cured product, which will be described later, could not be evaluated.
　硬化物の特性は以下の方法により評価した。
＜ガラス転移温度＞
　硬化物のガラス転移温度は、硬化物を長さ５０ｍｍ、幅５ｍｍにカットしたものについてセイコーインスツルメンツ（株）製 ＤＭＳ６１００を用い、振動周波数１０Ｈｚ、昇温速度２℃／分で動的粘弾性測定を行い、得られた損失弾性率のピークの温度とした。 The characteristics of the cured product were evaluated by the following method.
<Glass transition temperature>
The glass transition temperature of the cured product was measured by using DMS6100 manufactured by Seiko Instruments Co., Ltd. for the cured product cut to a length of 50 mm and a width of 5 mm at a vibration frequency of 10 Hz and a heating rate of 2 ° C / min. The temperature was taken as the peak temperature of the obtained loss elastic modulus.
＜誘電率、誘電正接＞
　硬化物の誘電率、誘電正接は、硬化物を長さ１００ｍｍ、幅０．８ｍｍにカットしたものについてＡｇｉｌｅｎｔ社製 ８７２２ＥＳ Ｎｅｔｗｏｒｋ Ａｎａｌｙｚｅｒを用いて、空洞共振器摂動法により、周波数１０ＧＨｚにおける値を測定した。 <Permittivity, dielectric loss tangent>
The dielectric constant and dielectric loss tangent of the cured product were measured at a frequency of 10 GHz by a cavity resonator perturbation method using an Agilent 8722ES Network Analyzer for the cured product cut to a length of 100 mm and a width of 0.8 mm. ..
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014

Claims (15)

  1. 水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂とハロゲン化メチル基を有するスチレンとを、塩基性化合物の存在下で反応させることを含む、ビニル基を有する樹脂の製造方法。 A method for producing a resin having a vinyl group, which comprises reacting a terpenphenol resin having a hydroxyl group equivalent of 260 to 580 g / eq with styrene having a methyl halide group in the presence of a basic compound.
  2. 前記塩基性化合物が、アルカリ金属アルコキシドおよびアルカリ金属水酸化物の少なくとも１種を含む、請求項１に記載のビニル基を有する樹脂の製造方法。 The method for producing a resin having a vinyl group according to claim 1, wherein the basic compound contains at least one of an alkali metal alkoxide and an alkali metal hydroxide.
  3. 前記ハロゲン化メチル基を有するスチレンが、式（１）で表される化合物を含む、請求項１または２に記載のビニル基を有する樹脂の製造方法。
    式（１）
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、Ｘは、塩素または臭素を表す。）     The method for producing a resin having a vinyl group according to claim 1 or 2, wherein the styrene having a methyl halide group contains a compound represented by the formula (1).
    Equation (1)
    Figure JPOXMLDOC01-appb-C000001
     (In formula (1), X represents chlorine or bromine.)
  4. 前記ハロゲン化メチル基を有するスチレンが、メタクロロメチルスチレンおよび／またはパラクロロメチルスチレンを含む、請求項１～３のいずれか１項に記載のビニル基を有する樹脂の製造方法。 The method for producing a resin having a vinyl group according to any one of claims 1 to 3, wherein the styrene having a methyl halide group contains metachloromethylstyrene and / or parachloromethylstyrene.
  5. 前記水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂のスチレン換算の数平均分子量（Ｍｎ）が４００以上９００以下である、請求項１～４のいずれか１項に記載のビニル基を有する樹脂の製造方法。 The resin having a vinyl group according to any one of claims 1 to 4, wherein the styrene-equivalent number average molecular weight (Mn) of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is 400 or more and 900 or less. Manufacturing method.
  6. 前記水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂のスチレン換算の重量平均分子量（Ｍｗ）が６５０以上１２００以下である、請求項１～５のいずれか１項に記載のビニル基を有する樹脂の製造方法。 The resin having a vinyl group according to any one of claims 1 to 5, wherein the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq has a styrene-equivalent weight average molecular weight (Mw) of 650 or more and 1200 or less. Manufacturing method.
  7. 水酸基当量が２６０～５８０ｇ／ｅｑであるテルペンフェノール樹脂のフェノール性水酸基の少なくとも一部がビニルベンジル基で変性された、ビニル基を有する樹脂。 A resin having a vinyl group in which at least a part of the phenolic hydroxyl group of the terpene phenol resin having a hydroxyl group equivalent of 260 to 580 g / eq is modified with a vinylbenzyl group.
  8. 式（２）で表される構成単位を有する、請求項７に記載のビニル基を有する樹脂。
    式（２）
    Figure JPOXMLDOC01-appb-C000002
     （式（２）中、＊は他の構成単位または末端基との結合部位を示す。）     The resin having a vinyl group according to claim 7, which has a structural unit represented by the formula (2).
    Equation (2)
    Figure JPOXMLDOC01-appb-C000002
     (In formula (2), * indicates a binding site with another structural unit or end group.)
  9. 式（３）で表される構成単位を有する、請求項７に記載のビニル基を有する樹脂。
    式（３）
    Figure JPOXMLDOC01-appb-C000003
     （式（３）中、＊は他の構成単位または末端基との結合部位を示す。ｍ、ｎおよびｏは、それぞれ独立に、構成単位のモル比率を表し、ｍは１以上の数であり、ｎは１以上の数であり、ｏは０以上の数を表す。）     The resin having a vinyl group according to claim 7, which has a structural unit represented by the formula (3).
    Equation (3)
    Figure JPOXMLDOC01-appb-C000003
     (In formula (3), * indicates a binding site with another structural unit or terminal group. m, n and o independently represent the molar ratio of the structural unit, and m is a number of 1 or more. , N is a number of 1 or more, and o represents a number of 0 or more.)
  10. スチレン換算数平均分子量（Ｍｎ）が７００以上１,２００以下である、請求項７～９のいずれか１項に記載のビニル基を有する樹脂。 The resin having a vinyl group according to any one of claims 7 to 9, wherein the styrene equivalent number average molecular weight (Mn) is 700 or more and 1,200 or less.
  11. スチレン換算重量平均分子量（Ｍｗ）が１,０００以上１,５００以下である、請求項７～１０のいずれか１項に記載のビニル基を有する樹脂。 The resin having a vinyl group according to any one of claims 7 to 10, wherein the styrene-equivalent weight average molecular weight (Mw) is 1,000 or more and 1,500 or less.
  12. 請求項７～１１のいずれか１項に記載のビニル基を有する樹脂を含む、硬化性樹脂組成物。 A curable resin composition comprising the resin having a vinyl group according to any one of claims 7 to 11.
  13. さらに、請求項７～１１のいずれか１項に記載のビニル基を有する樹脂以外の熱硬化性化合物を含む、請求項１２に記載の硬化性樹脂組成物。 The curable resin composition according to claim 12, further comprising a thermosetting compound other than the resin having a vinyl group according to any one of claims 7 to 11.
  14. 前記熱硬化性化合物が、請求項７～１１のいずれか１項に記載のビニル基を有する樹脂以外の化合物であって炭素炭素不飽和結合基を有する化合物およびエポキシ樹脂から選択される少なくとも１種を含む、請求項１３に記載の硬化性樹脂組成物。 The thermosetting compound is at least one selected from a compound other than the resin having a vinyl group according to any one of claims 7 to 11 and having a carbon-carbon unsaturated bond group and an epoxy resin. 13. The curable resin composition according to claim 13.
  15. 請求項１２～１４のいずれか１項に記載の硬化性樹脂組成物の硬化物。 The cured product of the curable resin composition according to any one of claims 12 to 14.
PCT/JP2021/025106 2020-08-12 2021-07-02 Manufacturing method for resin having vinyl group, resin having vinyl group, curable resin composition, and cured product WO2022034753A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09278867A (en) * 1996-04-10 1997-10-28 Toto Kasei Co Ltd Epoxy resin composition
JP2007015945A (en) * 2005-07-05 2007-01-25 Toto Kasei Co Ltd Vinylbenzyl ether compound and resin composition containing the compound as essential component
JP2020167258A (en) * 2019-03-29 2020-10-08 日東電工株式会社 Back grind tape

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09278867A (en) * 1996-04-10 1997-10-28 Toto Kasei Co Ltd Epoxy resin composition
JP2007015945A (en) * 2005-07-05 2007-01-25 Toto Kasei Co Ltd Vinylbenzyl ether compound and resin composition containing the compound as essential component
JP2020167258A (en) * 2019-03-29 2020-10-08 日東電工株式会社 Back grind tape

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