WO2024071047A1 - Résine vinylique polyfonctionnelle et procédé de production, composition et produit durci de celle-ci - Google Patents

Résine vinylique polyfonctionnelle et procédé de production, composition et produit durci de celle-ci Download PDF

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WO2024071047A1
WO2024071047A1 PCT/JP2023/034756 JP2023034756W WO2024071047A1 WO 2024071047 A1 WO2024071047 A1 WO 2024071047A1 JP 2023034756 W JP2023034756 W JP 2023034756W WO 2024071047 A1 WO2024071047 A1 WO 2024071047A1
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vinyl resin
formula
single bond
represented
polyfunctional vinyl
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PCT/JP2023/034756
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English (en)
Japanese (ja)
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昌己 大村
浩一郎 大神
ニランジャン クマール スレスタ
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日鉄ケミカル＆マテリアル株式会社
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Publication of WO2024071047A1 publication Critical patent/WO2024071047A1/fr

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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • 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 multifunctional vinyl resin, and more specifically to a multifunctional vinyl resin with excellent solvent solubility that is useful as an insulating material for electric and electronic components such as semiconductor encapsulation, laminates, and heat dissipation substrates, a method for producing the same, a resin composition, and a cured resin obtained by curing the same that has excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy.
  • the thermal conductivity of the inorganic filler is overwhelmingly higher than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is increased, it does not contribute significantly to improving the thermal conductivity of the composite material, and a sufficient effect of improving thermal conductivity has not been obtained.
  • Patent Document 7 discloses a tetrafunctional or higher vinyl resin having a biphenyl skeleton as a multifunctional vinyl resin that combines high thermal conductivity with a low dielectric tangent, but does not disclose the solvent solubility of the multifunctional vinyl resin or the polyhydric hydroxyl resin that is its raw material, nor does it mention the effect of impurities such as remaining polar groups on thermal conductivity.
  • JP 2009-170493 A International Publication No. 2013/100172 Japanese Patent Application Laid-Open No. 11-147936 JP 2002-309067 A Japanese Patent Application Laid-Open No. 11-323162 Japanese Patent Application Laid-Open No. 9-118673 International Publication No. 2021/200414
  • the object of the present invention is to provide a vinyl resin composition that is useful for sealing electric and electronic components, circuit board materials, etc., and that gives a cured product that has excellent solvent solubility as well as excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, and to provide the cured product.
  • Another object is to provide a vinyl resin used in this vinyl resin composition and a polyhydric hydroxyl resin that is suitable as an intermediate for this vinyl resin.
  • the present invention relates to a polyfunctional vinyl resin represented by the following general formula (1), characterized in that the polyfunctional vinyl resin has a vinyl equivalent of 200 to 450 g/eq, a hydroxyl group equivalent of 5000 g/eq or more, and a total chlorine content of 1000 ppm or less.
  • A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO- or a divalent hydrocarbon group having 1 to 6 carbon atoms
  • X represents an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring and a biphenyl ring
  • n represents a number from 0 to 20.
  • A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms, at least one of which is other than a single bond.
  • p and q each independently represent a number from 0 to 20.
  • the present invention also relates to a method for producing the polyfunctional vinyl resin, which comprises reacting 4,4'-dihydroxybiphenyl represented by formula (3) with an aromatic crosslinking agent represented by formula (4), and then further reacting the resulting mixture with a bifunctional phenol compound represented by formula (5) to obtain a polyhydric hydroxy resin represented by general formula (6), and then reacting the resulting polyhydric hydroxy resin with chloromethylstyrene.
  • X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms.
  • A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms.
  • A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms, at least one of which is other than a single bond.
  • p and q each independently represent a number from 0 to 20.
  • the present invention relates to a polyhydric hydroxy resin represented by the following general formula (6) and having a hydroxyl group equivalent of 100 to 350 g/eq.
  • A, p and q have the above meanings.
  • the present invention relates to a polyfunctional vinyl resin composition containing the above-mentioned polyfunctional vinyl resin and a radical polymerization initiator as essential components, and to a polyfunctional vinyl resin cured product obtained by curing this polyfunctional vinyl resin composition.
  • the multifunctional vinyl resin of the present invention has excellent solvent solubility and is suitable for use in vinyl resin compositions and their cured products for applications such as lamination, molding, casting, and adhesion. Furthermore, the cured products also have excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, making them suitable for sealing electric and electronic components, as circuit board materials, etc.
  • Example 1 is a GPC chart of the multifunctional vinyl resin obtained in Example 1.
  • the polyfunctional vinyl resin of the present invention is a vinyl resin represented by general formula (1), characterized in that it has a vinyl equivalent of 200 to 450 g/eq, a hydroxyl group equivalent of 5000 g/eq or more, and a total chlorine content of 1000 ppm or less.
  • n is the number of repetitions (number average) and is a number from 0 to 20.
  • the vinyl resin of the present invention is usually a mixture of components having different values of the number of repetitions (n), and the average value (number average) of n is preferably in the range of 0.1 to 15, more preferably in the range of 0.5 to 10.
  • A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO- or a divalent hydrocarbon group having 1 to 6 carbon atoms
  • X represents an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring and a biphenyl ring. From the viewpoint of thermal conductivity, it is preferable that A is a single bond and X is a biphenyl ring.
  • the polyfunctional vinyl resin of the present invention has, with respect to the polar groups, a hydroxyl group equivalent of 5000 g/eq or more and a total chlorine content of 1000 ppm or less.
  • the polyfunctional vinyl resin of the present invention can be obtained by reacting a polyhydric hydroxyl resin with chloromethylstyrene, but if the amount of unreacted hydroxyl groups remaining is less than 5000 g/eq, the curing is insufficient, and the thermal conductivity and heat resistance are reduced.
  • the hydroxyl groups are polar groups, the remaining hydroxyl groups inhibit the reduction of the dielectric constant and the dielectric loss tangent.
  • the hydroxyl equivalent is preferably 10,000 g/eq or more, more preferably 12,000 g/eq or more.
  • the chlorine components are derived from chloromethylstyrene and crosslinking agents in polyhydric hydroxy resins. These are difficult to remove when the vinyl resin has low solvent solubility. If the chlorine components remain in an amount of more than 1000 ppm, they tend to inhibit the reduction of dielectric constant and dielectric loss tangent, and inhibit the curing reaction, thereby decreasing thermal conductivity and heat resistance.
  • the total chlorine content is preferably 700 ppm or less, more preferably 500 ppm or less.
  • the polyfunctional vinyl resin of the present invention is preferably a polyfunctional vinyl resin represented by general formula (2).
  • p and q are the repeating numbers (number average) and are numbers from 0 to 20. Preferably, it is a mixture of components with different values of p and q.
  • the ratio (molar ratio) of p/(p+q) is preferably 0.50 to 0.95, more preferably 0.70 to 0.95. If it is less than 0.50, the effect of heat resistance and high thermal conductivity is small, and if it is more than 0.95, the crystallinity becomes strong and the solvent solubility decreases.
  • the average value of p is preferably 0.1 to 10, more preferably 0.5 to 5.
  • the average value of q is preferably 0.1 to 5, more preferably 0.1 to 2.
  • A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms. It is preferable that the substitution positions of the two vinylbenzyl ether groups bonded to the biphenyl structure having A include at least the 2,2' form.
  • the substitution positions of the two vinylbenzyl ether groups bonded thereto are preferably the 4,4' and 2,2' positions, and the ratio of the biphenyl at both ends is preferably 40 to 90 mol % at the 2,2' positions relative to the total.
  • A is other than a single bond, i.e., when both ends of the vinyl resin are other than biphenyl rings, for example, when the vinyl resin has a diphenylmethane structure, it is preferable that the substitution positions of the two vinylbenzyl ether groups bonded thereto are 30 to 100 mol % at the 4,4' positions.
  • the polyfunctional vinyl resin represented by the above formula (2) can be produced by reacting a polyhydric hydroxy resin represented by the formula (6) with chloromethylstyrene.
  • A, p, q, and the ratio of p/(p+q) are the same as those of the polyfunctional vinyl resin.
  • the polyhydric hydroxyl resin of the present invention represented by formula (6) preferably has a hydroxyl group equivalent of 100 to 350 g/eq. These polyhydric hydroxyl groups are partially or entirely vinylized to form the polyfunctional vinyl resin of the present invention represented by formula (2).
  • this polyhydric hydroxy resin can be produced by reacting 4,4'-dihydroxybiphenyl represented by formula (3) with an aromatic crosslinking agent having a biphenyl structure represented by formula (4), and then reacting the resulting mixture with a bifunctional phenol compound represented by formula (5).
  • X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms.
  • A represents a single bond, an oxygen atom, a sulfur atom, --SO ⁇ SUB>2 ⁇ /SUB>-, --CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms.
  • the molar ratio of 4,4'-dihydroxybiphenyl represented by formula (3) and the bifunctional phenol compound represented by formula (5) when the synthesis raw materials are charged is preferably 0.50 to 0.95, more preferably 0.70 to 0.95, for 4,4'-dihydroxybiphenyl. If the ratio of 4,4'-dihydroxybiphenyl is less than this range, the heat resistance and high thermal conductivity are insufficient, and if it is more than this range, the solvent solubility is reduced due to strong crystallinity.
  • bifunctional phenol compound of formula (5) examples include 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, dihydroxydiphenylmethanes, and 2,2-bis(4-hydroxyphenyl)propane.
  • 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and dihydroxydiphenylmethanes are preferred from the viewpoint of solvent solubility.
  • the dihydroxydiphenylmethane may be a mixture of ortho, meta, and para, but isomer ratios of 4,4'-dihydroxydiphenylmethane of 40% or less are preferred. If the amount of 4,4'-dihydroxydiphenylmethane is large, there is a concern that the crystallinity will be high and the solvent solubility will decrease.
  • X represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms.
  • aromatic condensing agents include 4,4'-bishydroxymethylbiphenyl, 4,4'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4,4'-bismethoxymethylbiphenyl, and 4,4'-bisethoxymethylbiphenyl.
  • 4,4'-bishydroxymethylbiphenyl or 4,4'-bischloromethylbiphenyl is preferred, and from the viewpoint of reducing ionic impurities, 4,4'-bishydroxymethylbiphenyl or 4,4'-bismethoxymethylbiphenyl is preferred.
  • the reaction between phenols and aromatic condensing agents can be carried out without a catalyst or in the presence of an acid catalyst such as an inorganic acid or an organic acid.
  • an acid catalyst such as an inorganic acid or an organic acid.
  • the reaction can be carried out without a catalyst, but it is generally better to carry out the reaction in the presence of an acid catalyst to suppress side reactions such as the reaction of a chloromethyl group with a hydroxyl group to form an ether bond.
  • This acid catalyst can be appropriately selected from well-known inorganic and organic acids, and examples of such acid catalysts include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethasulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids.
  • mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid
  • organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethasulfonic acid
  • Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids.
  • this reaction is carried out at 100 to 250°C for 1 to 20 hours. It is preferably carried out at 100 to 180°C, and more preferably at 140 to 180°C. If the reaction temperature is low, the reactivity will be poor and it will take time, and if the reaction temperature is high, there is a risk of the resin decomposing.
  • the solvent used during the reaction may be, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, or aromatic compounds such as benzene, toluene, chlorobenzene, or dichlorobenzene, of which ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, etc. are particularly preferred.
  • alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, or aromatic compounds such as benzene, toluene, chlorobenzene, or dichlorobenzene, of which ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, etc. are particularly
  • the solvent may be removed from the resulting polyhydric hydroxyl resin by methods such as vacuum distillation, washing with water, or reprecipitation in a poor solvent, but the solvent may also be left in the resin and used as a raw material for the vinylization reaction.
  • the polyfunctional vinyl resin of the present invention can be suitably obtained by reacting a polyhydric hydroxy resin with an aromatic vinylating agent.
  • the vinyl resin of the present invention represented by the above formula (2) can be obtained by reacting a polyhydric hydroxy resin represented by the above formula (6) with chloromethylstyrene. This reaction can be carried out in the same manner as the well-known vinylation reaction.
  • Aromatic vinylating agents are preferably halomethylstyrenes, particularly chloromethylstyrene.
  • Other examples include bromomethylstyrene and its isomers, and those with substituents.
  • the substitution position of the halomethyl compound for example, in the case of halomethylstyrene, the 4-position is preferred, and it is preferable that the 4-position compound accounts for 60% or more by weight of the total.
  • the reaction between the polyhydric hydroxy resin and the aromatic vinylating agent can be carried out in the absence of a solvent or in the presence of a solvent.
  • the reaction can be carried out by adding the aromatic vinylating agent to the polyhydric hydroxy resin, adding a metal hydroxide, and removing the generated metal salt by a method such as filtration or washing with water.
  • the solvent include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc. From the viewpoint of reactivity, methyl ethyl ketone is preferable.
  • Specific examples of the metal hydroxide include, but are not limited to, sodium hydroxide, potassium hydroxide, etc.
  • the vinylization reaction is carried out at a temperature of 90°C or less, preferably 70°C or less. If the temperature is higher than this, the heat of the vinyl benzyl ether group will cause self-polymerization, making it difficult to control the reaction.
  • polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso and nitrone compounds, and oxygen may be used.
  • the end point of the reaction can be determined by tracking the remaining amount of halomethylstyrene as an aromatic vinylating agent using various chromatograms such as GPC, and the reaction rate can be adjusted by the type and amount of metal hydroxide, the addition rate, solids concentration, etc.
  • it is desirable to purify the resulting polyfunctional vinyl resin by removing the solvent, etc., by a method such as distillation under reduced pressure, washing with water, or reprecipitation in a poor solvent.
  • the polyfunctional vinyl resin of the present invention can be cured alone, it is also suitable to use it as a polyfunctional resin composition containing various additives.
  • a radical polymerization initiator such as an azo compound or an organic peroxide may be blended to effect curing.
  • the polyfunctional vinyl resin of the present invention can be blended with other vinyl resins and other thermosetting resins, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoxazine resins.
  • thermosetting resins such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoxazine resins.
  • the polyfunctional vinyl resin composition may contain fillers such as glass cloth, carbon fiber, alumina, and boron nitride to increase thermal conductivity.
  • thermal conductivity is preferably 20 W/m.K or more, more preferably 30 W/m.K or more, and even more preferably 50 W/m.K or more. At least a portion of the inorganic filler, preferably 50 wt% or more, has a thermal conductivity of 20 W/m.K or more.
  • the average thermal conductivity of the inorganic filler as a whole increases in the order of desirability: 20 W/m.K or more, 30 W/m.K or more, and 50 W/m.K or more.
  • inorganic fillers with such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide.
  • additives may be added to improve adhesive strength and ease of handling of the composition, such as silane coupling agents, defoamers, internal release agents, and flow control agents.
  • the polyfunctional vinyl resin or polyfunctional vinyl resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg, which can then be hot-press molded to obtain a cured product.
  • a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone
  • the resin can be applied onto a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film to form a laminate, and the resin sheet obtained by heating and drying can be subjected to heat press molding to obtain a cured product.
  • a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film
  • GPC Measurement A main body (HLC-8220GPC, manufactured by Tosoh Corporation) equipped with four columns (TSKgel Super Multipore HZ-N, manufactured by Tosoh Corporation) in series was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was set to 0.35 mL/min, and a differential refractive index detector was used as the detector. 50 ⁇ L of the measurement sample was prepared by dissolving 0.1 g of sample in 10 mL of THF and filtering through a microfilter. Data processing was performed using GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation.
  • THF Tetrahydrofuran
  • Solvent solubility 2 g of resin and 1 g of cyclohexanone were weighed and placed in a sample bottle, and after heating and dissolving, the temperature was gradually lowered in a thermostatic chamber, and the temperature in the chamber at which the resin precipitated was measured. The higher the precipitation temperature (°C), the poorer the solvent solubility.
  • Tg Glass transition temperature
  • Td5 5% weight loss temperature
  • carbon residue ratio Using a thermogravimetric/differential thermal analyzer (EXSTAR TG/DTA7300, manufactured by SII Nano Technology), the 5% weight loss temperature (Td5) was measured under conditions of a nitrogen atmosphere and a heating rate of 10°C/min. The weight loss at 700°C was also measured and calculated as the carbon residue ratio.
  • Thermal Conductivity was measured by a non-steady hot wire method using a NETZSCH LFA447 type thermal conductivity meter.
  • Example 1 Into a 1000 ml four-neck flask, 65.3 g (0.35 mol) of 4,4'-dihydroxybiphenyl (structural formula below), Diethylene glycol dimethyl ether 121.2 g, 4,4'-bischloromethylbiphenyl (structural formula below) 58.7 g (0.23 mol) The mixture was heated to 170° C.
  • dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane (structural formula below): 36.2%, 2,4'-dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%) was added. was reacted to produce a polyhydric hydroxy resin (hydroxyl group equivalent: 129 g/eg). After the reaction was completed, 50.7 g of diethylene glycol dimethyl ether was recovered, 320 g of methyl ethyl ketone, and 135.5 g of chloromethylstyrene (structure shown below).
  • the mixture was heated to 60°C, and 49.8 g of potassium hydroxide dissolved in 150 g of methanol was added dropwise over 3 hours, followed by further reaction for 6 hours. After the reaction was completed, the mixture was filtered, the solvent was removed, and the mixture was reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 141 g of a white solid vinyl resin (vinyl resin A).
  • the vinyl equivalent of vinyl resin A was 275 g/eg., the hydroxyl equivalent was 15,000 g/eg., and the total chlorine was 300 ppm.
  • the GPC chart of the obtained multifunctional vinyl resin is shown in Figure 1. According to the charging ratio, the ratio (molar ratio) of p/(p+q) was 0.93, p was 4.2, and q was 0.3.
  • Example 2 instead of dihydroxydiphenylmethane, 7.3 g (0.04 mol) of 2,2'-dihydroxybiphenyl (structural formula below) The reaction was carried out in the same manner as in Example 1, except that polyhydric hydroxyl resin (hydroxyl equivalent: 116 g/eg) and further polyfunctional vinyl resin (138 g) were obtained (vinyl resin B).
  • the vinyl equivalent of vinyl resin B was 262 g/eg., the hydroxyl equivalent was 13,000 g/eg., and the total chlorine was 340 ppm.
  • the ratio (molar ratio) of p/(p+q) was 0.93, p was 4.0, and q was 0.3.
  • Example 3 instead of 4,4'-bischloromethylbiphenyl, 40.2 g (0.23 mol) of p-xylylene dichloride
  • the reaction was carried out in the same manner as in Example 1, except that polyhydric hydroxyl resin (hydroxyl equivalent: 105 g/eg) and 129 g of polyfunctional vinyl resin were obtained (vinyl resin C).
  • the vinyl equivalent of vinyl resin C was 252 g/eg., the hydroxyl equivalent was 13,400 g/eg., and the total chlorine was 320 ppm.
  • the ratio (molar ratio) of p/(p+q) was 0.93, p was 3.7, and q was 0.3.
  • the obtained resin was dissolved in toluene, neutralized, and washed with water to obtain 172 g of a multifunctional vinyl resin (vinyl resin D).
  • the vinyl equivalent of the obtained vinyl resin D was 256 g/eq., the hydroxyl equivalent was 1500 g/eq., and the total chlorine was 1270 ppm.
  • Comparative Example 2 The same procedure as in Comparative Example 1 was carried out except that 58.9 g of 4,4'-bis(chloromethyl)biphenyl was used and 63.0 g of phenol was used instead of 4,4'-dihydroxybiphenyl, to obtain 160 g of a multifunctional vinyl resin (vinyl resin E).
  • the vinyl equivalent of the obtained vinyl resin E was 331 g/eq, the hydroxyl equivalent was 2100 g/eq, and the total chlorine was 1680 ppm.
  • Example 3 The same procedure as in Example 1 was carried out except that 320 g of diethylene glycol dimethyl ether was used instead of 320 g of methyl ethyl ketone, and the reaction with chloromethylstyrene was carried out at 80°C, to obtain 135 g of a multifunctional vinyl resin (vinyl resin F).
  • the vinyl equivalent of vinyl resin F was 95 g/eg., the hydroxyl equivalent was 1000 g/eg., and the total chlorine was 260 ppm.
  • the ratio (molar ratio) of p/(p+q) was 0.90, and the mixture was in the range of p to 10 and q to 4.
  • Example 4 The same operation as in Example 1 was carried out, except that reprecipitation with methanol was not carried out in the operation after the end of the reaction in Example 1, to obtain 150 g of a multifunctional vinyl resin (vinyl resin G).
  • the vinyl equivalent of vinyl resin G was 285 g/eg., the hydroxyl equivalent was 16,000 g/eg., and the total chlorine was 3,000 ppm.
  • the ratio (molar ratio) of p/(p+q) was 0.90, and it was a mixture in which p was in the range of 0 to 8 and q was in the range of 0 to 2.
  • vinyl resin H a multifunctional vinyl resin
  • the vinyl equivalent of vinyl resin H was 217 g/eg., the hydroxyl equivalent was 17000 g/eg., and the total chlorine was 400 ppm.
  • Examples 4 to 6, Comparative Examples 6 to 11 As the polyfunctional vinyl resin, vinyl resins A to H and vinyl resin I (OPE-2ST: manufactured by Mitsubishi Gas Chemical Company, Inc., vinyl group equivalent: 590.0 g / eq, number average molecular weight 1187) obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were used, and Perbutyl P (manufactured by NOF Corporation), an organic peroxide, was used as a curing accelerator (radical polymerization initiator), and Adeka STAB AO-60 (manufactured by ADEKA Corporation) was used as an antioxidant in the blending ratio shown in Table 1. The composition was applied to a PET film and dried at 130 ° C. for 5 minutes to obtain a resin composition. The composition removed from the PET film was sandwiched between mirror plates and cured under reduced pressure at 130 ° C. for 15 minutes and at 210 ° C. for 80 minutes while applying a pressure of 2 MPa. The properties of the obtained cured product are shown in Table 1.
  • the multifunctional vinyl resin of the example exhibited excellent physical properties, including high thermal conductivity, low dielectric constant, and low dielectric tangent.
  • the multifunctional vinyl resin of the present invention is useful as an electronic material for high-speed communication devices, as it easily dissipates heat from electronic components and wiring and has little signal loss.

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Abstract

La présente invention concerne une résine vinylique qui présente une excellente solubilité par rapport aux solvants, qui fournit un produit durci présentant une excellente résistance à la chaleur, une excellente stabilité à la dégradation thermique, une excellente conductivité thermique, une faible permittivité, une faible tangente de perte diélectrique et une excellente résistance au feu, et qui est utile pour sceller des composants électriques/électroniques, et utile en tant que matériaux de carte de circuit imprimé et analogues.　Cette résine vinylique polyfonctionnelle est représentée par la formule générale (1) et est caractérisée en ce qu'elle présente un équivalent vinyle de 200 à 450 g/éq, un équivalent hydroxyle supérieur ou égal à 5000 g/éq et une quantité totale de chlore inférieure ou égale à 1000 ppm.
PCT/JP2023/034756 2022-09-29 2023-09-25 Résine vinylique polyfonctionnelle et procédé de production, composition et produit durci de celle-ci WO2024071047A1 (fr)

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Publication number Priority date Publication date Assignee Title
JP2020002293A (ja) * 2018-06-29 2020-01-09 日鉄ケミカル＆マテリアル株式会社 多価ヒドロキシ樹脂の製造方法
WO2021200414A1 (fr) * 2020-03-30 2021-10-07 日鉄ケミカル＆マテリアル株式会社 Résine vinylique polyfonctionnelle et procédé de production associé
WO2021241255A1 (fr) * 2020-05-28 2021-12-02 日鉄ケミカル＆マテリアル株式会社 Résine vinylique polyfonctionnelle et procédé de production associé

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020002293A (ja) * 2018-06-29 2020-01-09 日鉄ケミカル＆マテリアル株式会社 多価ヒドロキシ樹脂の製造方法
WO2021200414A1 (fr) * 2020-03-30 2021-10-07 日鉄ケミカル＆マテリアル株式会社 Résine vinylique polyfonctionnelle et procédé de production associé
WO2021241255A1 (fr) * 2020-05-28 2021-12-02 日鉄ケミカル＆マテリアル株式会社 Résine vinylique polyfonctionnelle et procédé de production associé

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