WO2023017855A1 - Composition de résine ainsi que procédé de fabrication de celle-ci, et matériau composite - Google Patents

Composition de résine ainsi que procédé de fabrication de celle-ci, et matériau composite Download PDF

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Publication number
WO2023017855A1
WO2023017855A1 PCT/JP2022/030721 JP2022030721W WO2023017855A1 WO 2023017855 A1 WO2023017855 A1 WO 2023017855A1 JP 2022030721 W JP2022030721 W JP 2022030721W WO 2023017855 A1 WO2023017855 A1 WO 2023017855A1
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Prior art keywords
resin composition
vinyl ester
resin
meth
ester resin
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PCT/JP2022/030721
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English (en)
Japanese (ja)
Inventor
健一 小林
直樹 後藤
尚人 岡田
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昭和電工株式会社
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Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to KR1020247002260A priority Critical patent/KR20240023162A/ko
Priority to JP2023541474A priority patent/JPWO2023017855A1/ja
Priority to CN202280054092.4A priority patent/CN117794966A/zh
Publication of WO2023017855A1 publication Critical patent/WO2023017855A1/fr

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Classifications

    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/064—Polymers containing more than one epoxy group per molecule
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide

Definitions

  • the present invention relates to a resin composition containing a vinyl ester resin, a method for producing the same, and a composite material.
  • Prepregs and sheet molding compounds which are made by impregnating fiber base materials such as reinforcing fibers with curable resins, are used in a wide variety of fields such as industrial parts, housing equipment parts, and automobile parts.
  • Thermosetting resins such as unsaturated polyester resins and vinyl ester resins are generally used as resin compositions for impregnating prepregs and SMCs.
  • the resin composition may contain a thickener.
  • a thickener for example, Patent Document 1 discloses a resin composition containing at least one of a vinyl ester resin and an unsaturated polyester resin, a thickener, a polymerization initiator, a polymerization inhibitor, and an ethylenically unsaturated compound. , disclose SMC impregnated with reinforcing fibers.
  • Patent Document 1 The SMC described in Patent Document 1 is said to be excellent in storage stability because the progress of curing before heat and pressure molding is suppressed. It cannot be said that the thickening rate from the process to the sheet forming process is sufficiently controlled.
  • the resin composition used for prepreg and SMC has an appropriate thickening rate from the step of impregnating the fiber base material to the sheet forming step, is excellent in handleability in the manufacturing process of prepreg and SMC, and is manufactured.
  • the prepreg and SMC are required to have good shape retention and to exhibit sufficient mechanical strength after curing.
  • the present invention has been made to solve the above-described problems, and has a low initial viscosity immediately after production, thickens at an appropriate rate, and has excellent handleability, and a method for producing the same.
  • An object of the present invention is to provide a composite material containing the resin composition.
  • the present invention is based on the discovery that by using a vinyl ester resin with a predetermined molecular weight distribution, a resin composition having a low initial viscosity immediately after production and thickening at an appropriate rate can be obtained.
  • the present invention provides the following means.
  • [1] Contains a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), and at least one metal compound (C) selected from oxides and hydroxides of Group 2 elements
  • the vinyl ester resin (A) has a weight average molecular weight Mw of 1,500 or more and a ratio Mw/Mn between the weight average molecular weight Mw and the number average molecular weight Mn of 2.0 or more.
  • [2] The resin composition according to [1] above, wherein the vinyl ester resin (A1) has a weight average molecular weight Mw of 35,000 or less.
  • the vinyl ester resin (A1) includes an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2) and a polybasic acid anhydride (a1-).
  • the resin precursor (P1) which is the reaction product of 3), and the addition reaction product of the polybasic acid anhydride (a1-4), and the total amount of epoxy groups of the epoxy compound (a1-1) is 100 mol.
  • the resin composition according to [6] above, wherein the epoxy compound (a1-1) is a bisphenol type epoxy resin.
  • a vinyl ester in which the vinyl ester resin (A) is a reaction product of an epoxy compound (a2-1) having two or more epoxy groups in one molecule and an unsaturated monobasic acid (a2-2) The resin composition according to any one of [6] to [10] above, further comprising a resin (A2).
  • the ethylenically unsaturated group-containing monomer (B) is styrene, methyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl.
  • any one of the above [1] to [11], which is at least one selected from (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tetraethylene glycol di(meth)acrylate The resin composition according to Item. [13] The resin composition according to any one of [1] to [12] above, wherein the metal compound (C) is magnesium oxide. [14] The content of the metal compound (C) is 0.01 to 6 parts by mass with respect to a total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). The resin composition according to any one of [1] to [13] above.
  • an epoxy compound (a1-1) having two epoxy groups in one molecule Saturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) are combined with the polybasic acid
  • a composite material comprising the resin composition according to any one of [1] to [16] above and a fiber base material.
  • a resin composition that has low initial viscosity immediately after production, thickens at an appropriate speed, and is excellent in handleability, a method for producing the same, and a composite material containing the resin composition.
  • (Meth)acrylic acid is a generic term for acrylic acid and methacrylic acid.
  • (meth)acrylate is a generic term for acrylate and methacrylate
  • (meth)acryloyl is a generic term for acryloyl and methacryloyl.
  • Weight average molecular weight Mw (hereinafter also simply referred to as "Mw)
  • “Number average molecular weight Mn” (hereinafter also simply referred to as "Mn”) are obtained by gel permeation chromatography (GPC) measurement. It is the standard polystyrene equivalent molecular weight that is used.
  • the "acid value" of the vinyl ester resin is the number of mg of potassium hydroxide required to neutralize 1 g of the vinyl ester resin, measured by a method conforming to JIS K6901:2008. Specifically, it is measured by the method described in Examples below.
  • the "viscosity" of the vinyl ester resin is expressed as the viscosity of a mixture of 65% by mass of the vinyl ester resin and 35% by mass of phenoxyethyl methacrylate. It is a value measured at a temperature of 25° C. using an E-type viscometer. Specifically, it is measured by the method described in Examples below.
  • the “viscosity” of the resin composition is a value measured at a temperature of 23° C. using a Brookfield viscometer. Specifically, it is measured by the method described in Examples below. "Initial viscosity” refers to the viscosity measured within 1 hour immediately after the production of the resin composition.
  • An acid group derived from a polybasic acid anhydride means a free acid group generated from a polybasic acid anhydride unless otherwise specified.
  • the resin composition of the present embodiment is at least one selected from vinyl ester resin (A), ethylenically unsaturated group-containing monomer (B), and oxides and hydroxides of Group 2 elements. It contains a metal compound (C).
  • the vinyl ester resin (A) has a weight average molecular weight Mw of 1,500 or more, and a vinyl ester resin (A1) having a ratio Mw/Mn between the weight average molecular weight Mw and the number average molecular weight Mn of 2.0 or more. including.
  • the resin composition has a low initial viscosity, thickens at an appropriate speed, and is excellent in handleability.
  • resin compositions used for prepregs and SMCs are required to have low viscosity so that they can easily impregnate fiber base materials such as reinforcing fibers.
  • the resin composition is required to have a viscosity that allows it to be uniformly distributed in the fiber base material without being unevenly distributed.
  • the resin composition of the present embodiment has a low viscosity when impregnated into a fiber base material, but increases in viscosity at an appropriate rate over time, and is uniformly distributed in the fiber base material during sheet molding. Since the viscosity can be high enough to maintain the state, it is suitable for the production of prepreg and SMC.
  • the resin composition of the present embodiment contains a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B) and a metal compound (C), and in addition to these components, may contain other components described later.
  • the total content of the vinyl ester resin (A), the ethylenically unsaturated group-containing monomer (B) and the metal compound (C) in 100 parts by mass of the resin composition is preferably is 85 to 100 parts by mass, more preferably 90 to 100 parts by mass, and still more preferably 95 to 100 parts by mass.
  • vinyl ester resin (A), ethylenically unsaturated group-containing monomer (B) and metal compound ( The total content of C) is preferably 30 to 80 parts by mass, more preferably 45 to 75 parts by mass, still more preferably 50 to 70 parts by mass.
  • Vinyl ester resin (A) contains vinyl ester resin (A1).
  • the vinyl ester resin (A1) may be used alone or in combination of two or more.
  • the vinyl ester resin (A) may contain a vinyl ester resin (A2) described later, if necessary.
  • the content of the vinyl ester resin (A) in the resin composition is preferably 30 to 75 parts by mass with respect to a total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B) described later. parts, more preferably 35 to 70 parts by mass, still more preferably 40 to 65 parts by mass.
  • the content of the vinyl ester resin (A) is 30 parts by mass or more, it is easy to control the thickening speed of the resin composition.
  • the content of the vinyl ester resin (A) is 75 parts by mass or less, the increase in the initial viscosity of the resin composition can be easily suppressed by the ethylenically unsaturated group-containing monomer (B).
  • the content of the vinyl ester resin (A) in the resin composition is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, still more preferably 100 parts by mass in total of the resin composition. is 40 to 55 parts by mass.
  • the vinyl ester resin (A) is 30 parts by mass or more, the vinyl ester resin (A1) tends to favorably accelerate the thickening speed of the resin composition.
  • the ethylenically unsaturated group-containing monomer (B) tends to suppress an increase in the initial viscosity of the resin composition.
  • the vinyl ester resin (A1) has a weight average molecular weight Mw of 1,500 or more.
  • the weight-average molecular weight Mw of the vinyl ester resin (A1) is a main factor in increasing the viscosity of the resin composition.
  • the weight average molecular weight Mw of the vinyl ester resin (A1) is preferably 2,000 or more, more preferably 4,000 or more, and still more preferably 6,000 or more, from the viewpoint of more efficiently thickening the resin composition. be.
  • it is preferably 35,000 or less, more preferably 25,000 or less, and still more preferably 15,000 or less.
  • Mw/Mn of the vinyl ester resin (A1) is 2.0 or more.
  • Mw/Mn is an index of molecular weight distribution, and when it is 1, it represents a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution.
  • Mw/Mn of the vinyl ester resin (A1) is 2.0 or more, it is easy to control the synthesis conditions of the vinyl ester resin (A1).
  • Mw/Mn of the vinyl ester resin (A1) is preferably 2.5 or more, more preferably 3.0 or more, and still more preferably 4 from the viewpoint of ease of control of the synthesis conditions of the vinyl ester resin (A1). .0 or more.
  • the rate of thickening, and suppressing variation in the physical properties of the resin composition it is preferably 18 or less, more preferably 12 or less, and still more preferably 10 or less.
  • the number average molecular weight Mn of the vinyl ester resin (A1) is preferably 500 or more, more preferably 700 or more, still more preferably 900 or more, from the viewpoint of efficiently thickening the resin composition. Moreover, from the viewpoint of suppressing the increase in the initial viscosity of the resin composition and controlling the thickening speed, it is preferably 2,500 or less, more preferably 1,800 or less, and still more preferably 1,600 or less.
  • the acid value of the vinyl ester resin (A1) is preferably 5 mg KOH/g or more, more preferably 10 mg KOH/g or more, and still more preferably 15 mg KOH/g or more. From the viewpoint of controlling the thickening rate of the resin composition, it is preferably 100 mg KOH/g or less, more preferably 90 mg KOH/g or less, and even more preferably 80 mg KOH/g or less.
  • the vinyl ester resin (A1) is preferably used after adjusting the viscosity using a solvent, a reactive diluent, or the like, from the viewpoint of controlling the initial viscosity of the resin composition and ease of mixing.
  • the adjusted viscosity is preferably 1 to 400 Pa ⁇ s, more preferably 10 to 300 Pa ⁇ s, still more preferably 20 to 150 Pa ⁇ s.
  • the vinyl ester resin (A1) is a reaction of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2) and a polybasic acid anhydride (a1-3). It is preferably an addition reaction product between the product resin precursor (P1) and the polybasic acid anhydride (a1-4).
  • the vinyl ester resin (A1) having such a structure is suitable for suppressing an increase in the initial viscosity of the resin composition and for efficiently thickening the resin composition by the action of the metal compound (C). can be used.
  • the resin precursor (P1) is a reaction of an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2) and a polybasic acid anhydride (a1-3). is a product.
  • the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is preferably from 5 to 25 mol with respect to the total amount of 100 mol of epoxy groups in the epoxy compound (a1-1), More preferably 7 to 23 mol, still more preferably 9 to 21 mol.
  • the resin precursor (P1) can stably produce the vinyl ester resin (A), and can also produce the vinyl ester resin (A1). Mw/Mn becomes moderately large, and the resin composition can be efficiently thickened.
  • the polybasic acid anhydride (a1-3) is a dibasic acid anhydride
  • the epoxy group of the epoxy compound (a1-1) and the carboxy group of the unsaturated monobasic acid (a1-2) the epoxy group of the epoxy compound (a1-1) is ring-opened to generate a hydroxy group, and the dibasic acid anhydride undergoes ring-opening addition to the hydroxy group.
  • the carboxy group produced by the ring-opening addition of the dibasic acid anhydride further reacts with the unreacted epoxy group of the epoxy compound (a1-1). Therefore, one molecule of the dibasic acid anhydride has one acid group capable of reacting with the epoxy group of the epoxy compound (a1-1).
  • Epoxy compound (a1-1) is a compound having two epoxy groups in one molecule, monomers, oligomers and polymers in general can be used, and the molecular weight and molecular structure thereof are not particularly limited.
  • the epoxy compounds (a1-1) may be used alone or in combination of two or more.
  • Examples of the epoxy compound (a1-1) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and bisphenol AF type epoxy resin, t-butylcatechol type epoxy resin, Naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin resins, spiro-ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, and the like.
  • bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and bisphenol AF type epoxy resin, t-butylcatechol type epoxy resin, Naphthalene type epoxy resin, naphthol type epoxy resin, anthrac
  • bisphenol type epoxy resins are preferable from the viewpoint of suppressing an increase in the initial viscosity of the resin composition and controlling the thickening speed, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and At least one selected from bisphenol AF type epoxy resins is more preferred, and bisphenol A type epoxy resins are even more preferred.
  • the epoxy equivalent of the epoxy compound (a1-1) is obtained without gelation of the vinyl ester resin (A1), and from the viewpoint of suppressing the increase in the initial viscosity of the resin composition and controlling the thickening speed, It is preferably 170-1000, more preferably 170-500, even more preferably 170-400, and even more preferably 170-300. From the viewpoint of the ease and efficiency of synthesizing the vinyl ester resin (A), the epoxy compound (a1-1) is preferably liquid at 25° C., and more preferably has an epoxy equivalent of 300 or less. be done.
  • the unsaturated monobasic acid (a1-2) is preferably a monocarboxylic acid having an ethylenically unsaturated group, and may be used alone or in combination of two or more.
  • the unsaturated monobasic acid (a1-2) include (meth)acrylic acid, crotonic acid, cinnamic acid and the like.
  • at least one selected from (meth)acrylic acid and crotonic acid is used.
  • (meth)acrylic acid is more preferable, and from the viewpoint of chemical resistance, methacrylic acid is even more preferable.
  • the amount of the unsaturated monobasic acid (a1-2) is such that the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 75 per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1). It is preferably an amount of up to 95 mol, more preferably 77 to 93 mol, still more preferably 79 to 91 mol. If the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 75 mol or more with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the vinyl ester resin (A1) is sufficiently Since a sufficient amount of ethylenically unsaturated groups are introduced, the resin composition tends to exhibit good curability.
  • the reaction product of the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) is sufficiently crosslinked to easily obtain a resin composition having good thickening properties.
  • the polybasic acid anhydride (a1-3) is a compound having a plurality of carboxy groups in one molecule, and at least two carboxy groups undergo dehydration condensation to form an acid anhydride.
  • dibasic acid anhydrides are preferred from the viewpoints of ease of synthesis of the vinyl ester resin (A1), ease of control of the molecular weight and acid value, and control of the viscosity of the resin composition.
  • Polybasic acid anhydrides (a1-3) may be used alone or in combination of two or more.
  • polybasic acid anhydrides (a1-3) examples include maleic anhydride, phthalic anhydride, succinic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3-methyl-1,2,3, 6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, methyl-3,6-endomethylene -1,2,3,6-tetrahydrophthalic anhydride, trimellitic anhydride and the like.
  • at least one selected from maleic anhydride and phthalic anhydride is preferred, and maleic anhydride is more preferred, from the viewpoint of availability, reactivity, ease of handling during synthesis, and the like.
  • the polybasic acid anhydride (a1-3) has a role of cross-linking the reaction product of the epoxy compound (a1-1) and the hydroxy group to polymerize the vinyl ester resin (A1).
  • the mechanism by which the vinyl ester resin (A1) polymerizes is presumed as follows.
  • the epoxy group of the epoxy compound (a1-1) reacts with the carboxyl group of the unsaturated monobasic acid (a1-2) to ring-open the epoxy group of the epoxy compound (a1-1) to generate a hydroxy group
  • the polybasic acid anhydride (a1-3) is ring-opening added to the hydroxy group.
  • the carboxy groups generated by the ring-opening addition of the polybasic acid anhydride (a1-3) further react with the unreacted epoxy groups of the epoxy compound (a1-1) to crosslink and polymerize.
  • the vinyl ester resin (A1) By polymerizing the vinyl ester resin (A1) in this way, the molecular weight distribution shifts to the polymer side, so that the thickening speed of the resin composition can be increased.
  • the amount of the polybasic acid anhydride (a1-3) is such that the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is The amount is preferably 5 to 25 mol, more preferably 7 to 23 mol, still more preferably 9 to 21 mol.
  • the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is 5 mol or more with respect to 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1), whereby the epoxy compound (a1-1) and the polybasic acid anhydride (a1-3), the molecular weight of the vinyl ester resin (A1) increases, and the resin composition can be effectively thickened.
  • the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is 25 mol or less, it is easy to control the degree of crosslinking of the epoxy compound (a1-1), and the vinyl ester resin (A1) Gelation during synthesis is suppressed, and the thickening speed of the resin composition can be moderately controlled.
  • an acid group derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) (the "acid group” referred to herein is the polybasic acid anhydride (a1 -3) is an acid group generated by hydrolysis.
  • the polybasic acid anhydride (a1-3) is a dibasic acid anhydride, the number of acid groups generated from one molecule is 2.
  • the total amount of is preferably 105 to 125 mol, more preferably 107 to 123 mol, and still more preferably 109 to 121 mol, per 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1). is.
  • the total amount of acid groups derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) is 105 mol or more per 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1). , the amount of unreacted epoxy groups in the epoxy compound (a1-1) is suppressed, making it easier to control the thickening rate of the resin composition.
  • the total amount of acid groups derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) is 125 mol or less, gelation during synthesis of the vinyl ester resin (A1) is prevented.
  • the remaining unreacted unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) in the vinyl ester resin (A1) is suppressed, and the thickening rate of the resin composition can reduce the impact on
  • Polybasic acid anhydride (a1-4) Polybasic acid anhydride (a1-4) is a compound having a plurality of carboxy groups in one molecule, if at least two carboxy groups form an acid anhydride by dehydration condensation, especially Not limited. Examples include those similar to the polybasic acid anhydride (a1-3). Among these, from the viewpoint of ease of control of the molecular weight and acid value of the vinyl ester resin (A1), ease of handling during synthesis, and good viscosity characteristics of the resin composition, dibasic acid anhydride is preferred. Polybasic acid anhydrides (a1-4) may be used alone or in combination of two or more.
  • polybasic acid anhydride (a1-4) examples include those similar to the polybasic acid anhydride (a1-3), and maleic anhydride is more preferred.
  • the polybasic acid anhydride (a1-3) and the polybasic acid anhydride (a1-4) may be the same or different.
  • Polybasic acid anhydride (a1-4) is a reaction obtained by sequentially reacting epoxy compound (a1-1), unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3) By reacting with the product resin precursor (P1), the epoxy compound (a1-1) can be crosslinked or the resin precursor (P1 ) to introduce a carboxyl group. That is, the polybasic acid anhydride (a1-4) is added to the hydroxy group produced by the ring-opening of the epoxy group of the epoxy compound (a1-1) and produces a carboxy group.
  • This carboxy group reacts with the unreacted epoxy group of the epoxy compound (a1-1) to proceed with crosslinking, and after all the epoxy groups have reacted, the carboxy group derived from the polybasic acid anhydride (a1-4) is It remains as it is, and a carboxy group is introduced into the vinyl ester resin (A1).
  • the polybasic acid anhydride (a1-4) is preferably 3 to 60 mol, more than 100 mol of the epoxy group of the epoxy compound (a1-1). It is preferably 5 to 50 mol, more preferably 7 to 45 mol. If the polybasic acid anhydride (a1-4) is 3 mol or more with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the amount necessary for increasing the viscosity thickening rate of the resin composition.
  • the vinyl ester resin (A1) is sufficiently introduced into the vinyl ester resin (A1), and the hydroxy groups generated by ring-opening the epoxy groups derived from the epoxy compound (a1-1) are polybasic acid anhydride (a1-4) is consumed by the addition of, it is possible to suppress the increase in the initial viscosity of the resin composition. Moreover, since the polybasic acid anhydride (a1-4) is 60 mol or less, it is easy to control the thickening speed of the resin composition.
  • the vinyl ester resin (A) may further contain a vinyl ester resin (A2) other than the vinyl ester resin (A1).
  • the vinyl ester resin (A2) is a reaction product of an epoxy compound (a2-1) having two or more epoxy groups per molecule and an unsaturated monobasic acid (a2-2).
  • the content of the vinyl ester resin (A2) is the vinyl ester resin (A1) and the It is preferably 10 to 65 parts by mass, more preferably 15 to 60 parts by mass, still more preferably 20 to 55 parts by mass, based on 100 parts by mass of the vinyl ester resin (A2).
  • the weight average molecular weight Mw of the vinyl ester resin (A2) is preferably 500 to 6,000, more preferably 500 to 5,000, still more preferably 500 to 4,500.
  • the weight average molecular weight Mw of the vinyl ester resin (A2) is 500 or more, the mechanical strength of the cured product of the resin composition can be easily improved. Also, when the weight average molecular weight Mw is 6,000 or less, the compatibility with the ethylenically unsaturated group-containing monomer (B) is good.
  • the number average molecular weight Mn of the vinyl ester resin (A2) is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more. From the viewpoint of speed control, it is preferably 1,500 or less, more preferably 1,200 or less, and even more preferably 1,000 or less.
  • Mw/Mn of the vinyl ester resin (A2) is preferably 1.05 or more, more preferably 1.1 or more, from the viewpoint of ease of control of the synthesis conditions, and suppresses variations in the physical properties of the resin composition. From the viewpoint of controlling the thickening rate, it is preferably 2.0 or less, more preferably 1.7 or less, and still more preferably 1.5 or less.
  • Mw/Mn is an index of molecular weight distribution, and when it is 1, it indicates a monodisperse polymer, and the larger this ratio, the wider the molecular weight distribution.
  • Epoxy compound (a2-1) is a compound having two or more epoxy groups in one molecule, and monomers, oligomers and polymers in general can be used, and the molecular weight and molecular structure thereof are not particularly limited.
  • the number of epoxy groups in one molecule of the epoxy compound (a2-1) may be two, or three or more.
  • the epoxy compound (a2-1) may be used alone or in combination of two or more.
  • Examples of the epoxy compound (a2-1) include, for example, those similar to the epoxy compound (a1-1) in the vinyl ester resin (A1) described above, as well as stilbene type epoxy resins; novolac type epoxy resins; polyfunctional epoxy resins; aralkyl type epoxy resins; triazine nucleus-containing epoxy resins; bridged cyclic hydrocarbon compound-modified phenol type epoxy resins, glycidyl ester type epoxy resins, oxazolidone ring-containing epoxy resins, and the like.
  • the unsaturated monobasic acid (a2-2) is preferably a monocarboxylic acid having an ethylenically unsaturated group, and may be used alone or in combination of two or more.
  • Examples of the unsaturated monobasic acid (a2-2) include those similar to the unsaturated monobasic acid (a1-2) in the vinyl ester resin (A1). Examples thereof include (meth)acrylic acid, crotonic acid, cinnamic acid, etc. Among these, (meth)acrylic acid is preferred.
  • the amount of the unsaturated monobasic acid (a2-2) is such that the total amount of acid groups of the unsaturated monobasic acid (a2-2) is 80 per 100 moles of the total amount of epoxy groups of the epoxy compound (a2-1).
  • the amount is preferably up to 100 mol, more preferably 90 to 100 mol, still more preferably 99 to 100 mol.
  • the total amount of acid groups of the unsaturated monobasic acid (a2-2) is 80 mol or more with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a2-1), thereby producing a vinyl ester resin.
  • the unreacted epoxy group contained in (A2) reacts with the carboxy group contained in the vinyl ester resin (A1), and it is easy to suppress the thickening rate of the resin composition from becoming excessively large. Further, from the viewpoint of controlling the thickening speed and the viewpoint of production stability, it is preferable that no unreacted epoxy groups remain in the vinyl ester resin (A2), and the total amount of epoxy groups in the epoxy compound (a2-1) is The total amount of acid groups of the unsaturated monobasic acid (a2-2) is preferably 100 mol per 100 mol.
  • the content of the vinyl ester resin (A1) is preferably 35 parts per 100 parts by mass in total of the vinyl ester resin (A1) and the vinyl ester resin (A2). ⁇ 90 parts by mass, more preferably 40 to 85 parts by mass, still more preferably 45 to 80 parts by mass.
  • the content of the vinyl ester resin (A2) is preferably 10 to 65 parts by mass, more preferably 15 to 60 parts by mass, based on a total of 100 parts by mass of the vinyl ester resin (A1) and the vinyl ester resin (A2). More preferably 20 to 55 parts by mass. If the content of the vinyl ester resin (A1) and the vinyl ester resin (A2) in the resin composition is within the above range, it is easier to control the thickening speed of the resin composition.
  • the ethylenically unsaturated group-containing monomer (B) is not particularly limited as long as it has an ethylenically unsaturated group, but preferably has a vinyl group, and more preferably has a (meth)acryloyl group.
  • the ethylenically unsaturated group-containing monomer (B) may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated group-containing monomer (B) increases, the increase in the initial viscosity of the resin composition tends to be suppressed, and the increase in the thickening speed and the attained viscosity after thickening tends to be suppressed.
  • the hardness, strength, chemical resistance, water resistance, etc. of the cured product of the resin composition can be improved.
  • those having a (meth)acryloyl group include, for example, (meth)acrylic acid and (meth)acrylate.
  • (Meth)acrylates may be monofunctional or polyfunctional.
  • Monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl , Lauryl (meth)acrylate, Cyclohexyl (meth)acrylate, Benzyl (meth)acrylate, Stearyl (meth)acrylate, Tridecyl (meth)acrylate, Phenoxyethyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, Ethylene glycol Monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono-2-eth
  • polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, (meth)acrylates, alkanediol di(meth)acrylates such as neopentyl glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate , polyoxyalkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate; Trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate,
  • those having a (meth)acryloyl group include acryloylmorpholine, 2-hydroxyethyl (meth)acrylamide, 2-hydroxyethyl-N -methyl (meth)acrylamide, 3-hydroxypropyl (meth)acrylamide and the like.
  • examples of those having a vinyl group other than those having a (meth)acryloyl group include styrene, p-chlorostyrene, vinyltoluene, ⁇ -methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, and acetic acid.
  • Examples include vinyl, diallyl fumarate, diallyl phthalate, triallyl isocyanurate, and vinylbenzyl compounds such as vinylbenzyl butyl ether, vinylbenzylhexyl ether, and divinylbenzyl ether.
  • ethylenically unsaturated group-containing monomer (B) control of the thickening speed of the resin composition, curability, production cost, mechanical strength of the cured product of the resin composition, heat resistance, resistance
  • styrene methyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diethylene glycol di(meth) )
  • At least one selected from acrylate, triethylene glycol di(meth)acrylate and tetraethylene glycol di(meth)acrylate is preferred.
  • At least one selected from phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol di(meth)acrylate, and neopentyl glycol (meth)acrylate is more preferable.
  • At least one selected from phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol di (meth) acrylate and neopentyl glycol (meth) acrylate is more preferable, and the chemical resistance of the cured product of the resin composition From the viewpoint, at least one selected from phenoxyethyl methacrylate, benzyl methacrylate, diethylene glycol dimethacrylate, and neopentyl glycol (meth)acrylate is more preferable.
  • the content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 25 to 100 parts by mass in total of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). 70 parts by mass, more preferably 30 to 65 parts by mass, still more preferably 35 to 60 parts by mass.
  • the content of the ethylenically unsaturated group-containing monomer (B) is 25 parts by mass or more, it is easy to suppress an increase in the initial viscosity of the resin composition.
  • the content of the ethylenically unsaturated group-containing monomer (B) is 70 parts by mass or less, it is easy to control the thickening speed of the resin composition.
  • the content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 25 to 70 parts by mass, more preferably 30 to 65 parts by mass, with respect to 100 parts by mass of the total amount of the resin composition. It is preferably 35 to 60 parts by mass.
  • the amount of the ethylenically unsaturated group-containing monomer (B) is 25 parts by mass or more, the increase in the initial viscosity of the resin composition can be easily suppressed, resulting in good workability. Further, when the ethylenically unsaturated group-containing monomer (B) is 70 parts by mass or less, the resin composition has better thickening properties.
  • the metal compound (C) is at least one selected from oxides and hydroxides of Group 2 elements, and may be used alone or in combination of two or more.
  • the metal compound (C) has the effect of increasing the viscosity of the resin composition over time by interacting with the carboxyl groups and hydroxyl groups of the vinyl ester resin (A) and the carboxyl groups and hydroxyl groups of other component compounds. have.
  • oxides of Group 2 elements include magnesium oxide, calcium oxide, and barium oxide.
  • hydroxides of Group 2 elements include magnesium hydroxide, calcium hydroxide, barium hydroxide and the like. Among these, magnesium oxide is preferable from the viewpoints of thickening effect, versatility, cost, and the like.
  • the content of the metal compound (C) in the resin composition is preferably 0.01 to 6 parts by mass with respect to a total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). , more preferably 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass.
  • the content of the metal compound (C) is 0.01 parts by mass or more, the thickening property of the resin composition becomes better.
  • the content of the metal compound (C) is 6 parts by mass or less, it is easy to suppress excessive thickening of the resin composition, and it becomes easy to control the thickening speed, and the viscosity increases to a predetermined viscosity. enough time to do so.
  • the resin composition of the present embodiment contains 30 to 75 parts by mass of the vinyl ester resin (A) with respect to a total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). It is preferable that the unsaturated group-containing monomer (B) is 25 to 70 parts by mass and the metal compound (C) is contained in 0.01 to 6 parts by mass.
  • the content of the metal compound (C) in the resin composition is preferably 0.01 to 6 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 100 parts by mass of the total amount of the resin composition. is 0.1 to 4 parts by mass.
  • the amount of the metal compound (C) is 0.01 parts by mass or more, the thickening property of the resin composition becomes better.
  • the metal compound (C) is 6 parts by mass or less, it is easy to suppress excessive thickening of the resin composition, and it becomes easy to control the thickening speed, and the time to thicken to a predetermined viscosity is more sufficient. can be secured to
  • the resin composition of the present embodiment may further contain a polymerization initiator (D).
  • a polymerization initiator (D) either a photopolymerization initiator or a thermal polymerization initiator can be used, and one of them may be used alone, or two or more of them may be used in combination. It is preferable to contain a photopolymerization initiator from the viewpoint of controlling the thickening speed and securing the time for thickening to a predetermined viscosity.
  • the content of the photopolymerization initiator in the resin composition is a total of 100 mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass.
  • the content of the photopolymerization initiator is 0.01 parts by mass or more, a resin composition with better curability can be obtained.
  • the content of the photopolymerization initiator is 10 parts by mass or less, a rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks in the cured product are easily suppressed, and mechanical strength and heat resistance are improved. It is easy to obtain a cured product with a good balance of physical properties such as toughness and chemical resistance.
  • the content of the photopolymerization initiator in the resin composition is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the resin composition. , more preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.
  • the content of the photopolymerization initiator is 0.01 parts by mass or more, a resin composition with better curability can be obtained.
  • the content of the photopolymerization initiator is 10 parts by mass or less, a rapid curing reaction and heat generation are unlikely to occur during curing of the resin composition, cracks in the cured product are easily suppressed, and mechanical strength and heat resistance are improved. An excellent cured product can be easily obtained due to the balance of physical properties such as toughness and chemical resistance.
  • the content of the thermal polymerization initiator in the resin composition is a total of 100 mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). parts, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and still more preferably 0.5 to 5 parts by mass.
  • the content of the thermal polymerization initiator is 0.05 parts by mass or more, a resin composition with better curability can be obtained.
  • the content of the thermal polymerization initiator is 5 parts by mass or less, rapid curing reaction and heat generation are less likely to occur during curing of the resin composition, cracking of the cured product is likely to be suppressed, and mechanical strength, heat resistance and It is easy to obtain a cured product with excellent balance of physical properties such as chemical resistance.
  • the content of the thermal polymerization initiator in the resin composition is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin composition. , more preferably 0.1 to 8 parts by mass, and still more preferably 0.5 to 5 parts by mass.
  • the content of the thermal polymerization initiator is 0.05 parts by mass or more, a resin composition with better curability can be obtained.
  • the content of the thermal polymerization initiator is 10 parts by mass or less, rapid curing reaction and heat generation are less likely to occur during curing of the resin composition, cracking of the cured product is likely to be suppressed, and mechanical strength, heat resistance and An excellent cured product can be easily obtained due to the balance of physical properties such as chemical resistance.
  • the photopolymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light.
  • benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether; -methylethyl)acetophenone; ⁇ -hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 2-methylanthraquinone, 2- Anthraquinones such as amyl anthraquinone, 2-t-butyl anthraquinone and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Acetophenone dimethyl ketal, benzyl dimethyl ketal and the like Benz
  • the photopolymerization initiator is preferably an intramolecular cleavage type photopolymerization initiator that does not require a hydrogen donor.
  • active species are generated by absorbing light with a wavelength of 315 to 460 nm, 2,2-dimethoxy-2-phenylacetophenone, phenylbis(2, At least one selected from 4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone and 1-hydroxycyclohexylphenyl ketone is preferred.
  • thermal polymerization initiator is not particularly limited, and known radical polymerization initiators can be used.
  • thermal polymerization initiators include organic peroxides, azo compounds, persulfates, redox compounds and the like. Among these, organic peroxides are preferred.
  • organic peroxides include ketone peroxide, perbenzoate, hydroperoxide, diacyl peroxide, peroxyketal, hydroperoxide, diallyl peroxide, peroxyester and peroxydicarbonate.
  • methyl ethyl ketone peroxide cumene hydroperoxide
  • t-butyl perbenzoate 1,1,3,3-tetramethylbutyl 2-ethylhexaneperoxyate
  • dibenzoyl peroxide also called benzoyl peroxide
  • bis(4-t-butylcyclohexyl)peroxydicarbonate, 2-ethylhexaneperoxyacid 1,1,3 are preferred from the viewpoint of ease of control of the curing reaction, availability and ease of handling.
  • 3-tetramethylbutyl, dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide and t-butyl peroxybenzoate are preferred.
  • resin composition of the present embodiment include, for example, other resins, polymerization inhibitors, thixotropic agents, curing accelerators, catalysts, thickening aids, curing retardants, surfactants, surface modifiers, Wetting and dispersing agents, antifoaming agents, leveling agents, coupling agents, light stabilizers, waxes, flame retardants, plasticizers, fillers, internal release agents, low shrinkage agents, toners, viscosity reducers, anti-separation agents, phases
  • Additives such as solubilizers can be included.
  • the content of the additive is not particularly limited as long as it does not impair the effects of the present invention. From the viewpoint of obtaining good thickening properties, the resin composition of the present embodiment preferably contains as little water as possible. It is 1% by mass or less.
  • the resin composition in the present embodiment has a radically polymerizable unsaturated group in one molecule, and may contain other resins different from the vinyl ester resin (A). good.
  • Other resins include, for example, urethane (meth)acrylate resins, polyester (meth)acrylate resins, (meth)acrylate resins, unsaturated polyester resins, and the like. These other resins may be used singly or in combination of two or more.
  • the urethane (meth)acrylate resin is polyurethane having a (meth)acryloyloxy group. Specifically, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxy group-containing (meth)acrylic compound and optionally a hydroxy group-containing allyl ether compound are further added to the unreacted isocyanato groups. A radically polymerizable unsaturated group-containing oligomer obtained by the reaction is mentioned.
  • the polyester (meth)acrylate resin is polyester having a (meth)acryloyloxy group.
  • a polyester (meth)acrylate resin can be obtained, for example, by the method (1) or (2) shown below. (1) A method of reacting a polyester having a terminal carboxyl group with an epoxy group-containing (meth)acrylate or a hydroxyl group-containing (meth)acrylate (2) A polyester having a terminal hydroxy group is added with (meth)acrylic acid or isocyanate.
  • an excess amount of saturated polybasic acid and / or unsaturated polybasic acid examples include those obtained by reacting with a hydric alcohol.
  • the polyester having a hydroxy group at the end used as a raw material in the above method (2) is obtained by reacting a saturated polybasic acid and/or an unsaturated polybasic acid with an excess amount of polyhydric alcohol. is mentioned.
  • the unsaturated polyester resin is obtained by subjecting a dibasic acid component containing an unsaturated dibasic acid and, if necessary, a saturated dibasic acid, to an esterification reaction with a polyhydric alcohol.
  • the content of the other resins in the resin composition is a total of 100 mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). parts by weight, preferably 1 to 45 parts by weight, more preferably 5 to 40 parts by weight, and even more preferably 10 to 35 parts by weight.
  • a polymerization inhibitor can be used to suppress the progress of the polymerization reaction of the resin composition.
  • a known polymerization inhibitor can be used, and examples thereof include hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-t-butylcatechol. These may be used singly or in combination of two or more.
  • the content of the polymerization inhibitor in the resin composition is epoxy compound (a1-1), unsaturated monobasic acid (a1-2) and polybasic It is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, and still more preferably 0.03 to 3 parts by mass with respect to a total of 100 parts by mass of the acid anhydride (a1-3). .
  • thixotropic agent A thixotropic agent can be used to adjust the mixability and fluidity of the resin composition.
  • the thixotropic agent may be either an organic thixotropic agent or an inorganic thixotropic agent. These may be used singly or in combination of two or more.
  • the resin composition of the present embodiment contains a thixotropic agent, the total content of the thixotropic agent in the resin composition is 100 for the vinyl ester resin, (A), and the ethylenically unsaturated group-containing monomer (B). It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.
  • Organic thixotropic agents include, for example, hydrogenated castor oil, amide, polyethylene oxide, polymerized vegetable oil, surfactant, and composites using these together. Specific examples include “Floron (registered trademark) SP-1000AF” (manufactured by Kyoeisha Chemical Co., Ltd.), “Disparon (registered trademark) 6900-20X” (manufactured by Kusumoto Kasei Co., Ltd.), and the like. Inorganic thixotropic agents include, for example, hydrophobically or hydrophilically treated silica and bentonite.
  • hydrophobic inorganic thixotropic agents include “Rheolosil (registered trademark) PM-20L” (manufactured by Tokuyama Corporation), “Aerosil (registered trademark) R-106" (Nippon Aerosil Co., Ltd.), “CAB-O-SIL (registered trademark)” (manufactured by Cabot Corporation) and the like.
  • hydrophilic inorganic thixotropic agents include “Aerosil (registered trademark)-200” (manufactured by Nippon Aerosil Co., Ltd.).
  • Curing accelerators can be used to adjust the curing speed.
  • the curing accelerator is not particularly limited, and for example, known organometallic compounds such as organometallic salts, amine compounds, ⁇ -diketones, etc. can be used, and these can be used alone. Also, two or more kinds may be used in combination.
  • the content of the curing accelerator in the resin composition is a total of 100 mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass. Curability adjustment is easy as it is content in the said range.
  • organometallic compounds include copper compounds such as copper naphthenate; cobalt compounds such as cobalt octylate, cobalt naphthenate and cobalt hydroxide; zinc compounds such as zinc hexoate; and manganese compounds such as manganese octylate.
  • Amine compounds include anilines, toluidines, benzaldehydes, triethanolamine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylbenzylamine. etc.
  • ⁇ -diketones include acetylacetone, ethyl acetoacetate, ⁇ -acetyl- ⁇ -butyrolactone, N-pyrosininoacetoacetamide, N,N-dimethylacetoacetamide and the like.
  • the initial viscosity of the resin composition of the present embodiment is preferably 0.1 to 3.0 Pa s, more preferably 0.2 to 2.5 Pa s, still more preferably 0.5 to 2.0 Pa s. be.
  • the fiber base material can be efficiently and sufficiently impregnated with the resin composition, and a homogeneous composite material can be obtained in which there is no portion of resin omission.
  • the viscosity is preferably 1,000 to 40,000 Pa s, more preferably 2,000 to 30,000 Pa s, More preferably, it is 3,000 to 20,000 Pa ⁇ s.
  • the method for producing the resin composition of the present embodiment includes an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride ( and a1-3) so that the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is 5 to 25 mol with respect to 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1).
  • a vinyl ester resin having a broad molecular weight distribution can be obtained, and the resin composition having the above-mentioned good viscosity characteristics can be suitably obtained. can be manufactured.
  • Step 1 in the production method of the present embodiment includes an epoxy compound (a1-1) having two epoxy groups in one molecule, an unsaturated monobasic acid (a1-2), and a polybasic acid anhydride (a1 -3) is reacted so that the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is 5 to 25 mol with respect to 100 mol of the epoxy group of the epoxy compound (a1-1). is a step of obtaining a resin precursor (P1). For example, in a reaction vessel capable of being heated and stirred, the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2), and 100 moles of the epoxy group of the epoxy compound (a1-1) are treated with a polybasic acid.
  • an esterification catalyst preferably at 70 to 150 ° C., more preferably 80 to 140 ° C., still more preferably 90 to 130 ° C.
  • Esterification catalysts include, for example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol and diazabicyclooctane.
  • At least one selected from phosphorus compounds and quaternary ammonium salts from the viewpoint of moderately promoting the synthesis reaction rate of vinyl ester resins, suppressing gelation, and facilitating control of the molecular weight distribution. species are preferred, and at least one selected from quaternary ammonium salts is more preferred.
  • the amount of the esterification catalyst used is such that the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2) and the polybasic It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, still more preferably 0.1 to 3 parts by mass, relative to the total 100 parts by mass of the acid anhydride (a1-3). .
  • Solvents and/or reactive diluents include epoxy compounds (a1-1), unsaturated monobasic acids (a1-2), polybasic acid anhydrides (a1-3), and polybasic acid anhydrides (a1-4 ) is used as necessary from the viewpoint of facilitating uniform mixing.
  • the mixing method is not particularly limited, and can be performed by a known method.
  • the solvent is a solvent inert to the epoxy compound (a1-1), unsaturated monobasic acid (a1-2), polybasic acid anhydride (a1-3) and polybasic acid anhydride (a1-4). If there is, it is not particularly limited. Examples thereof include known solvents having a boiling point of 70 to 150° C. at 1 atm, such as methyl isobutyl ketone.
  • a solvent may be used individually by 1 type, and may use 2 or more types together.
  • Reactive diluents include epoxy compounds (a1-1), unsaturated monobasic acids (a1-2), polybasic acid anhydrides (a1-3), and polybasic acid anhydrides (a1-4).
  • Active ethylenically unsaturated group-containing monomers (B) are preferred.
  • a polymerization inhibitor may be added from the viewpoint of suppressing the progress of the polymerization reaction of the resin precursor (P1).
  • the polymerization inhibitor those described in the section [Other components] above are preferably used.
  • the amount added is, for example, the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) with respect to a total of 100 parts by mass. 0.0001 to 10 parts by mass, preferably 0.001 to 1 part by mass.
  • Step 2 in the production method of the present embodiment is a step of subjecting the resin precursor (P1) to an addition reaction with the polybasic acid anhydride (a1-4) to obtain the vinyl ester resin (A1).
  • a polybasic acid anhydride (a1-4) is added to the reaction vessel in which the resin precursor (P1) was synthesized, and in the presence of an esterification catalyst, 70 to 150 ° C., preferably 80 to 140 ° C., and further Vinyl ester resin (A1) is obtained by reacting preferably at 90 to 130° C. for 30 minutes to 4 hours.
  • esterification catalyst those described above are preferably used, and the esterification catalyst added to the synthesis of the resin precursor (P1) in step 1 can be used continuously, or alternatively, the polybasic acid anhydride (a1- When adding 4), the same or different esterification catalyst as that added in step 1 may be additionally added.
  • step 2 as in step 1, a polymerization inhibitor, solvent and/or reactive diluent may be added as required.
  • the mixing method can also be performed by a known method as in step 1.
  • the vinyl ester resin (A), the ethylenically unsaturated group-containing monomer (B) and the metal compound (C) are easily mixed uniformly and the viscosity is adjusted. Alternatively, it may be diluted with a reactive diluent.
  • the viscosity of the vinyl ester resin (A1) (viscosity adjusted by solvent and/or reactive diluent) is preferably 1 to 400 Pa s, more preferably 10 to 300 Pa s, and still more preferably 20 to 150 Pa s. .
  • the vinyl ester resin (A) may contain the vinyl ester resin (A2) as described above, in which case, for example, in a reaction vessel capable of being heated and stirred, the epoxy compound (a2-1) and the unsaturated Monobasic acid (a2-2), if necessary, mixed with a solvent and / or reactive diluent, in the presence of an esterification catalyst, preferably 70 ⁇ 150 ° C., more preferably 80 ⁇ 140 ° C., still more preferably
  • the vinyl ester resin (A2) is obtained by reacting at 90 to 130° C. for 1 to 8 hours.
  • the same esterification catalyst, solvent and reactive diluent as in step 1 can be used, and as in step 1, a polymerization inhibitor may be added if necessary.
  • the mixing method can also be performed by a known method as in step 1.
  • Step 3 in the production method of the present embodiment includes mixing a vinyl ester resin (A) containing a vinyl ester resin (A1), an ethylenically unsaturated group-containing monomer (B), and a metal compound (C) to produce a resin. This is the step of obtaining the composition.
  • step 3 in addition to the vinyl ester resin (A), the ethylenically unsaturated group-containing monomer (B) and the metal compound (C), optional components such as the polymerization initiator (D) and other components may be mixed. good.
  • the mixing order is not particularly limited, for example, a vinyl ester resin (A) produced using an ethylenically unsaturated group-containing monomer (B) as a reactive diluent, if necessary, an ethylenically unsaturated group-containing monomer A resin composition is obtained by adding (B) and adding and mixing the metal compound (C) and the optional component. From the viewpoint of facilitating viscosity control, the metal compound (C) is preferably added last.
  • the mixing method is not particularly limited, and can be performed using, for example, a disper, planetary mixer, kneader, or the like.
  • the mixing temperature is preferably 10 to 50°C, more preferably 15 to 40°C, and more preferably 20 to 30°C from the viewpoint of ease of mixing.
  • the composite material in this embodiment contains the above-described resin composition and a fiber base material.
  • a fiber base material for example, one obtained by impregnating a fiber base material with a resin composition and storing (curing) it for a certain period of time to increase its viscosity is preferable.
  • Such a composite material has good shape retention and gives a cured product (molded article) having excellent mechanical strength.
  • Specific examples of composite materials include prepreg, SMC, preform, and lining materials for pipe rehabilitation such as reinforcement and repair of existing pipes. can.
  • a prepreg or SMC is particularly preferable as the composite material of the present embodiment.
  • the content of the resin composition in the composite material is preferably 20 to 95% by mass, more preferably 100% by mass of the composite material, from the viewpoint of moldability, ease of handling, mechanical strength, etc. of the composite material. 25 to 85% by mass, more preferably 25 to 75% by mass.
  • the resin composition contains, for example, fillers such as calcium carbonate and aluminum hydroxide, low-shrinkage agents such as polystyrene, viscosity reducing agents, and additives such as coloring agents. may also be used as a mixture with the addition of these additives, in which case the composite material may also contain these additives.
  • the fiber material of the fiber base material includes, for example, synthetic fibers such as amide, nylon, aramid, vinylon, polyester and phenol resin, carbon fiber, glass fiber, metal fiber, ceramic fiber, etc. So-called reinforcing fibers and composite fibers of these may also be mentioned. These may be used singly or in combination of two or more. Among these, aramid fiber, carbon fiber, and glass fiber are preferred, and glass fiber is more preferred from the viewpoints of strength, hardness, availability, price, and the like.
  • the resin composition impregnated into the fiber base material is photocured, glass fiber or polyester fiber having light transmittance is preferable.
  • the commonly used filament diameter is preferably 1-15 ⁇ m, more preferably 3-10 ⁇ m.
  • Examples of the form of the fiber base include sheet, chopped strand, chop, milled fiber and the like.
  • As the sheet for example, a sheet formed by arranging a plurality of reinforcing fibers in one direction, bidirectional fabrics such as plain weaves and twill weaves, multiaxial fabrics, non-crimp fabrics, nonwoven fabrics, mats, knits, braids, reinforcing fibers, etc. and the like.
  • the fiber base material may be used singly or in combination of two or more types, and may be a single layer or a laminate of multiple layers.
  • the thickness of the sheet is preferably 0.01 to 5 mm in the case of a single layer, and preferably the total thickness in the case of a multilayer lamination. 1 to 20 mm, more preferably 1 to 15 mm.
  • the mechanical strength required for the cured composite material varies depending on the purpose of use.
  • the bending strength of FRP is preferably 100 to 1000 MPa, more preferably 120 to 900 MPa, still more preferably 150 to 800 MPa.
  • the bending elastic modulus of FRP is preferably 5 to 40 GPa, more preferably 7 to 35 GPa, still more preferably 8 to 30 GPa.
  • the bending strength and bending elastic modulus values are measured values according to JIS K7171:2016.
  • a fiber base material sheet
  • a release film is attached to both sides of this sheet, and the resin composition reaches a target viscosity and can be applied.
  • a method of curing the resin composition at a predetermined temperature until it becomes a smooth material and increasing the viscosity of the resin composition can be mentioned.
  • the curing temperature is appropriately set in consideration of the target viscosity, the timing of use of the composite material, etc., and is usually 10 to 55°C, preferably 15 to 50°C, more preferably 20 to 45°C.
  • a cured product is obtained by thermoforming the composite material produced as described above.
  • a cured product can be produced by pressurized heat molding using a mold.
  • this resin precursor was cooled to 110° C., and 176 g of maleic anhydride (20 mol per 100 mol of the total amount of epoxy groups in the epoxy compound (a1-1)) was added as polybasic acid anhydride (a1-4). and reacted at 110° C. for about 2 hours to obtain a reaction product (vinyl ester resin (A1-1)).
  • This reaction product was cooled to 90° C., 1717 g of phenoxyethyl methacrylate was added as a reactive diluent (ethylenically unsaturated group-containing monomer (B)), and 65% by mass of vinyl ester resin (based on total mass of blending components) and A mixture with 35% by weight of phenoxyethyl methacrylate was obtained.
  • a reactive diluent ethylenically unsaturated group-containing monomer (B)
  • vinyl ester resin based on total mass of blending components
  • Mw/Mn ⁇ Weight average molecular weight Mw, number average molecular weight Mn and molecular weight distribution Mw/Mn>
  • the Mw and Mn of the vinyl ester resin were measured by GPC under the following conditions and determined as standard polystyrene equivalent molecular weights. Mw/Mn was calculated from the values of Mn and Mw.
  • ⁇ Viscosity> The viscosity of a mixture of 65% by mass of vinyl ester resin and 35% by mass of phenoxyethyl methacrylate was measured using an E-type viscometer ("RE-85U” (manufactured by Toki Sangyo Co., Ltd.), cone plate type, cone rotor: 1 ° 34 ' ⁇ R24, rotation speed: 50 to 0.5 rpm) at a temperature of 25°C. Depending on the measured viscosity, the rotation speed of the cone rotor was set as shown in Table 1 below.
  • a resin composition was produced using the vinyl ester resin (mixture of 65% by mass of vinyl ester resin and 35% by mass of phenoxyethyl methacrylate) produced in the above Synthesis Example and Comparative Synthesis Example.
  • Example 1 A mixture of 44 parts by mass of vinyl ester resin (A1-1) and 23 parts by mass of phenoxyethyl methacrylate, 33 parts by mass of benzyl methacrylate, and a thixotropic agent (“Furnon (registered trademark) SP-1000AF”, manufactured by Kyoeisha Chemical Co., Ltd.; The same applies hereinafter.) 1.7 parts by mass was added and mixed for 20 minutes with a disper (“Homodisper 2.5 type”, manufactured by Primix Co., Ltd.; 2000 to 3000 rpm).
  • a disper Homodisper 2.5 type
  • magnesium oxide (“Magmicron MD-4AM-2”, manufactured by Mikuni-Color Co., Ltd., content 30% by mass (estimated); hereinafter the same) as a metal compound (C) 2.5 parts by mass, and polymerization 0.2 parts by mass of 2,2-dimethoxy-2-phenylacetophenone and 0.2 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide were added as the initiator (D), and the mixture was further stirred for about 1 minute. They were mixed to produce a resin composition X-1.
  • Example 2 A mixture of 36 parts by mass of vinyl ester resin (A1-1) and 19 parts by mass of phenoxyethyl methacrylate, a mixture of 9 parts by mass of vinyl ester resin (A2) and 5 parts by mass of phenoxyethyl methacrylate, 31 parts by mass of benzyl methacrylate, and 1.7 parts by mass of the modified agent was mixed in the same manner as in Example 1 with a disper (“Homo Disper 2.5 type”, manufactured by Primix Co., Ltd.; 2000 to 3000 rpm) for 20 minutes.
  • a disper Homo Disper 2.5 type”, manufactured by Primix Co., Ltd.; 2000 to 3000 rpm
  • the viscosity is good if the initial viscosity is 3.0 Pa s or less and the viscosity after 5 days is in the range of 1,000 to 40,000 Pa s. It was determined that there is.
  • the case where the thickening property is good is indicated by “ ⁇ ”, and the case of other cases is indicated by “x”.
  • the resin compositions of Examples 1 to 5 had low initial viscosities and exhibited good thickening properties over time.
  • the resin compositions (Comparative Examples 1 to 10) using vinyl ester resins having a small Mw and a small Mw/Mn did not exhibit good thickening properties.
  • Example 6 The resin composition X-5 produced in Example 5 was polymerized with respect to a total of 100 parts by mass of the vinyl ester resin (A1-1), the vinyl ester resin (A2) and the ethylenically unsaturated group-containing monomer (B). 0.2 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as an initiator (D) and 0.2 parts by mass of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide were added and mixed to contain a polymerization initiator. A resin composition was prepared.
  • the resulting polymerization initiator-containing resin composition was irradiated with light from a 250 W metal halide lamp (peak wavelength: 420 nm, illuminance: 20 to 30 mW/cm 2 ; hereinafter the same) for 30 minutes to cure a 170 mm ⁇ 170 mm, 4 mm thick film.
  • a product (cast product) was obtained.
  • the illuminance was measured using an illuminometer (“IL1400A”, photodetector “SEL005”, manufactured by International Light Technologies; measurement wavelength range 380 to 450 nm (median value 415 nm)).
  • Example 7 A glass fiber chopped strand mat ("MC 450A", manufactured by Nitto Boseki Co., Ltd.) was impregnated with the resin composition prepared in Example 6, and three sheets were stacked and cured at 23 ° C. for 5 days. Similarly, it was irradiated with light from a 250 W metal halide lamp for 30 minutes to obtain a cured product (FRP: glass fiber content: 31% by mass) of 170 mm ⁇ 170 mm and 3 mm thickness.
  • FRP glass fiber content: 31% by mass
  • the cured product (cast product) of the resin composition (X-5) has a bending strength of 122 MPa and a bending elastic modulus of 3.3 GPa
  • the cured product (FRP) has a bending strength of 163 MPa and a bending elastic modulus of 8.47 GPa. Met.
  • the deflection temperature under load of the cured product (cast product) of the resin composition (X-5) was 86°C.
  • the cured product (FRP) of the resin composition (X-5) had a Barcol hardness of 45.

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Abstract

L'invention fournit une composition de résine dotée d'excellentes propriétés de manipulation de sorte qu'elle présente une viscosité initiale faible immédiatement après fabrication et épaissit à une vitesse adéquate. L'invention fournit également un procédé de fabrication de cette composition de résine, et un matériau composite contenant ladite composition de résine. La composition de résine de l'invention contient une résine vinylester (A), un monomère à teneur en groupe éthyléniquement insaturé (B), et au moins une sorte de composé métallique (C) choisie parmi des oxydes et des hydroxydes des éléments du groupe 2. La résine vinylester (A) contient une résine vinylester (A1) qui présente une masse moléculaire moyenne en poids (Mw) supérieure ou égale à 1500, et un rapport (Ｍｗ／Ｍｎ) entre sa masse moléculaire moyenne en poids (Mw) et sa masse moléculaire moyenne en nombre (Mn) supérieur ou égal à 2,0.
PCT/JP2022/030721 2021-08-13 2022-08-12 Composition de résine ainsi que procédé de fabrication de celle-ci, et matériau composite WO2023017855A1 (fr)

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JPH09110948A (ja) * 1995-08-11 1997-04-28 Takeda Chem Ind Ltd ビニルエステル樹脂組成物及び硬化物
KR20140079601A (ko) * 2012-12-17 2014-06-27 애경화학 주식회사 광경화 시트용 우레탄 하이브리드 비닐에스테르 수지 조성물 및 그 제조방법
CN108192077A (zh) * 2017-12-18 2018-06-22 盐城艾肯科技有限公司 一种具有阻燃性能的感光树脂的制备方法及其在线路板上的应用
KR20200069193A (ko) * 2018-12-06 2020-06-16 재단법인 한국탄소융합기술원 시트몰딩 컴파운드 조성물 및 이를 이용한 시트몰딩 컴파운드
JP2021039202A (ja) * 2019-09-02 2021-03-11 味の素株式会社 感光性樹脂組成物
JP2021039201A (ja) * 2019-09-02 2021-03-11 味の素株式会社 感光性樹脂組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019017254A1 (fr) 2017-07-20 2019-01-24 三菱ケミカル株式会社 Composé pour moulage de feuille, matériau composite renforcé par fibres, et procédé de production d'un matériau composite renforcé par fibres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09110948A (ja) * 1995-08-11 1997-04-28 Takeda Chem Ind Ltd ビニルエステル樹脂組成物及び硬化物
KR20140079601A (ko) * 2012-12-17 2014-06-27 애경화학 주식회사 광경화 시트용 우레탄 하이브리드 비닐에스테르 수지 조성물 및 그 제조방법
CN108192077A (zh) * 2017-12-18 2018-06-22 盐城艾肯科技有限公司 一种具有阻燃性能的感光树脂的制备方法及其在线路板上的应用
KR20200069193A (ko) * 2018-12-06 2020-06-16 재단법인 한국탄소융합기술원 시트몰딩 컴파운드 조성물 및 이를 이용한 시트몰딩 컴파운드
JP2021039202A (ja) * 2019-09-02 2021-03-11 味の素株式会社 感光性樹脂組成物
JP2021039201A (ja) * 2019-09-02 2021-03-11 味の素株式会社 感光性樹脂組成物

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