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
• • 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
  • 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
  • C08G59/1461—Unsaturated monoacids
  • C08G59/1466—Acrylic or methacrylic acids
• • 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.
• Patent Document 1 a tubular lining material is brought into close contact with the inner wall surface of an existing pipe buried in the ground, and while compressed air is supplied to the inside of the lining material, air is introduced into the lining material.
• a method for repairing an existing pipe is disclosed, which includes a curing step of curing the lining material by irradiating the inner surface of the lining material with light using a mobile light irradiation device.
• an impregnated substrate made of fibers or the like impregnated with a photocurable resin composition can be used as a material for the lining material. It is described that a polymerizable resin dissolved in a solvent such as styrene can be used.
• a resin composition having a low viscosity is preferred so that the resin composition can be easily impregnated when impregnating the impregnated base material with the resin composition.
• the resin composition has such a viscosity that it can be uniformly distributed and maintained in the impregnated substrate so that the resin composition is not unevenly distributed. That is, when the resin composition is impregnated into the impregnated base material, the viscosity is low, but the viscosity increases with the passage of time, and when the existing pipe is repaired, the resin composition is kept in a state that can be maintained.
• a resin composition having a high viscosity is desirable.
• An object of the present invention is to provide a resin composition which is easy to Another object of the present invention is to provide a composite material containing the resin composition and a method for producing the resin composition.
• the vinyl ester resin (A) contains a vinyl ester resin (A1),
• the vinyl ester resin (A1) has a weight average molecular weight (Mw) of 1,500 or more and a ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 2.0 or more. thing.
• the vinyl ester resin (A1) is an addition reaction product of a resin precursor (P1) and a polybasic acid anhydride (a1-4),
• the resin precursor (P1) 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 the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1).
• the vinyl ester resin (A) further includes a vinyl ester resin (A2),
• the vinyl ester resin (A2) 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) [6] above.
• the resin composition according to any one of [10].
• the vinyl ester resin (A1) is 35 to 90 parts by mass, and the vinyl ester resin (A2) is The resin composition according to [11] above, which is 10 to 65 parts by mass.
• the vinyl ester resin (A) contains a vinyl ester resin (A1), A method for producing a resin composition, comprising steps 1 to 3 below.
• Step 1 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) are combined with the epoxy compound ( A resin precursor (P1 )
• Step 2 Addition reaction of the resin precursor (P1) and the polybasic acid anhydride (a1-4) to obtain the vinyl ester resin (A1)
• Step 3 The vinyl ester resin (A ), the ethylenically unsaturated group-containing monomer (B), the compound (C), and the compound (D) are mixed to obtain a resin composition [18] above [1] to [16]
• a composite material comprising the resin composition according to any one of 1 above and a fiber base sheet (F). [19] The composite material according to [18] above, which is for pipe rehabilitation.
• a resin composition that has a low initial viscosity, increases in viscosity over time, and is easy to control the rate of increase in viscosity, and a method for producing the same. Also, a composite material containing the resin composition can be provided.
• (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 a value obtained by measuring using a mixed solution of bromothymol blue and phenol red as an indicator in accordance with JIS K6901: 2008, and neutralizing 1 g of the vinyl ester resin. is the number of milligrams of potassium hydroxide required for Specifically, it is measured by the method described in Examples below.
• the "viscosity" of the vinyl ester resin is represented by 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.
• 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.
• the term "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 comprises a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), and at least one selected from oxides and hydroxides of metals belonging to Group 2 elements. and a compound (D) which is at least one selected from water and a hydroxy group-containing compound.
• the vinyl ester resin (A) has a weight average molecular weight Mw of 1,500 or more and a ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 2.0 or more.
• the resin composition of the present embodiment contains a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), a compound (C) and a compound (D), and in addition to these, other components described later.
• the total content of vinyl ester resin (A), ethylenically unsaturated group-containing monomer (B), compound (C) and compound (D) in the resin composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.
• the vinyl ester resin (A) of the present embodiment 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 vinyl ester resin (A1) of the present embodiment has a weight average molecular weight (Mw) of 1,500 or more, and a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 2.5. 0 or more.
• 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 efficient thickening. It is preferably 35,000 or less, more preferably 25,000 or less, still more preferably 15,000 or less, from the viewpoint of reducing the initial viscosity of the composition to an appropriate range and controlling the thickening speed.
• 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.
• the vinyl ester resin (A1) has a wide Mw/Mn of 2.0 or more, which facilitates optimization of various production conditions during synthesis 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 4.0 or more from the viewpoint of facilitating optimization of various production conditions. It is preferably 18 or less, more preferably 12 or less, and still more preferably 10 or less from the viewpoint of suppressing variations in the physical properties of the resin composition, reducing the initial viscosity to an appropriate range, and controlling the thickening speed.
• the number average molecular weight (Mn) of the vinyl ester resin (A1) is preferably 500 or more, more preferably 700 or more, and still more preferably 900 or more. It is preferably 2,500 or less, more preferably 1,800 or less, still more preferably 1,600 or less, from the viewpoint of reducing the initial viscosity to an appropriate range and controlling the thickening speed.
• 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, still more preferably 15 mg KOH/g or more, and even more preferably, from the viewpoint of improving the thickening speed of the resin composition. is 25 KOH mg/g or more, and from the viewpoint of controlling the thickening rate of the resin composition, it is preferably 100 KOH mg/g or less, more preferably 90 KOH mg/g or less, even more preferably 80 KOH mg/g or less, and even more preferably 70 KOH mg/g. 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 appropriate control of 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 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 resin precursor (P1), which is a reaction product, and the polybasic acid anhydride (a1-4).
• the resin precursor (P1) is 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 a reaction product.
• the resin precursor (P1) is used from the viewpoint of stably producing the vinyl ester resin (A), and from the viewpoint of appropriately widening the Mw/Mn of the vinyl ester resin (A1) and accelerating the thickening speed of the resin composition.
• the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2), and the polybasic acid anhydride (a1-3), and the total amount of epoxy groups of the epoxy compound (a1-1) is 100 It is preferably a reaction product obtained by reacting such that the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is 5 to 25 mol, more preferably 7 mol, per mol. ⁇ 23 mol, more preferably 9-21 mol.
• 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) By the reaction, the epoxy group of the epoxy compound (a1-1) is ring-opened to generate a hydroxy group
• the dibasic acid anhydride, which is a polybasic acid anhydride (a1-3) is ring-opened with respect 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).
• the polybasic acid anhydride (a1-3) is a dibasic acid anhydride, it is derived from a dibasic acid anhydride that can react with the epoxy group contained per molecule of the dibasic acid anhydride.
• the number of acid groups is one.
• the epoxy compound (a1-1) is a compound having two epoxy groups in one molecule, and monomers, oligomers and polymers in general can be used, and the molecular weight and molecular structure 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; tert-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 butadiene structure, Alicyclic epoxy resin, Heterocyclic epoxy resin Epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, and the like can be mentioned.
• bisphenol type epoxy resins are preferable from the viewpoint of suppressing the increase in 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, bisphenol AF.
• One or more selected from type epoxy resins are 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), suppresses the increase in the initial viscosity of the resin composition, and moderately controls the thickening speed.
• the epoxy compound (a1-1) that is liquid at 25°C and has an epoxy equivalent of 300 or less is preferably used.
• 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.
• unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, cinnamic acid and the like. Among them, at least one selected from (meth)acrylic acid and crotonic acid is preferable from the viewpoint of versatility, reactivity during synthesis of the vinyl ester resin (A), and obtaining a resin composition having good curability. , (meth)acrylic acid is more preferred, and from the viewpoint of chemical resistance, methacrylic acid is even more preferred.
• 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 preferable to carry out the reaction so that the amount is up to 95 mol, more preferably 77 to 93 mol, and 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 per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the vinyl ester resin (A1) contains Since a sufficient amount of ethylenically unsaturated groups are introduced, the resin composition tends to exhibit good curability.
• the total amount of acid groups of the unsaturated monobasic acid (a1-2) is 95 mol or less per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), the epoxy compound (a1-1) and the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) are 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 anhydride is used from the viewpoint 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 within an appropriate range. things are preferred.
• 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. These may be used independently and may use 2 or more types. Among these, maleic anhydride and phthalic anhydride are preferred, and maleic anhydride is more preferred, from the viewpoints of availability, reactivity during synthesis of the vinyl ester resin (A1), 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 reaction between the epoxy group of the epoxy compound (a1-1) and the carboxyl group of the unsaturated monobasic acid (a1-2) causes ring-opening of the epoxy group of the epoxy compound (a1-1) to generate a hydroxy group.
• 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 It is preferable to react so as to obtain 5 to 25 mol, more preferably 7 to 23 mol, still more preferably 9 to 21 mol.
• the epoxy compound ( Crosslinking between a1-1) and the polybasic acid anhydride (a1-3) increases the molecular weight of the vinyl ester resin (A1) and effectively thickens the resin composition.
• the total amount of acid groups derived from the polybasic acid anhydride (a1-3) is 25 mol or less with respect to 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1), It becomes easier to control the amount of cross-linking of the epoxy compound (a1-1), suppress gelation during synthesis of the vinyl ester resin (A1), and easily control the thickening rate of the resin composition.
• the unsaturated monobasic acid (a1-2) and polybasic acid anhydride (a1-3)-derived acid groups ( The "acid group” referred to here is an acid group produced by hydrolysis of the polybasic acid anhydride (a1-3).
• 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 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 derived from the epoxy compound (a1-1) is suppressed, and the thickening speed of the resin composition can be easily controlled.
• the total amount of acid groups derived from the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride (a1-3) is 125 mol per 100 mol of the total amount of epoxy groups of the epoxy compound (a1-1).
• the reaction can be controlled without gelation, and unreacted unsaturated monobasic acid (a1-2) and polybasic acid anhydride in vinyl ester resin (A1) It is possible to suppress the remaining of the product (a1-3), and it is possible to suppress the influence on the thickening speed of the resin composition
• the polybasic acid anhydride (a1-4) is a compound having a plurality of carboxy groups in one molecule, especially if at least two carboxy groups form an acid anhydride by dehydration condensation. Not limited. For example, the same polybasic acid anhydride (a1-3) can be mentioned. A dibasic acid anhydride is preferable from the viewpoint of good viscosity characteristics of the composition. Polybasic acid anhydrides (a1-4) may be used alone or in combination of two or more. Specific examples of the polybasic acid anhydride (a1-4) 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.
• the polybasic acid anhydride (a1-4) is obtained by sequentially reacting the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2), and the polybasic acid anhydride (a1-3).
• the resin precursor (P1) which is the reaction product obtained by the reaction
• the polybasic acid anhydride (a1-3) is subsequently crosslinked with the epoxy compound (a1-1) by the same reaction mechanism. or introduce a carboxyl group into the resin precursor (P1). That is, the polybasic acid anhydride (a1-4) is added to the hydroxy group produced by the ring-opening of the epoxy group derived from the epoxy compound (a1-1) and produces a carboxy group.
• the resulting carboxy group reacts with an unreacted epoxy group derived from the epoxy compound (a1-1) to proceed with crosslinking, and after all the epoxy groups have reacted, the polybasic acid anhydride (a1-4) derived remains as it is without further cross-linking, and the carboxy group is introduced into the vinyl ester resin (A1).
• the polybasic acid anhydride (a1-4) is preferably 3 to 60 mol per 100 mol of the total epoxy group of the epoxy compound (a1-1). more preferably 5 to 50 mol, still more preferably 7 to 45 mol.
• the vinyl ester resin (A1) is not added. Sufficient amount necessary for suppressing the residual reaction epoxy group to suppress the increase in the initial viscosity of the resin composition, and to improve the thickening speed of the resin composition by introducing the carboxy group.
• the vinyl ester resin (A1) is introduced into the vinyl ester resin (A1), and the hydroxy group generated by ring-opening the epoxy group derived from the epoxy compound (a1-1) is added to the polybasic acid anhydride (a1-4).
• the initial viscosity of the resin composition can be reduced.
• the viscosity of the resin composition is increased by reacting the polybasic acid anhydride (a1-4) in an amount of 60 mol or less per 100 mol of the total epoxy group of the epoxy compound (a1-1). Easier to control speed.
• the vinyl ester resin (A2) 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).
• an epoxy compound (a2-1) having two or more epoxy groups in one molecule and an unsaturated monobasic acid (a2-2).
• 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. If the weight average molecular weight (Mw) is 500 or more, the mechanical strength of the cured product of the resin composition can be easily improved. Also, if the weight average molecular weight (Mw) is 6,000 or less, when forming a resin composition, it is easily dissolved in other components contained in the resin composition, and handling becomes easier.
• the weight average molecular weight (Mw) of the vinyl ester resin (A2) can be measured by the same method as for the vinyl ester resin (A1).
• 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 those used for the epoxy compound (a1-1) of the vinyl ester resin (A1) described above, as well as stilbene type epoxy resins; novolac type epoxy resins; epoxy resins; phenol aralkyl type epoxy resins; triazine nucleus-containing epoxy resins; bridged cyclic hydrocarbon compound-modified phenol type epoxy resins; glycidyl ester type epoxy resins;
• 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.
• a known unsaturated monobasic acid (a2-2) can be used.
• the same as those used for (a1-1) of the vinyl ester resin (A1) described above can be used, including (meth)acrylic acid, crotonic acid, cinnamic acid and the like. Among these, (meth)acrylic acid is preferred.
• the unsaturated monobasic acid (a2-2) is such that the total amount of acid groups of the unsaturated monobasic acid (a2-2) is 80 to 100 per 100 mol of the total amount of epoxy groups of the epoxy compound (a2-1). It is preferable to react so that the total amount is 1 mol, more preferably 90 to 100 mol, and still more preferably 99 to 100 mol.
• a vinyl ester resin It is easy to prevent the unreacted epoxy group contained in A2) from reacting with the carboxyl group contained in the vinyl ester resin (A1), resulting in an excessive increase in the thickening rate of the resin composition.
• the total amount of acid groups in the unsaturated monobasic acid (a2-2) is 100 mols per 100 mols of the total amount of epoxy groups in the epoxy compound (a2-1).
• the content of the vinyl ester resin (A1) is 100 parts by mass in total of the vinyl ester resin (A1) and the vinyl ester resin (A2), and the vinyl ester resin ( A1) is preferably 35 to 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 with respect to the total of 100 parts by mass of the vinyl ester resin (A1) and the vinyl ester resin (A2). parts, more preferably 20 to 55 parts by mass.
• the content of the vinyl ester resin (A) in the resin composition is 20 to 80 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. is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass.
• the vinyl ester resin (A) is 20 parts by mass or more, the vinyl ester resin (A1) tends to favorably accelerate the thickening speed of the resin composition.
• the initial viscosity of the resin composition is easily reduced by the ethylenically unsaturated group-containing monomer (B).
• the content of the vinyl ester resin (A) in the resin composition is preferably 20 to 75 parts by mass, more preferably 30 to 65 parts by mass, still more preferably 100 parts by mass in total of the resin composition. is 40 to 60 parts by mass.
• the vinyl ester resin (A) is 20 parts by mass or more, the vinyl ester resin (A1) tends to favorably accelerate the thickening speed of the resin composition.
• the vinyl ester resin (A) is 75 parts by mass or less, the initial viscosity of the resin composition is easily reduced by the ethylenically unsaturated group-containing monomer (B).
• the ethylenically unsaturated group-containing monomer (B) is not particularly limited as long as it has an ethylenically unsaturated group, but preferably has a (meth)acryloyl group or a vinyl group.
• 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-ethylhex
• polyfunctional (meth)acrylates examples include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and 1,4-butylene glycol.
• those having a (meth)acryloyl group other than (meth)acrylate include, for example, acryloylmorpholine, 2-hydroxyethyl (meth)acrylamide, 2-hydroxy ethyl-N-methyl(meth)acrylamide, 3-hydroxypropyl(meth)acrylamide and the like.
• those having a vinyl group include, for example, styrene, p-chlorostyrene, vinyltoluene, ⁇ -methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, Examples include diallyl fumarate, triallyl isocyanurate, and vinylbenzyl compounds such as vinylbenzyl butyl ether, vinylbenzylhexyl ether, vinylbenzyloctyl ether, and divinylbenzyl ether.
• the content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is 20 to 80 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). parts, more preferably 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass.
• the amount of the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the initial viscosity of the resin composition can be easily reduced, resulting in good workability.
• the ethylenically unsaturated group-containing monomer (B) is 80 parts by mass or less, the resin composition has better thickening properties.
• the content of the ethylenically unsaturated group-containing monomer (B) in the resin composition is preferably 20 to 75 parts by mass, more preferably 30 to 65 parts by mass with respect to the total amount of 100 parts by mass of the resin composition. parts, more preferably 40 to 60 parts by mass.
• the amount of the ethylenically unsaturated group-containing monomer (B) is 20 parts by mass or more, the initial viscosity of the resin composition can be easily reduced, resulting in good workability.
• the ethylenically unsaturated group-containing monomer (B) is 75 parts by mass or less, the resin composition has better thickening properties.
• the compound (C) is at least one selected from oxides and hydroxides of metals belonging to Group 2 elements, and may be used alone or in combination of two or more.
• the compound (C) has the effect of increasing the viscosity of the resin composition over time by interacting with the carboxyl group and hydroxyl group of the vinyl ester resin (A) and the compound having the carboxyl group and hydroxyl group as an auxiliary agent.
• metal oxides belonging to Group 2 elements include magnesium oxide, calcium oxide, and barium oxide.
• hydroxides of metals belonging to Group 2 elements include hydroxides of magnesium, calcium, barium, and the like.
• magnesium oxide is preferable from the viewpoint of thickening effect, versatility, cost, and the like.
• the content of the compound (C) in the resin composition is preferably 0.01 to 6 parts by mass, relative to a total of 100 parts by mass of the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). It is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 4 parts by mass.
• the amount of the compound (C) is 0.01 parts by mass or more, the thickening property of the resin composition becomes better.
• the compound (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition, and it becomes easy to control the speed of thickening over time, thereby ensuring a more sufficient pot life. can do.
• the content of the compound (C) in the resin composition is preferably 0.01 to 6 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 4 parts by mass.
• the amount of the compound (C) is 0.01 parts by mass or more, the thickening property of the resin composition becomes better.
• the compound (C) is 6 parts by mass or less, it becomes easy to suppress excessive thickening of the resin composition, and it becomes easy to control the speed of thickening over time, thereby ensuring a more sufficient pot life. can do.
• Compound (D) is at least one or more selected from water and hydroxy group-containing compounds.
• the compound (D) is used for the purpose of controlling the thickening rate with respect to changes in the thickening rate over time.
• hydroxy group-containing compounds include alcohols having a boiling point of 50° C. or higher, such as benzyl alcohol, stearyl alcohol, and isostearyl alcohol.
• Other examples include hydroxycarboxylic acids such as lactic acid, glycerin, polyols, and (meth)acrylates containing a hydroxy group. These may be used individually by 1 type, and may use 2 or more types together. Among these, water and alcohol are preferred, and water is more preferred, from the viewpoint of availability, cost, and the like.
• the content of the compound (D) in the resin composition is preferably 0.01 to 3 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). It is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass.
• the compound (D) is 0.01 parts by mass or more, it becomes easier to control the thickening speed of the resin composition, and it becomes easier to suppress excessive thickening.
• the compound (D) is 3 parts by mass or less, physical properties such as strength, toughness, heat resistance, and chemical resistance of the composite material containing the resin composition become better.
• the content of the compound (D) in the resin composition is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, still more preferably It is 0.1 to 1 part by mass.
• the compound (D) is 0.01 parts by mass or more, it becomes easier to control the thickening speed of the resin composition, and it becomes easier to suppress excessive thickening.
• the compound (D) is 3 parts by mass or less, physical properties such as strength, toughness, heat resistance, and chemical resistance of the composite material containing the resin composition become better.
• the resin composition may further contain a polymerization initiator (E). Both a photopolymerization initiator and a thermal polymerization initiator can be used as the polymerization initiator (E). It is preferable that the resin composition contains 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 less likely to occur during curing of the resin composition, cracks are more likely to be suppressed, and the obtained composite material has strength, It has an excellent balance of physical properties such as toughness, heat resistance, 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 less likely to occur during curing of the resin composition, cracks are more likely to be suppressed, and the obtained composite material has strength, It has an excellent balance of physical properties such as toughness, heat resistance, 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 even 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 composite material containing the resin composition has an excellent balance of physical properties such as strength, toughness, heat resistance and 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 composite material containing the resin composition has an excellent balance of physical properties such as strength, toughness, heat resistance and chemical resistance.
• the photopolymerization initiator is not particularly limited as long as it generates radicals upon irradiation with light.
• examples include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether; - Acetophenones such as 2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone; 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- ⁇ -hydroxyalkylphenones such as phenyl-propan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2 , thioxanthones such as 4-diisoprop
• 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(2,4, 6-trimethylbenzoyl)phosphine oxide and 1-hydroxycyclohexylphenyl ketone, 1-hydroxycyclohexylphenyl ketone are 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
• Other components of the resin composition of the present embodiment include, for example, other resins, catalysts, thickening aids, polymerization inhibitors, thixotropic agents, curing accelerators, curing retarders, 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.
• 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) from the viewpoint of controlling the thickening speed.
• 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 can 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 an epoxy group-containing (meth)acrylate or a hydroxy group-containing (meth)acrylate with a carboxy-terminated polyester (2)
• a method of reacting (meth)acrylate with a carboxyl-terminated polyester used as a raw material in the above method (1) is obtained from an excess amount of saturated polybasic acid and/or unsaturated polybasic acid and polyhydric alcohol. What can be obtained is mentioned.
• the hydroxy-terminated polyester used as a raw material in the above method (2) includes those obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and an excess amount of a polyhydric alcohol.
• 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.
• urethane (meth)acrylate resins, polyester (meth)acrylate resins, and (meth)acrylate resins are preferable from the viewpoint of controlling the thickening speed.
• the content of the other resins in the resin composition is 100 in total for the vinyl ester resin (A) and the ethylenically unsaturated group-containing monomer (B). It is preferably 1 to 45 parts by mass, more preferably 5 to 40 parts by mass, still more preferably 10 to 35 parts by mass.
• 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 individually by 1 type, and may use 2 or more types together.
• 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). .
• the resin composition in this embodiment can contain a thixotropic agent, if necessary.
• a thixotropic agent is used to adjust the mixability and fluidity of the resin composition.
• the thixotropic agents include organic thixotropic agents and inorganic thixotropic agents. These can be used singly or in combination of two or more.
• the content thereof is preferably based on a total of 100 parts by mass of the vinyl ester resin, (A), and the ethylenically unsaturated group-containing monomer (B). is 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” (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. , may be used in combination of two or more.
• the content thereof 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. When the content is within the above range, it is easy to adjust the curability.
• 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 resin composition in the present embodiment contains 20 to 80 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), and ethylene
• a compound (D) which contains 20 to 80 parts by mass of a polyunsaturated group-containing monomer (B), 0.01 to 6 parts by mass of a compound (C), and is at least one selected from water and a hydroxy group-containing compound. It is preferable to contain 0.01 to 3 parts by mass.
• the initial viscosity of the resin composition 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. If the initial viscosity is within the above range, the fiber base sheet (G) described below is efficiently and sufficiently impregnated with the resin composition to obtain a composite material having no resin-free portion (no resin-missing portion). be able to.
• the viscosity (after thickening) is preferably 100 to 2,200 Pa s, more preferably 200 to 2,000 Pa s, still more preferably 400 to 1,800 Pa ⁇ s, more preferably 500 to 1,500 Pa ⁇ s. If the viscosity after thickening is within the above range, the resin composition becomes difficult to flow when applied as a composite material. That is, the resin composition and the fiber base sheet (G) do not separate from the resin composition and the fiber base sheet (G), and the resin composition is not unevenly distributed in the fiber base sheet (G). It is possible to suitably obtain a composite material having excellent adhesion to.
• the method for producing a resin composition in the present embodiment is selected from a vinyl ester resin (A), an ethylenically unsaturated group-containing monomer (B), and a metal oxide and hydroxide belonging to Group 2 elements.
• the vinyl ester resin (A) contains at least vinyl ester resin (A1).
• Step 1 in this 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 the total amount of 100 mol of the epoxy groups of the epoxy compound (a1-1). is a step of obtaining a resin precursor (P1).
• step 1 for example, in a reaction vessel capable of being heated and stirred, in the presence of an esterification catalyst, an epoxy compound (a1-1), an unsaturated monobasic acid (a1-2), and an epoxy compound (a1-1) If necessary, an amount of polybasic acid anhydride (a1-3) such that the total amount of acid groups derived from polybasic acid anhydride (a1-3) is 5 to 25 moles per 100 moles of epoxy groups of ). Dissolve in a solvent or reactive diluent, react at 70 to 150° C., preferably 80 to 140° C., more preferably 90 to 130° C. for 1 to 8 hours to obtain resin precursor (P1). be done.
• esterification catalysts examples include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, and cyazabicyclooctane.
• Phosphorus compounds such as primary amines, triphenylphosphine and benzyltriphenylphosphonium chloride, diethylamine hydrochloride, trimethylbenzylammonium chloride, lithium chloride and the like. These can be used singly or in combination of two or more. Among these, from the viewpoints of slowing the reaction rate, preventing gelation of the resin, and facilitating control of the molecular weight distribution, phosphorus-based and ammonium salt-based catalysts are preferred, and ammonium salts are more preferred.
• the amount of the catalyst used is the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2) and the polybasic acid anhydride. 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, based on 100 parts by mass of the substance (a1-3).
• the epoxy compound (a1-1), the unsaturated monobasic acid (a1-2), the polybasic acid anhydride (a1-3), and the polybasic acid anhydride (a1-4) may be diluted with solvents and/or reactive diluents.
• 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) Although there is no particular limitation as long as the is possible.
• 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.
• the mixing method is not particularly limited, and can be performed by a known method.
• 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 present embodiment is a step of subjecting the resin precursor (P1) and the polybasic acid anhydride (a1-4) to an addition reaction to obtain the vinyl ester resin (A1).
• step 2 for example, in the reaction vessel in which the resin precursor (P1) was synthesized, polybasic acid anhydride (a1-4) is added in the presence of a catalyst, and the temperature is maintained at 70 to 150°C, preferably 80 to 140. ° C., more preferably 90 to 130° C. for 30 minutes to 4 hours to obtain the vinyl ester resin (A1).
• the catalyst those described in the section ⁇ Step 1> (catalyst) above are preferably used, and the catalyst used in the synthesis of the resin precursor (P1) in Step 1 can be used continuously.
• the acid anhydride (a1-4) the same or different one added in step 1 may be newly added.
• step 2 similarly to step 1, a solvent and/or a reactive diluent and a polymerization inhibitor may be added, if necessary.
• 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 method for producing the vinyl ester resin (A2) includes, for example, an epoxy compound ( a2-1) and unsaturated monobasic acid (a2-2) are dissolved in a solvent or reactive diluent as necessary, and heated to 70 to 150°C, preferably 80 to 140°C, more preferably 90 to 130°C. and a method of reacting for 1 to 8 hours.
• the same catalyst as in step 1 can be used, and a solvent and/or reactive diluent and polymerization inhibitor may be added as in step 1, if necessary.
• the mixing method can also be performed by a known method as in step 1.
• Step 3 in the present embodiment includes vinyl ester resin (A) containing vinyl ester resin (A1), ethylenically unsaturated group-containing monomer (B), and oxides and hydroxides of metals belonging to Group 2 elements.
• a polymerization initiator (E) in addition to the vinyl ester resin (A), the ethylenically unsaturated group-containing monomer (B), the compound (C), and the compound (D), a polymerization initiator (E), a catalyst, and the other You may mix arbitrary components, such as a component of.
• step 3 the order of mixing is not limited, but for example, vinyl ester resin (A) is produced using ethylenically unsaturated group-containing monomer (B) as a reactive diluent, and then, if necessary, additional A method of adding and mixing the ethylenically unsaturated group-containing monomer (B) added in (1), the compound (C), the compound (D), and the optional components. From the viewpoint of facilitating viscosity control, compound (C) is preferably added last.
• the mixing method is not particularly limited, and can be carried out using, for example, a disper, a planetary mixer, a kneader, or the like.
• the kneading temperature is preferably 10 to 40°C, more preferably 15 to 30°C, and more preferably 20 to 30°C from the viewpoint of ease of mixing.
• the composite material in this embodiment includes the resin composition and the fiber base sheet (F).
• the composite 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.
• the composite material containing the resin composition and the fiber base sheet (F) is used for construction on structures as a material such as preform, prepreg, lining material for pipe rehabilitation such as reinforcement and repair of existing pipes. be able to. Among these, it is preferable to use it as a material such as a lining material. That is, the composite material is preferably for pipe rehabilitation.
• various known construction methods can be applied. Specifically, a cylindrical photo-curing composite material is used as a lining material and is pulled in as it is, or the lining material is turned over from the tip side and pushed into the existing pipe to be pulled into the existing pipe, and air pressure etc. is applied to the existing pipe.
• the inner surface of the lining material is irradiated with ultraviolet rays or visible light using a mobile light irradiation device installed inside the lining material to harden the lining material and reinforce the existing pipe. , can be repaired.
• the content of the resin composition in the composite material is preferably 20 to 95% by mass, more preferably 25 to 85% by mass, still more preferably 25 to 75% by mass, relative to 100% by mass of the composite material.
• the content of the resin composition is 20% by mass or more, the workability of the composite material becomes better.
• the content of the resin composition is 95% by mass or less, the content of the fiber base sheet (F) can be sufficiently ensured, and sufficient strength can be easily obtained as a cured product of the composite material.
• the content of the fiber base sheet (F) in the composite material is preferably 5 to 80% by mass, more preferably 15 to 75% by mass, still more preferably 25 to 75% by mass, relative to 100% by mass of the composite material. is.
• the content of the fiber base sheet (F) is 5% by mass or more, it is easy to obtain sufficient strength as a cured product of the composite material.
• the content of the fiber base sheet (F) is 80% by mass or less, the content of the resin composition can be sufficiently ensured, and the workability of the composite material becomes better.
• the fiber base sheet (F) from the viewpoint of mechanical strength, for example, organic fibers such as amide, alanide, vinylon, polyester, phenol, etc., carbon fibers, glass fibers, metal fibers, ceramic fibers, etc. fibers, and composite fibers thereof. Among these, aramid fiber, carbon fiber, and glass fiber are preferred, and glass fiber is more preferred from the viewpoints of strength, availability, price, and the like. In particular, when the resin composition impregnated into the fiber base material is photocured, glass fiber or polyester fiber having light transmittance is preferable.
• the fiber base sheet (F) can be used singly or in combination of two or more.
• 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 fiber base sheet (F) is preferably 0.01 to 5 mm in the case of a single layer from the viewpoint of the impregnating property of the resin composition, and the total thickness in the case of a multilayer lamination. is preferably 1 to 20 mm, more preferably 1 to 15 mm.
• These fiber base sheets (F) may contain a known sizing agent in a known content.
• 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 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.
• the fiber base sheet (F) is impregnated with the resin composition, films are laminated on both sides of the fiber base sheet (F) impregnated with the resin composition, and the resin composition has a target viscosity.
• a method of thickening the resin composition by curing at a constant temperature until it reaches a workable material is exemplified.
• the storage temperature and target viscosity are as described in the section on the resin composition.
• a storage method a method of folding the sheet-like composite material into a bellows shape or a method of winding and storing the same can be mentioned.
• Epoxy compound (1) bisphenol A type epoxy resin
• "Epomic (registered trademark) R140P” manufactured by Mitsui Chemicals, Inc.
• Epoxy compound (2) bisphenol A type epoxy resin
• "jER (registered trademark) 834" manufactured by Mitsubishi Chemical Corporation
• Epoxy compound (3) phenolic novolak type epoxy resin
• EPICLON (registered trademark) N-740” manufactured by DIC Corporation
• epoxy equivalent 172 an epoxy equivalent is the value measured based on JISK7236:2001.
• the acid value of the vinyl ester resin is vinyl ester resin (A1-1) ⁇ (A1-4) and (A1'-1) ⁇ in accordance with JIS K6901: 2008 "partial acid value (indicator titration method)" Measure the mass of potassium hydroxide required to neutralize the acid component contained in (A1'-4), vinyl ester resins (A1-1) to (A1-4), and (A1'-1) to The acid value of (A1'-4) was determined.
• the ethylenically unsaturated group-containing monomer (B), phenoxyethyl methacrylate (Showa Denko Materials Co., Ltd.) was used to prepare a diluted mixture, and the mass of potassium hydroxide required to neutralize the acid component contained in the mixture was measured. Then, the acid value of the vinyl ester resin was obtained by converting the measured value.
• "Autoburette UCB-2000" (manufactured by Hiranuma Sangyo Co., Ltd.) was used as the titrator, and a mixed indicator of bromothymol blue and phenol red was used as the indicator.
• thixotropic agent (1) Organic thixotropic agent; “Floronon SP-1000AF”, manufactured by Kyoeisha Chemical Co., Ltd.
• Thixotropic agent (2) Hydrophobic silica; “Reolosil PM-20L”, manufactured by Tokuyama Corporation
• a vinyl ester resin (A2) used in the following examples and comparative examples was synthesized as follows. 2068 g of epoxy compound (1) and 1.2 g of methylhydroquinone as a polymerization inhibitor (total of epoxy compound and methacrylic acid: 100 0.04 parts by mass with respect to parts by mass), and 2,4,6-tris (dimethylaminomethyl) phenol (“Seikuol TDMP” manufactured by Seiko Chemical Co., Ltd., purity greater than 95% by mass) as a catalyst 9.0 g ( 0.3 parts by mass with respect to a total of 100 parts by mass of the epoxy compound and methacrylic acid) was added and heated to 110°C.
• Example 1 A mixture (1) of 25 parts by mass of a vinyl ester resin (A1-1) and 13.5 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B), and 25 parts by mass of a vinyl ester resin (A2) and 13.5 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B) to prepare a mixture (2).
• a mixture (1) of 25 parts by mass of a vinyl ester resin (A1-1) and 13.5 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B) 25 parts by mass of a vinyl ester resin (A2) and 13.5 parts by mass of phenoxyethyl methacrylate as an ethylenically unsaturated group-containing monomer (B) to prepare a mixture (2).
• Example 2 Comparative Examples 1 to 14
• resin compositions (X-2) to (X-18) and (X'-1) to were produced in the same manner except that the raw materials and blending ratios shown in Tables 5 and 6 were used (X'-14) was obtained.
• the Brookfield viscometer one of the following two types was appropriately selected and used according to the measurement viscosity range. (1) "RB80 type viscometer" manufactured by Toki Sangyo Co., Ltd.; Rotor No. 3-4 The rotor used and the number of revolutions were set as shown in Table 3 below according to the measured viscosity.
• Example 19 The resin composition (X-1) produced in Example 1 was irradiated with light for 60 minutes using a 250 W metal halide lamp (peak wavelength 420 nm, illuminance 20 mW/cm 2 ) to cure a 170 mm ⁇ 170 mm, 4 mm thick film. A product 1 (cast product) was obtained. The illuminance was measured using an illuminance meter "IL1400A" (manufactured by International Light Technologies, photodetector model SEL005, measurement wavelength range: 380 to 450 nm, median value: 415 nm).
• IL1400A manufactured by International Light Technologies, photodetector model SEL005, measurement wavelength range: 380 to 450 nm, median value: 415 nm.
• Example 20 A photopolymerization initiator-containing resin composition (Y-2) was obtained in the same manner as in Example 19, except that the resin composition shown in Table 4 was blended instead of the resin composition (X-1). After that, a cured product 2 was obtained.
• Example 21 A glass fiber chopped strand mat (“MC 450A”, manufactured by Nitto Boseki Co., Ltd.) was impregnated with the resin composition (X-1) produced in Example 1, and three sheets were stacked and cured at 23 ° C. for 5 days. , a 250 W metal halide lamp (peak wavelength: 420 nm, illuminance: 25 mW/cm 2 ) was used to obtain a cured product 3 (FRP: glass fiber content: 31% by mass) having a size of 170 mm ⁇ 170 mm and a thickness of 3.1 mm.
• FRP glass fiber content: 31% by mass
• Example 22 A cured product 4 was obtained in the same manner as in Example 21, except that the resin composition (X-15) produced in Example 15 was used instead of the resin composition (X-1).
• a resin composition that has a low initial viscosity and increases in viscosity over time is provided. Also provided is a composite material in which a fiber base sheet is impregnated with the resin composition.
• the composite material has a resin composition that can retain its shape by increasing its viscosity, has good workability, and can give a cured product with excellent strength. Therefore, it is suitable for reinforcing or repairing fixed structures, and can be preferably used as prepreg, preform, lining material, liner material, and the like.

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