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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters

Definitions

• the present disclosure relates to an unsaturated polyester resin composition and a cured product of the composition.
• Patent Document 1 an aromatic tertiary amine or a ⁇ -diketone compound as an accelerator for curing in an unsaturated polyester resin, and to cure it at room temperature or a temperature close thereto to shorten the curing time.
• Patent Document 2 an aromatic tertiary amine or a ⁇ -diketone compound
• quinone compounds have been used as polymerization inhibitors to improve storage stability, but there was a problem that gel time drift occurs when used in large amounts.
• the present disclosure aims to provide an unsaturated polyester resin composition capable of preventing gelation during long-term storage at high temperature and maintaining curing performance even when stored for a long time. To do.
• the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by adding a cobalt soap, an inorganic tin compound and an amine-based antioxidant to an unsaturated polyester resin, storage stability at a higher temperature than before can be achieved. It has been found that it has excellent properties and maintains an appropriate gelation time even when stored for a long period of time, and can maintain the curing performance.
• the present disclosure includes the following aspects [1] to [11].
• the content of the cobalt soap (C) is 0.001 to 10 parts by mass based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) [1].
• the content of the cobalt coordinating compound (D) is 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) [ [1] or the unsaturated polyester resin composition according to [2].
• the content of the inorganic tin compound (E) is 0.001 to 1 part by mass based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) [1].
• ⁇ The unsaturated polyester resin composition according to any one of [3].
• the content of the amine antioxidant (F) is 0.001 to 1 part by mass based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) [ The unsaturated polyester resin composition according to any one of 1] to [4]. [6] The unsaturated polyester resin composition according to any one of [1] to [5], wherein the cobalt soap (C) contains at least one selected from the group consisting of cobalt octylate and cobalt naphthenate.
• a composite material comprising the unsaturated polyester resin composition according to any one of [1] to [9] and at least one selected from the group consisting of a fiber reinforcing material, a filler and an aggregate.
• an unsaturated polyester resin composition having excellent storage stability at high temperature and capable of maintaining curing performance even when stored for a long period of time as compared with a conventional unsaturated polyester resin composition is provided. be able to.
• (meth)acrylic is a generic term for acrylic and methacrylic
• (meth)acrylate is a generic term for acrylate and methacrylate.
• the “ethylenically unsaturated bond” and the “ethylenically unsaturated group” have a double bond formed between carbon atoms other than carbon atoms forming an aromatic ring and a double bond such as such.
• Each means a group
• the "ethylenically unsaturated monomer” means a monomer having an ethylenically unsaturated bond.
• the unsaturated polyester resin composition of one embodiment includes an unsaturated polyester resin (A), an ethylenically unsaturated monomer (B), a cobalt soap (C), a cobalt coordinating compound (D), and an inorganic tin compound ( E) and an amine-based antioxidant (F).
• the unsaturated polyester resin (A) is obtained by polycondensing a polyhydric alcohol, an unsaturated polybasic acid, and, if necessary, at least one selected from a saturated polybasic acid and a monobasic acid, It is not particularly limited.
• the unsaturated polybasic acid is a polybasic acid having an ethylenically unsaturated bond
• the saturated polybasic acid is a polybasic acid having no ethylenically unsaturated bond. Only one unsaturated polyester resin may be used, or two or more unsaturated polyester resins may be used in combination.
• the polyhydric alcohol (a) is not particularly limited as long as it is a compound having two or more hydroxyl groups.
• glycols More preferred are glycols, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, bisphenol A ethylene oxide adducts, and bisphenol A propylene oxide adducts.
• the polyhydric alcohol may be used alone or in combination of two or more kinds.
• the unsaturated polybasic acid (b) is not particularly limited as long as it is a compound having an ethylenically unsaturated bond and having two or more carboxy groups or an acid anhydride thereof.
• Examples of the unsaturated polybasic acid include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid, endomethylenetetrahydrophthalic anhydride, and tetrahydrophthalic anhydride.
• maleic anhydride, fumaric acid, citraconic acid, itaconic acid and chloromaleic acid are preferable, and maleic anhydride and fumaric acid are more preferable, from the viewpoints of heat resistance and mechanical strength of the cured product.
• the unsaturated polybasic acids may be used alone or in combination of two or more.
• the saturated polybasic acid (c) is not particularly limited as long as it is a compound having no ethylenically unsaturated bond and having two or more carboxy groups or its acid anhydride.
• Examples of the saturated polybasic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, nitrophthalic acid, halogenated phthalic anhydride. , Oxalic acid, malonic acid, azelaic acid, glutaric acid, and hexahydrophthalic anhydride.
• phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, and adipic acid are preferable from the viewpoints of heat resistance and mechanical strength of the cured product, and phthalic anhydride, isophthalic acid, and terephthalic acid are preferable. Is more preferable.
• Dicyclopentadiene maleate can be synthesized from maleic anhydride and dicyclopentadiene by a known method. By using the monobasic acid (d), the viscosity of the unsaturated polyester resin (A) can be reduced and the amount of styrene used can be reduced.
• the unsaturated polyester resin can be synthesized by a known method using the raw materials (a) to (d) above.
• Various conditions in the synthesis of the unsaturated polyester resin can be appropriately set depending on the raw material used and the amount thereof.
• an esterification reaction can be used at a temperature of 140 to 230° C. in an inert gas stream such as nitrogen gas under normal pressure, increased pressure or reduced pressure.
• an esterification catalyst can be used if necessary.
• esterification catalysts include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate.
• the esterification catalyst may be used alone or in combination of two or more kinds.
• the weight average molecular weight (Mw) of the unsaturated polyester resin is not particularly limited.
• the weight average molecular weight of the unsaturated polyester resin is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and further preferably 7,000 to 18,000.
• the weight average molecular weight of the unsaturated polyester resin is preferably 1,000 to 25,000, more preferably 2,000 to 20,000, and further preferably 3,000 to 18, It is 000.
• the “weight average molecular weight” is a standard polystyrene conversion value measured by gel permeation chromatography (GPC).
• the unsaturated degree of the unsaturated polyester resin is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and further preferably 70 to 100 mol %. In another embodiment, the unsaturated degree of the unsaturated polyester resin is preferably 30 to 100 mol %, more preferably 40 to 100 mol %, and further preferably 50 to 100 mol %. When the degree of unsaturation is in the above range, the moldability of the unsaturated polyester resin composition is better.
• the degree of unsaturation of the unsaturated polyester resin can be calculated by the following formula using the unsaturated polybasic acid used as a raw material and the number of moles of the saturated polybasic acid.
• Unsaturation degree (mol %) ⁇ (mol number of unsaturated polybasic acid ⁇ number of ethylenically unsaturated groups in unsaturated polybasic acid)/(mol number of unsaturated polybasic acid+saturated polybasic acid Number of moles) ⁇ 100
• the unsaturated polyester resin composition contains an ethylenically unsaturated monomer (B).
• the ethylenically unsaturated monomer (B) is not particularly limited as long as it is a monomer compound having an ethylenically unsaturated group. There may be one or more ethylenically unsaturated groups.
• ethylenically unsaturated monomer (B) examples include ⁇ -, schreib-, m-, p-alkyl of styrene such as styrene, vinyltoluene, and tert-butylstyrene, nitro, cyano, amide, or Ester derivatives, vinyl compounds such as methoxystyrene, divinylbenzene, vinylnaphthalene and acenaphthylene; diene compounds such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth) ) Acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl
• the content of the ethylenically unsaturated monomer (B) is 10 to 95% by mass, more preferably 30 to 95% by mass based on the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). It is 90% by mass, more preferably 50 to 80% by mass. If the content of the ethylenically unsaturated monomer (B) is 10 to 95% by mass based on the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), the cured product is The mechanical strength can be further improved.
• Cobalt soap (C) has a high effect of suppressing the deactivation of radicals as compared with the curing accelerators of other metal soaps, and therefore has good air-drying property. Further, among the metal soaps, cobalt has the highest activity as a central metal, and is therefore suitable as a curing accelerator. As the cobalt soap (C), commercially available products can be used. Examples of the cobalt soap (C) include cobalt octylate, cobalt naphthenate, and cobalt neodecanoate. Of these, cobalt octylate and cobalt naphthenate are preferable. The cobalt soap (C) may be dissolved in a commonly used organic solvent and added, or may be dissolved in the ethylenically unsaturated monomer (B) and added.
• the content of the cobalt soap (C) is preferably 0.001 to 10 parts by mass, more preferably 100 parts by mass with respect to the total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B).
• the amount is 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass.
• Unsaturated polyester resin composition if the content of the cobalt soap (C) is 0.001 parts by mass or more based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B)
• the gelling time can be further shortened, the surface curability can be improved, and if it is 10 parts by mass or less, the unsaturated polyester resin composition can be cured with an appropriate gelling time. is there.
• the cobalt coordinating compound (D) has a coordinative bondability with the divalent or trivalent cation of cobalt.
• the cobalt soap (C) is activated as a curing accelerator and the radical polymerization initiator (G) It is thought to accelerate decomposition.
• Examples of the cobalt coordinating compound (D) include aromatic tertiary amines, ⁇ -diketones, carboxylic acids, thiols, pyridine analogs, trivalent organic phosphorus compounds, and inorganic halides.
• aromatic tertiary amines include N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, N,N-dibutylaniline, N,N-dimethylaminonaphthalene, N,N -Diethylaminonaphthalene, N,N-dipropylaminonaphthalene, N,N-dibutylaminonaphthalene, N,N-dimethylaminoanthracene, N,N-diethylaminoanthracene, N,N-dipropylaminoanthracene, N,N-dibutyl Aminoanthracene, and derivatives thereof.
• ⁇ -diketones include acetylacetone, ⁇ -acetyl- ⁇ -butyl lactone, N,N-dimethylacetoacetamide, N-pyrrolidinoacetoacetamide, 2-acetylcyclopentanone, 2-acetylcyclohexanone, 1,3- Bis(4-methoxyphenyl)-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, 1-(4-bromophenyl) -1,3-butanedione, 3-chloroacetylacetone, 1-(4-chlorophenyl)-4,4,4-trifluoro-1,3-butanedione, dipivaloylmethane, 2,2-dimethyl-6,6 , 7,7,8,8,8-heptafluoro-3,5-octanedione, and
• Carboxylic acids include aliphatic carboxylic acids such as formic acid, acetic acid and propionic acid, and aromatic carboxylic acids such as benzoic acid and cinnamic acid.
• Thiols include methanethiol, ethanethiol, aliphatic thiols such as propanethiol, and aromatic thiols such as benzenethiol.
• Examples of the pyridine analog include pyridine, chloropyridine, bromopyridine and the like.
• Examples of the trivalent organic phosphorus compound include triphenylphosphine and tricyclohexylphosphine.
• the inorganic halide include calcium chloride, magnesium chloride, calcium bromide, magnesium bromide and the like.
• aromatic tertiary amines and ⁇ -diketones are preferable, and N,N-dimethylaniline, N,N-dimethylacetoacetamide, and N-pyrrolidinoacetoacetamide are more preferable.
• the cobalt coordinating compound (D) may be dissolved in a generally used organic solvent and added, or may be dissolved in the ethylenically unsaturated monomer (B) and added.
• the content of the cobalt coordinating compound (D) is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), The amount is more preferably 0.01 to 1 part by mass, further preferably 0.05 to 0.5 part by mass.
• the content of the cobalt coordinating compound (D) is 0.001 part by mass or more based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B)
• the unsaturated The gelling time of the polyester resin composition can be shortened, and the amount of residual monomers in the resin cured product can be reduced. If it is 5 parts by mass or less, the unsaturated polyester resin composition is cured with an appropriate gelling time. It is possible to
• Inorganic tin compound (E) A commercially available compound can be used as the inorganic tin compound (E).
• the inorganic tin compound (E) include a divalent inorganic tin compound such as tin (II) chloride (SnCl 2 ), and a tetravalent inorganic tin compound such as tin (IV) chloride (SnCl 4 ).
• a divalent inorganic tin compound such as tin (II) chloride (SnCl 2 )
• tetravalent inorganic tin compound such as tin (IV) chloride (SnCl 4 .
• divalent inorganic tin compound examples include tin (II) fluoride (SnF 2 ), tin (II) chloride (SnCl 2 ), tin (II) bromide (SnBr 2 ), tin (II) iodide ( SnI 2), tin oxide (II) (SnO), and the like tin sulfide (II) (SnS) is.
• tin (II) chloride, tin (II) bromide, and tin (II) fluoride are preferable, and tin (II) chloride and tin (II) bromide are more preferable.
• the inorganic tin compound (E) may be dissolved in a generally used organic solvent and added, or may be dissolved in the ethylenically unsaturated monomer (B) and added.
• the content of the inorganic tin compound (E) is preferably 0.001 to 1 part by mass, more preferably 100 parts by mass with respect to the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). Is 0.005 to 0.5 parts by mass, more preferably 0.01 to 0.3 parts by mass.
• the content of the inorganic tin compound (E) is 0.001 parts by mass or more based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), the unsaturated polyester resin If the storage stability of the composition can be increased and the content is 5 parts by mass or less, a cured resin product having excellent water resistance can be obtained.
• amine-based antioxidant (F) As the amine-based antioxidant (F), commercially available products can be used.
• the amine-based antioxidant (F) include primary aliphatic amines such as ethylamine, propylamine and butylamine, secondary aliphatic amines such as diethylamine, dipropylamine and dibutylamine, aniline and its derivatives.
• primary aromatic amines and secondary aromatic amines such as phenothiazine. Among these, it is preferable to use a secondary aromatic amine.
• Examples of the secondary aromatic amine include 3-methoxydiphenylamine, phenothiazine, N,N′-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-phenyl-1-naphthylamine. , Dioctyldiphenylamine, p-(p-toluenesulfonylamido)diphenylamine, and N,N′-dinaphthyl-p-phenylenediamine.
• 3-methoxydiphenylamine, phenothiazine, N,N'-diphenyl-p-phenylenediamine, and N-isopropyl-N'-phenyl-p-phenylenediamine are preferable, and 3-methoxydiphenylamine and phenothiazine are more preferable.
• the amine-based antioxidant (F) may be dissolved in a generally used organic solvent and added, or may be dissolved in the ethylenically unsaturated monomer (B) and added.
• the content of the amine-based antioxidant (F) is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), The amount is more preferably 0.003 to 0.1 part by mass, further preferably 0.004 to 0.05 part by mass. If the content of the amine-based antioxidant (F) is 0.001 parts by mass or more based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), it is unsaturated.
• the storage stability of the polyester resin composition can be increased, and if it is 1 part by mass or less, the unsaturated polyester resin composition can be cured in an appropriate curing time.
• the unsaturated polyester resin composition may contain a radical polymerization initiator (G) as a curing agent in order to accelerate curing.
• a radical polymerization initiator (G) as a curing agent in order to accelerate curing.
• the unsaturated polyester resin composition is added with the radical polymerization initiator (G)
• the unsaturated polyester resin composition starts to be cured.
• the radical polymerization initiator is used. It is desirable to add (G) to the composition immediately before curing the unsaturated polyester resin composition.
• the radical polymerization initiator (G) may be appropriately selected according to the application, curing conditions, etc., and is not particularly limited.
• the radical polymerization initiator for example, a known thermal radical initiator or photo radical initiator can be used. Of these, thermal radical initiators are preferable.
• thermal radical initiator examples include diacyl peroxides such as benzoyl peroxide; peroxyesters such as tert-butylperoxybenzoate; hydroperoxides such as cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide; Examples thereof include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; peroxyketals; alkylperesters; organic peroxides such as percarbonates.
• diacyl peroxides such as benzoyl peroxide
• peroxyesters such as tert-butylperoxybenzoate
• hydroperoxides such as cumene hydroperoxide
• dialkyl peroxides such as dicumyl peroxide
• ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide
• peroxyketals alkylperesters
• the content of the radical polymerization initiator (G) is 0.1 to 10.0 parts by mass based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). Is more preferable, 0.2 to 6.0 parts by mass is more preferable, and 0.3 to 3.5 parts by mass is particularly preferable. Within such a range, the radical polymerization reaction of the unsaturated polyester resin composition is promoted, so that a cured product having high hardness can be obtained.
• the unsaturated polyester resin composition may include a solvent (H).
• the solvent (H) may be derived from the solvent used in the synthesis of the unsaturated polyester resin (A).
• the solvent include organic solvents such as esters such as n-butyl acetate and n-propyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene.
• the above-mentioned ethylenically unsaturated monomer (B) such as styrene may be used.
• the content of the solvent (H) is preferably 5 to 60 parts by mass, more preferably 10 to 10 parts by mass based on 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B).
• the amount is 50 parts by mass, more preferably 20 to 40 parts by mass.
• the content of the solvent (H) does not include the ethylenically unsaturated monomer (B).
• additives can be appropriately added to the unsaturated polyester resin composition within the range that does not affect the effects of the present invention or within the range that does not reduce the mechanical strength of the cured product.
• the additives include thixotropic agents, thixotropic agents, thickeners, colorants, plasticizers, waxes, polymerization inhibitors, and the like.
• thixotropic agent examples include inorganic powders such as silica and clay.
• thixotropic agent examples include polyethylene glycol, glycerin, polyhydroxycarboxylic acid amide, organic quaternary ammonium salt and the like.
• polyhydroxycarboxylic acid amide is BYK-R-605 (manufactured by BYK Japan KK).
• thickener examples include metal oxides such as magnesium oxide, calcium oxide and zinc oxide, and metal hydroxides such as magnesium hydroxide and calcium hydroxide.
• colorant examples include organic pigments, inorganic pigments, dyes and the like.
• plasticizer examples include chlorinated paraffin, phosphoric acid ester, phthalic acid ester and the like.
• Wax can be added for the purpose of improving the surface dryness due to the air blocking effect on the surface of the cured product.
• waxes include petroleum wax, olefin wax, polar wax, and special wax.
• Known polymerization inhibitors such as hydroquinone, trimethylhydroquinone, p-benzoquinone, naphthoquinone, tert-butylhydroquinone, catechol, p-tert-butylcatechol, and 2,6-di-tert-butyl-4-methylphenol. Can be used.
• the composite material can be obtained by combining the unsaturated polyester resin composition with at least one selected from the group consisting of a fiber reinforcing material, a filler and an aggregate.
• fiber reinforcing material examples include organic or inorganic synthetic or natural fiber reinforcing materials such as glass fiber, carbon fiber, polyester fiber, aramid fiber, vinylon fiber and cellulose nanofiber.
• the fiber reinforcing material examples include short fibers, long fibers, twisted yarns, chops, chopped strand mats, continuous strand mats, rovings, nonwoven fabrics such as spunbonded nonwoven fabrics or meltblown nonwoven fabrics, roving cloths, plain weaves, satin weaves, or twill weaves.
• the shape of the woven fabric, the braid, the three-dimensional woven fabric, or the three-dimensional braid can be used.
• the content of the fiber reinforcing material can be appropriately specified according to the intended use of the composite material, required performance, etc., and is not particularly limited. For example, it can be 0.1 to 500 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.
• filler examples include calcium carbonate, aluminum hydroxide, fly ash, barium sulfate, talc, clay, glass powder, wood powder, and the like, glass microballoons, microballoons of saran resin, microballoons of acrylonitrile, and shirasu. Hollow fillers such as balloons can also be used.
• the content of the filler can be appropriately specified according to the intended use of the composite material, required performance, etc., and is not particularly limited. For example, it can be 10 to 500 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.
• aggregates examples include general aggregates such as silica sand, crushed stone, and gravel, synthetic aggregates synthesized from incinerated ash, lightweight aggregates, and the like.
• the content of the aggregate can be appropriately specified according to the intended use of the composite material and the required performance, and is not particularly limited. For example, it can be 10 to 500 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition.
• the cured product is obtained by curing the unsaturated polyester resin composition or the composite material.
• the unsaturated polyester resin composition is produced, for example, by a method of kneading the respective components (A) to (F) and, if necessary, one or more of the respective components (G) to (I). be able to.
• the kneading method is not particularly limited, and for example, a double-arm kneader, a pressure kneader, a planetary mixer or the like can be used.
• the kneading temperature is preferably -10°C to 80°C, more preferably 0°C to 60°C, and most preferably 20°C to 60°C.
• the kneading temperature is -10°C or higher, the kneading property is further improved.
• the kneading temperature is 80° C. or lower, the curing reaction during the kneading of the unsaturated polyester resin composition can be further suppressed.
• the kneading time can be appropriately selected according to each component and its ratio.
• the order of kneading each component when manufacturing the unsaturated polyester resin composition is no particular limitation on the order of kneading each component when manufacturing the unsaturated polyester resin composition.
• the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) are mixed and then other components are mixed, a uniformly mixed unsaturated polyester resin composition is obtained. It is preferable because it is easily damaged.
• the manufacturing method of the composite material may be appropriately selected according to the purpose and is not particularly limited.
• the composite material is, for example, a method of kneading an unsaturated polyester resin composition and at least one selected from a fiber reinforcing material, a filler and an aggregate, or selected from a filler and an aggregate as necessary. It can be produced by a method of impregnating a fiber reinforcement with an unsaturated polyester resin composition containing at least one kind.
• the kneading method is not particularly limited, and for example, a double-arm kneader, a pressure kneader, a planetary mixer or the like can be used.
• the kneading temperature is preferably ⁇ 10° C. to 80° C., more preferably 0° C. to 60° C. When the kneading temperature is -10°C or higher, the kneading property is further improved. When the kneading temperature is 80° C. or lower, the curing reaction during the kneading of the unsaturated polyester resin composition can be further suppressed.
• the kneading time can be appropriately selected according to each component and its ratio.
• the unsaturated polyester resin composition and the composite material can be cured by a known method.
• Examples of the method for curing the unsaturated polyester resin composition or the composite material include a method in which a radical polymerization initiator (G) is added to the unsaturated polyester resin composition or the composite material, and the mixture is cured at room temperature or by heating, radical polymerization initiation.
• G radical polymerization initiator
• Method of curing a composite material prepared by using an unsaturated polyester resin composition containing an agent (G) at room temperature or by heating, and containing a component other than the cobalt soap (C) of the unsaturated polyester resin composition or the composite material A method in which cobalt soap (C) is added to and mixed with an unsaturated polyester resin precursor composition or a composite precursor, and then a radical polymerization initiator (G) is further added and cured at room temperature or by heating, or the above-mentioned unsaturated A composite material prepared by using an unsaturated polyester resin composition obtained by adding a cobalt soap (C) to a polyester resin precursor composition and mixing and then further adding a radical polymerization initiator (G) is cured at room temperature or by heating. And the like.
• the specific temperature range of room temperature and heating may be, for example, a temperature range of 15°C to 200°C.
• the method of using the unsaturated polyester resin composition and the composite material is not particularly limited.
• it can be used as a raw material of general fiber reinforced plastic (hereinafter referred to as “FRP”) applied to pipes of chemical plants, chemical storage tanks, concrete repair materials and the like.
• FRP general fiber reinforced plastic
• the unsaturated polyester resin composition and the composite material have a short curing time and can exhibit an action of reducing or preventing gel time drift, and therefore, in particular, applications requiring fast curing property, such as a decorative plate, a corrugated plate, and various substrates. It is preferably used as a material such as a primer for a material.
• the FRP manufacturing method may be appropriately selected according to the purpose and is not particularly limited. For example, a method of applying or mechanically molding and curing while impregnating a fiber reinforcement with an unsaturated polyester resin composition, or a method of applying or mechanically molding and curing a composite material can be used.
• Examples of methods for coating or mechanically molding the unsaturated polyester resin composition while impregnating the fiber reinforcing material and curing the resin include a hand layup molding method, a resin transfer molding method, and a vacuum assist resin transfer molding method.
• the unsaturated polyester resin composition can be applied using a known application means such as a brush, roll, trowel, spatula, or syringe.
• Examples of the method of coating or mechanically molding the composite material and curing it include a spray-up molding method, a filament winding molding method, a sheet winding molding method, a pultrusion molding method, and an injection molding method.
• Example 1 The components shown in Table 1 were added to and mixed with 100 parts by mass of the obtained mixture AB-1 using a planetary mixer to obtain an unsaturated polyester resin composition. The storage stability and curing performance of the obtained unsaturated polyester resin composition were evaluated. The results are shown in Table 1.
• Example 1 Comparative Examples 1 to 5 Evaluation was performed by the same method as in Example 1 except that the formulation shown in Table 1 was changed. The results are shown in Table 1.
• the unsaturated polyester resin compositions of Examples 1 to 7 could be stably stored for 30 days or longer.
• Comparative Examples 1 to 5 gelation occurred early and storage stability was low.
• Examples 1 to 7 using the divalent inorganic tin compound had better storage stability than Comparative Examples 4 and 5 using the organic tin compound, and the curing performance was hard to change with the storage time.
• the storage stability at high temperature is excellent, and the curing performance can be maintained even when stored for a long period of time.
• the unsaturated polyester resin composition described above can be suitably used in the field of applications such as decorative boards, resin concrete, and primers that require fast curing.

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