JP2021021017A - Unsaturated polyester resin composition and composite material containing unsaturated polyester resin composition - Google Patents

Abstract

To provide an unsaturated polyester resin composition that gives a cured product having a reduced amount of residual styrene and having excellent surface dryability and stain resistance.SOLUTION: An unsaturated polyester resin composition contains an unsaturated polyester resin (A), an ethylenic unsaturated monomer (B), a metallic soap (C), a bidentate ligand compound (D) having coordination bonding properties to a central metal included in the metallic soap (C), and having no amide bond, and polysiloxane (E).SELECTED DRAWING: None

Description

The present disclosure relates to an unsaturated polyester resin composition and a cured product thereof, and a composite material containing the unsaturated polyester resin composition and a cured product thereof.

The unsaturated polyester resin composition has excellent hardness and moldability, and for example, FRP (fiber reinforced plastic) base material, paint, adhesive, resin concrete, etc. used for construction materials, transportation equipment, industrial equipment, etc. It is widely used for decorative boards and the like. The unsaturated polyester resin composition is processed, for example, by casting.

Many unsaturated polyester resin compositions contain styrene as an ethylenically unsaturated monomer, but from the viewpoint of environmental protection, it is required to further reduce the amount of styrene emitted.

However, when styrene is replaced with another ethylenically unsaturated monomer in order to reduce the amount of styrene emitted, some ethylenically unsaturated monomers are more susceptible to curing inhibition by oxygen than styrene, and are coated. There was a problem that the stain resistance of the film was lowered.

In order to improve the stain resistance of the coating film, for example, an unsaturated polyester resin composition to which paraffin wax is added (Non-Patent Document 1) can be obtained by using a compound having three or more allyl ether groups in one molecule. An unsaturated polyester resin composition (Patent Document 1) containing a dry unsaturated polyester and a monomer having two or more (meth) acryloyl groups in one molecule, and a curable resin component as main components. A curable resin composition (Patent Document 2) containing a urethane-based and / or ester-based fluorine compound having at least one perfluoroalkyl group in the molecule has been proposed.

Japanese Unexamined Patent Publication No. 2004-189876 Japanese Unexamined Patent Publication No. 2006-152189

"Polyester Resin Handbook", Eiichiro Takiyama, Nikkan Kogyo Shimbun, 1988, p. 745

However, the composition described in Patent Document 1 has a problem that it has poor storage stability and gelation occurs during long-term storage at room temperature. Further, Patent Documents 1 and 2 do not mention any surface drying property of the cured product, and in the method described in Patent Document 2, a perfluoroalkyl compound having no radically polymerizable unsaturated group is used as an additive. Since it is used, there is a problem that the surface drying property is poor. On the other hand, there is a strong demand for the use of styrene, which is low in cost and has excellent mechanical properties of the cured product.

In view of the above, it is an object of the present invention to provide an unsaturated polyester resin composition that gives a cured product having a small amount of residual styrene in the cured product and excellent surface drying property and stain resistance.

The low surface dryness and stain resistance of the cured product are considered to be due to the low reactivity of the unsaturated polyester resin and the ethylenically unsaturated monomer. That is, it is presumed that segregation of the unreacted unsaturated polyester resin on the surface of the cured product causes a decrease in the surface dryness and surface smoothness of the cured product, which in turn leads to a decrease in stain resistance and the like. To.

As a result of diligent studies to solve the above problems, the present inventors have added metal soap, a specific bidentate ligand compound, and polysiloxane to the unsaturated polyester resin composition, so that the cured product remains. It has been found that an unsaturated polyester resin composition having a small amount of styrene and giving a cured product having excellent surface drying property and stain resistance can be obtained.
That is, the content of the present disclosure includes the following embodiments.
[1] It has a coordination bond with an unsaturated polyester resin (A), an ethylenically unsaturated monomer (B), a metal soap (C), and a central metal contained in the metal soap (C). An unsaturated polyester resin composition containing a bidentate ligand compound (D) and a polysiloxane (E) having no amide bond.
[2]
[1] The amount of the metal soap (C) is 0.001 to 10 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). Unsaturated polyester resin composition.
[3]
The bidentate ligand compound (D) is 0.001 to 5 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) [ The unsaturated polyester resin composition according to 1] or [2].
[4]
The polysiloxane (E) is 0.001 to 1 part by mass with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) [1] to [ 3] The unsaturated polyester resin composition according to any one of.
[5]
The unsaturated polyester resin composition according to any one of [1] to [4], wherein the central metal contained in the metal soap (C) is at least one selected from iron, cobalt, manganese and copper.
[6]
The unsaturated polyester resin composition according to any one of [1] to [5], wherein the bidentate ligand compound (D) is at least one selected from β-diketone and α-ketolactone.
[7]
The unsaturated polyester resin composition according to any one of [1] to [6], wherein the bidentate ligand compound (D) is an α-acetyl lactone.
[8]
The unsaturated polyester resin composition according to any one of [1] to [7], wherein the polysiloxane (E) has a weight average molecular weight of 3,000 to 20,000.
[9]
The unsaturated polyester resin composition according to any one of [1] to [8], further comprising a radical polymerization initiator (F).
[10]
A cured product of the unsaturated polyester resin composition according to any one of [1] to [9].
[11]
A composite material containing the unsaturated polyester resin composition according to any one of [1] to [9] and at least one selected from a fiber reinforcing material, a filler and an aggregate.
[12]
The cured product of the composite material according to [11].

According to this embodiment, it is possible to provide an unsaturated polyester resin composition that gives a cured product having a smaller amount of residual styrene in the cured product and excellent surface drying property and stain resistance as compared with the conventional unsaturated polyester resin composition.

Hereinafter, the present invention will be described in more detail.

In the present disclosure, "-" means a value equal to or greater than the value before the description of "-" and a value after the description of "-".

In the present disclosure, "(meth) acrylic" is a general term for acrylic and methacrylic, and "(meth) acrylate" is a general term for acrylate and methacrylate.

In the present disclosure, the "ethylenically unsaturated bond" means a double bond formed between carbon atoms other than the carbon atom forming the aromatic ring, and the "ethylenically unsaturated monomer" means ethylene. It means a monomer having a sex unsaturated bond.

(Unsaturated polyester resin composition)
The unsaturated polyester resin composition of one embodiment includes an unsaturated polyester resin (A), an ethylenically unsaturated monomer (B), a metal soap (C), a bidentate ligand compound (D) and a polysiloxane ( E) is included.

[Unsaturated polyester resin (A)]
The unsaturated polyester resin (A) is at least one selected from a polyhydric alcohol (a), an unsaturated polybasic acid (b), and optionally a saturated polybasic acid (c) and a monobasic acid (d). It is obtained by polycondensing the acid, and is not particularly limited. The unsaturated polybasic acid (b) is a polybasic acid having an ethylenically unsaturated bond, and the saturated polybasic acid (c) is a polybasic acid having no ethylenically unsaturated bond. The unsaturated polyester resin (A) may be used alone or in combination of two or more.

<Multivalent alcohol (a)>
The polyhydric alcohol (a) is not particularly limited as long as it is a compound having two or more hydroxyl groups. Among them, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentanediol, tetraethylene glycol, polyethylene glycol, neopentyl glycol, 2-methyl-1,3- Propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, hydride bisphenol A, bisphenol A, glycerin, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A Is preferable, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydride bisphenol A, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are more preferable. The polyhydric alcohol (a) may be used alone or in combination of two or more.

<Unsaturated polybasic acid (b)>
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. For example, maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid and the like can be mentioned. Among them, maleic anhydride, fumaric acid, citraconic acid, itaconic acid and chloromaleic acid are preferable, and maleic anhydride and fumaric acid are more preferable, from the viewpoint of heat resistance and mechanical strength of the cured product. The unsaturated polybasic acid (b) may be used alone or in combination of two or more.

<Saturated polybasic acid (c)>
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 an acid anhydride thereof. For example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endomethylene tetrahydrophthalic anhydride, nitrophthalic acid, tetrahydrophthalic anhydride, Examples thereof include halogenated phthalic anhydride, oxalic acid, malonic acid, azelaic acid, glutaric acid and hexahydrophthalic anhydride. Among them, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, endomethylene tetrahydrophthalic anhydride and tetrahydrophthalic anhydride are preferable, and anhydrous, from the viewpoint of heat resistance and mechanical strength of the cured product. Phthalic anhydride, isophthalic acid and terephthalic acid are more preferred.

<monobasic acid (d)>
Examples of the monobasic acid (d) include dicyclopentadiene malate, benzoic acid and its derivative, and cinnamic acid and its derivative, and dicyclopentadiene malate is preferable. Dicyclopentadiene malate 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 lowered, and the amount of styrene used can be reduced.

The unsaturated polyester resin (A) can be synthesized by a known method using the raw materials (a) to (d) described above. Various conditions in the synthesis of the unsaturated polyester resin (A) can be appropriately set according to the raw materials used and the amount thereof. Generally, an esterification reaction under pressure or reduced pressure at a temperature of 140 to 230 ° C. in an inert gas stream such as nitrogen gas can be used. In the esterification reaction, an esterification catalyst can be used if necessary. Examples of 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.

The weight average molecular weight (Mw) of the unsaturated polyester resin (A) is not particularly limited. The weight average molecular weight of the unsaturated polyester resin (A) is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and even more preferably 7,000 to 18,000. .. When the weight average molecular weight is 3,000 to 25,000, the moldability of the unsaturated polyester resin composition becomes even better. In the present disclosure, the "weight average molecular weight" is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC: gel permeation chromatography).

The degree of unsaturation of the unsaturated polyester resin (A) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 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 (A) can be calculated by the following formula using the number of moles of the unsaturated polybasic acid (b) and the saturated polybasic acid (c) used as raw materials.

Degree of unsaturation (mol%) = {(number of moles of unsaturated polybasic acid (b) x number of unsaturated groups in unsaturated polybasic acid (b)) / (moles of unsaturated polybasic acid (b)) Number + number of moles of saturated polybasic acid (c))} × 100

[Ethylene unsaturated monomer (B)]
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. The ethylenically unsaturated group may be one or more. Examples of the ethylenically unsaturated monomer (B) include α-, о-, m-, p-alkyl, nitro, cyano, amide, or ester derivatives of styrenes such as styrene, vinyltoluene, and t-butylstyrene. , Vinyl compounds such as methoxystyrene, divinylbenzene, vinylnaphthalene, acenaphthylene; butadiene, 2,3-dimethylbutadiene, isoprene, diene compounds such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , N-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (Meta) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy Ethyl (meth) acrylate, allyl (meth) acrylate, isobornyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (Meta) acrylates such as tricyclodecanoldi (meth) acrylate and trimethylpropantri (meth) acrylate; (meth) acrylamide, N, N'-dimethyl (meth) acrylamide, N, N'-diisopropyl (meth) Examples thereof include (meth) acrylamide such as acrylamide; unsaturated dicarboxylic acid diesters such as diethyl citraconate; monomaleimide compounds such as N-phenylmaleimide; and N- (meth) acryloylphthalimide. Of these, styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate are preferable from the viewpoint of physical properties and surface dryness of the cured product. , Styrene, vinyltoluene and methyl (meth) acrylate are more preferred.

The content of the ethylenically unsaturated monomer (B) is 10 to 95% by mass, more preferably 20 to 95% by mass, based on the total of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). It is 90% by mass, more preferably 25 to 80% by mass. If the content of the ethylenically unsaturated monomer (B) is 10 to 95% by mass with respect to the total of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), the machine of the cured product Target strength can be further increased.

[Metal soap (C)]
The metal soap (C) is a metal salt of a long chain fatty acid or other organic acid. The metal soap generally does not include sodium salt and potassium salt, but in the present disclosure, these metal salts are also included. The metal soap (C) may be used alone or in combination of two or more. The metal soap (C) can function as a curing accelerator in the unsaturated polyester resin composition.

The long-chain fatty acid in the metal soap (C) may be either a saturated fatty acid or an unsaturated fatty acid. The number of carbon atoms of the long chain fatty acid is not particularly limited, but is preferably 6 to 30 from the viewpoint of uniform dissolution and dispersibility of the metal soap (C) in the unsaturated polyester resin composition. , More preferably 6 to 20, even more preferably 6 to 16. Specifically, octanoic acids such as heptanic acid, caprylic acid and 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid. , Tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacanthic acid, naphthenic acid and other saturated fatty acids having a chain or cyclic structure; Further, rosin acid derived from other natural products, linseed oil extracted fatty acid, soybean oil extracted fatty acid, tall oil extracted fatty acid and the like can also be mentioned. Of these, octanoic acid and naphthenic acid are preferable, and 2-ethylhexanoic acid and naphthenic acid are more preferable.

As the other organic acid, for example, a weak acid having a carboxy group, a hydroxy group, an enol group and the like, which is soluble in an organic solvent, is preferable.

Examples of weak acids having a carboxy group include carboxylic acids such as formic acid, acetic acid and oxalic acid; hydroxy acids such as citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxysilic acid and folic acid; alanine and arginine. Amino acids such as benzoic acid, aromatic acids such as phthalic acid and the like.

Examples of the compound having a hydroxy group or an enol group include ascorbic acid, α acid, imic acid, erythorbic acid, croconic acid, kodi acid, squaric acid, sulfic acid, tycoic acid, dehydroacetic acid, delta acid, uric acid and hydroxamic acid. , Fumic acid, fluboic acid, phosphonic acid and the like.

The central metal contained in the metal soap (C) is not particularly limited. Examples thereof include vanadium, iron, copper, cobalt, manganese, titanium, ittrium, tin, lead, bismuth, zirconium, calcium, etc. From the viewpoint of storage stability of the unsaturated polyester resin composition, vanadium, iron, copper, etc. Cobalt, manganese and zirconium are preferred, with iron, cobalt, manganese and copper being more preferred.

Specific examples of the metal soap (C) include cobalt octylate, manganese octylate, yttrium octylate, tin octylate, lead octylate, cobalt naphthenate, lead naphthenate, bismuth naphthenate (III), and naphthenic acid. Examples thereof include ittrium, calcium naphthenate, and cobalt neodecanoate. Of these, cobalt octylate, manganese octylate and cobalt naphthenate are preferably used from the viewpoint of curability and tackiness.

The metal soap (C) may be added by dissolving it in a generally used organic solvent, or it may be added by dissolving it in an ethylenically unsaturated monomer (B).

The content of the metallic soap (C) is preferably 0.001 to 10 parts by mass, more preferably 0.001 to 10 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). It is 0.005 to 5 parts by mass, more preferably 0.05 to 3 parts by mass. If the content of the metallic soap (C) is 0.001 part by mass or more with respect to 100 parts by mass of the total of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), the unsaturated polyester resin composition The gelation time of ethylene can be shortened, the degree of curing can be improved, and the tackiness can be reduced. If the gelation time is 10 parts by mass or less, the unsaturated polyester resin composition can be prepared with an appropriate gelation time. It can be cured.

[Bidentate ligand compound (D)]
The bidentate ligand compound (D) is a compound having a coordination bond to the central metal contained in the metal soap (C) and having no amide bond. The bidentate ligand compound (D) can coordinate with the central metal contained in the metal soap (C) in the unsaturated polyester resin composition to change the electronic state of the central metal.

Examples of the bidentate ligand compound (D) include β-diketone and α-ketolactone. Examples of α-ketolactone include α-acetyl lactone such as α-acetyl-γ-butyrolactone, α-acetyl-δ-valerolactone, and α-acetyl-ε-caprolactone. Examples of β-diketone include acetylacetone, 2,2,6,6-tetramethylheptane-3,5-dione, 2,6-dimethyl-3,5-heptanedione and the like. From the viewpoint of reducing the amount of residual styrene after curing of the unsaturated polyester resin composition, it is particularly preferable to use α-ketolactone, and more preferably α-acetyllactone.

The bidentate ligand compound (D) may be added by dissolving it in a generally used organic solvent, or it may be added by dissolving it in an ethylenically unsaturated monomer (B). The content of the bidentate ligand compound (D) is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass in total of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). , More preferably 0.005 to 1 part by mass, still more preferably 0.01 to 0.5 part by mass. If the content of the bidentate ligand compound (D) is 0.001 part by mass or more with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B), it is not possible. The gelation time of the saturated polyester resin composition can be shortened, and the amount of residual styrene in the cured product can be further reduced. Appropriate gel if the content of the bidentate ligand compound (D) is 5 parts by mass or less based on 100 parts by mass of the total of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). It is possible to cure the unsaturated polyester resin composition in the conversion time.

[Polysiloxane (E)]
Commercially available polysiloxane (E) can be used, for example, polydimethylsiloxane, polydiethylsiloxane, polydipropylsiloxane, polydibutylsiloxane, polydipentylsiloxane, polyhexylsiloxane, polyheptylsiloxane, polyoctylsiloxane, polynonyl. Examples thereof include siloxane, polymethylethylsiloxane, polymethylpropylsiloxane, polymethylbutylsiloxane, polyethylpropylsiloxane, polyethylbutylsiloxane, polypropylbutylsiloxane, and polydiphenylsiloxane. The polysiloxane (E) may be added by dissolving it in a generally used organic solvent, or it may be added by dissolving it in an ethylenically unsaturated monomer (B). From the viewpoint of surface smoothness and surface dryness, the content of the polysiloxane (E) is preferably 100 parts by mass based on the total of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). It is 0.001 to 1 part by mass, more preferably 0.005 to 0.5 part by mass, and further preferably 0.01 to 0.3 part by mass.

The weight average molecular weight (Mw) of the polysiloxane (E) is not particularly limited. The weight average molecular weight of the polysiloxane (E) is preferably 3,000 to 20,000, more preferably 3,000 to 15,000, and even more preferably 3,000 to 13,000. When the weight average molecular weight is 3,000 to 20,000, both surface smoothness and surface dryness are excellent.

[Radical polymerization initiator (F)]
The unsaturated polyester resin composition may contain a radical polymerization initiator (F). Curing can be promoted by using the radical polymerization initiator (F). When the radical polymerization initiator (F) is added to the unsaturated polyester resin composition, the curing of the unsaturated polyester resin composition starts. Therefore, the radical polymerization initiator (F) is immediately before curing the unsaturated polyester resin composition. It is desirable to add it.

The radical polymerization initiator (F) may be appropriately selected depending on the application, curing conditions and the like, and is not particularly limited. For example, known thermal radical initiators and photoradical initiators can be used. Of these, thermal radical initiators are preferred. Examples of the thermal radical initiator include diacyl peroxides such as benzoyl peroxide; peroxyesters such as t-butyl peroxybenzoate; hydroperoxides such as cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide; Ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; peroxyketal; alkyl peroxides; organic peroxides such as percarbonate can be mentioned.

The content of the radical polymerization initiator (F) is 0.1 to 10.0 parts by mass with respect to 100 parts by mass in total 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 the above range, the radical polymerization reaction of the unsaturated polyester resin composition is promoted, so that a cured product having higher hardness can be obtained.

[Solvent (G)]
The unsaturated polyester resin composition may contain a solvent (G). The solvent (G) may be derived from the solvent used in the synthesis of the unsaturated polyester resin (A). Examples of the solvent (G) include esters such as n-butyl acetate and n-propyl acetate; and organic solvents such as aromatic hydrocarbons such as benzene, toluene and xylene. As the solvent (G), the above-mentioned ethylenically unsaturated monomer (B) such as styrene may be used. The content of the solvent (G) 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 of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). It is 50 parts by mass, more preferably 20 to 40 parts by mass. The content of the solvent (G) does not include the ethylenically unsaturated monomer (B).

[Acetamide (H)]
The unsaturated polyester resin composition may contain acetamide (H) from the viewpoint of surface smoothness and surface dryness. Examples of acetamide (H) include N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide, N, N-dibutylacetamide, N-methyl-N-ethylacetamide. Examples thereof include acetamide, N-methyl-N-butylacetamide, N-methyl-N-propylacetamide, N-ethyl-N-propylacetamide, N-ethyl-N-butylacetamide and the like. Of these, N, N-dimethylacetamide is preferably used from the viewpoint of surface drying property.

From the viewpoint of surface smoothness and surface dryness, the content of acetamide (H) is preferably 0 with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). It is 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass, and further preferably 0.05 to 0.3 part by mass. Within the above range, the radical polymerization reaction of the unsaturated polyester resin composition is promoted.

[Additive]
One or more additives can be appropriately added to the unsaturated polyester resin composition as long as it does not affect the effects of the present invention and does not reduce the mechanical strength of the cured product. Examples of the additive include a shaking denaturing agent, a shaking denaturing aid, a thickener, a colorant, a plasticizer, a wax, a polymerization inhibitor and the like.

Examples of the rocking denaturing agent include inorganic powders such as silica and clay.

Examples of the rock denaturation aid include polyethylene glycol, glycerin, polyhydroxycarboxylic acid amide, and organic quaternary ammonium salt. A specific example of the polyhydroxycarboxylic acid amide is BYK-R-605 (manufactured by Big Chemie Japan Co., Ltd.).

Examples of the thickener include metal oxides such as magnesium oxide, calcium oxide and zinc oxide, and metal hydroxides such as magnesium hydroxide and calcium hydroxide.

Examples of the colorant include organic pigments, inorganic pigments, dyes and the like.

Examples of the plasticizer include chlorinated paraffin, phosphoric acid ester, phthalate ester and the like.

Wax can be added for the purpose of improving the surface drying property by the air blocking effect on the surface of the cured product. Examples of such waxes include petroleum wax, olefin wax, polar wax, special wax and the like.

Conventionally known polymerization inhibitors include hydroquinone, trimethylhydroquinone, p-benzoquinone, naphthoquinone, t-butylhydroquinone, catechol, pt-butylcatechol, and 2,6-di-t-butyl-4-methylphenol. Can be used.

(Composite material)
The composite material of one embodiment includes the unsaturated polyester resin composition and at least one selected from fiber reinforcing materials, fillers and aggregates.

The composite material can be used as a raw material for general fiber reinforced plastics (hereinafter referred to as "FRP") applied to, for example, pipes of chemical plants, chemical storage tanks, concrete repair materials and the like. Since the composite material has a short curing time and can suppress a decrease in the curing rate after long-term storage, various applications such as a decorative board, a corrugated sheet, and a primer for various substrates are particularly required. It is preferably used as a material.

[Fiber reinforcement]
Examples of the fiber reinforcing material 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 shape of the fiber reinforcing material includes, for example, short fibers, long fibers, twisted yarns, chops, chopped strand mats, continuous strand mats, rovings, spunbonded non-woven fabrics, melt blown non-woven fabrics and other non-woven fabrics, roving cloths, plain weaves, satin weaves or twill weaves. Woven fabrics such as, braids, three-dimensional textiles, and three-dimensional braids can be used.

The content of the fiber reinforcing material can be appropriately specified according to the intended use of the composite material, the required performance, and the like, 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 of the filler include calcium carbonate, aluminum hydroxide, fly ash, barium sulfate, talc, clay, glass powder, wood powder, etc., such as glass microballoons, saran resin microballoons, acrylonitrile microballoons, and silas. 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, the required performance, and the like, 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.

[aggregate]
Examples of the aggregate include general aggregates such as silica sand, crushed stone, and gravel, synthetic aggregates synthesized from incineration ash, and lightweight aggregates.

The content of the aggregate can be appropriately specified according to the intended use of the composite material, the required performance, and the like, 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.

(Cured product)
The cured product is obtained by curing an unsaturated polyester resin composition or a composite material by heating or the like.

(Manufacturing method of unsaturated polyester resin composition)
The unsaturated polyester resin composition is produced, for example, by a method of kneading the above-mentioned components (A), (B), (C), (D), and (E) with additives contained as necessary. it can. The kneading method is not particularly limited, and for example, a double-armed kneader, a pressurized 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. 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 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.

There is no particular limitation on the order in which each component is kneaded when producing the unsaturated polyester resin composition. For example, when a part or all of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B) are mixed and then the other components are mixed, a uniformly mixed unsaturated polyester resin composition is obtained. It is preferable because it is easy to get rid of.

(Manufacturing method of composite material)
The method for producing the composite material may be appropriately selected depending on the intended purpose, and is not particularly limited. The composite material is, for example, a method of kneading an unsaturated polyester resin composition with at least one selected from a fiber reinforced concrete, a filler and an aggregate, and at least one selected from the filler and the aggregate if necessary. It can be produced by a method of impregnating a fiber reinforcing material with an unsaturated polyester resin composition to which a seed has been added. The kneading method is not particularly limited, and for example, a double-armed kneader, a pressurized 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 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.

(Curing method of unsaturated polyester resin composition and composite material)
The unsaturated polyester resin composition and the composite material can be cured by a known method. As a curing method, for example, a method of adding a radical polymerization initiator (F) to an unsaturated polyester resin composition or a composite material and curing it at room temperature or by heating, or an unsaturated polyester to which a radical polymerization initiator (F) is added. A method of curing a composite material prepared using a resin composition at room temperature or by heating, an unsaturated polyester resin composition or an unsaturated polyester resin precursor composition or composite containing components other than the metal soap (B) of the composite material. A method in which the metal soap (B) is added to the precursor material and mixed, and then the radical polymerization initiator (F) is further added and cured at room temperature or by heating, or the metal soap (the unsaturated polyester resin precursor composition is added to the metal soap (F). Examples thereof include a method of curing a composite material prepared by using an unsaturated polyester resin composition in which B) is added and mixed, and then a radical polymerization initiator (F) is further added, at room temperature or by heating. Here, the temperature range of normal temperature and heating can be, for example, a temperature range of 15 ° C. to 200 ° C.

(How to use unsaturated polyester resin composition and composite material)
The method of using the unsaturated polyester resin composition and the composite material is not particularly limited. For example, it can be used as a raw material for general fiber reinforced plastics (hereinafter referred to as "FRP") applied to pipes of chemical plants, chemical storage tanks, concrete repair materials and the like. FRP produced from an unsaturated polyester resin composition and a composite material has excellent surface drying resistance and stain resistance. In particular, it is preferably used as a raw material for applications requiring quick curing, such as decorative boards, corrugated sheets, and primers for various substrates.

The method for producing the FRP may be appropriately selected depending on the intended purpose, and is not particularly limited. For example, a method of applying or mechanically molding the unsaturated polyester resin composition while impregnating the fiber reinforcing material and curing the composition, or a method of applying or mechanically molding the composite material and curing the composite material can be mentioned.

Examples of the method of applying or mechanically molding the unsaturated polyester resin composition while impregnating the fiber reinforcing material and curing the composition include a hand lay-up molding method, a resin transfer molding method, and a vacuum assisted resin transfer molding method. Here, the unsaturated polyester resin composition can be applied by using a known application means such as a brush, a roll, a trowel, a spatula, and a syringe.

Examples of the method of applying 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, an injection molding method and the like.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples.
(1) Raw material [Method for measuring weight average molecular weight of unsaturated polyester resin (A)]
The weight average molecular weight of the unsaturated polyester resin (A) was measured by gel permeation chromatography (Showa Denko KK Shodex® GPC-101) under the following conditions, and a standard polystyrene calibration curve was used. Ask.
Column: Showa Denko LF-804
Column temperature: 40 ° C
Sample: 0.2 mass% tetrahydrofuran solution of unsaturated polyester resin Flow rate: 1 mL / min Eluent: tetrahydrofuran Detector: RI-71S

The raw materials used in Examples and Comparative Examples were produced or obtained as follows.

[Synthesis of unsaturated polyester resin (A)]
(UPE-1)
372 g of propylene glycol and 519 g of fumaric acid were placed in a 1 L flask equipped with a stirrer, a distilling condenser, a thermometer, and a nitrogen gas introduction tube, and heated and stirred at 200 ° C. under a nitrogen gas stream to distill off the generated water. At the same time, when the acid value reached 43.0 mgKOH / g, the mixture was cooled, and by further adding 270 g of styrene and 0.02 g of hydroquinone, an unsaturated polyester resin (weight average molecular weight 3,200, degree of unsaturation 100 mol%) was added. ) And an ethylenically unsaturated monomer to obtain UPE-1. The content of styrene in UPE-1 is 27% by mass.

(UPE-2)
372 g of propylene glycol and 519 g of fumaric acid were placed in a 1 L flask equipped with a stirrer, a distilling condenser, a thermometer, and a nitrogen gas introduction tube, and heated and stirred at 200 ° C. under a nitrogen gas stream to distill off the generated water. At the same time, when the acid value reached 43.0 mgKOH / g, the mixture was cooled, and by further adding 270 g of methyl methacrylate and 0.02 g of hydroquinone, an unsaturated polyester resin (weight average molecular weight 3,200, degree of unsaturation 100) was added. A mixture UPE-2 of (molar%) and ethylenically unsaturated monomer was obtained. The content of methyl methacrylate in UPE-2 is 27% by mass.

Cobalt octylate was used as the metal soap (C).

Α-Acetyl-γ-butyrolactone was used as the bidentate ligand compound (D).

Polydimethylsiloxane BYK-320 (manufactured by Big Chemie Japan Co., Ltd., Mw13,600) was used as the polysiloxane (E).

Permec N (methyl ethyl ketone peroxide, manufactured by NOF CORPORATION) was used as the radical polymerization initiator (F).

N, N-dimethylacetamide was used as acetamide (H).

(2) Evaluation Method The amount of residual styrene in the cured product of the unsaturated polyester resin composition, surface drying property, stain resistance, pencil hardness and storage stability of the unsaturated polyester resin composition were measured by the following methods.

[Amount of residual styrene]
The unsaturated polyester resin composition was applied to a glass plate of 150 mm × 300 mm in a constant temperature and humidity chamber at 23 ° C. and 50% humidity with an applicator so as to have a thickness of 150 μm. From this point in time, 24 hours later, it is contained in the cured product based on JIS K6904: 2016 [Plastic-unsaturated polyester resin-quantification method of residual styrene monomer and other volatile aromatic hydrocarbons by gas chromatography]. The amount of residual styrene produced was quantified. The conditions for gas chromatography are as follows.
Gas Chromatography: GC-2014 manufactured by Shimadzu Corporation
Column: ULBON HR-1 (30m x 0.53mm ID x 0.5mm)
Carrier gas: Nitrogen gas Pressure: 52.0 kPa
Vaporization chamber temperature: 130.0 ° C
Column temperature: 80.0 ° C
Detector: FID (130.0 ° C)

[Surface dryness]
The unsaturated polyester resin composition was applied to a glass plate of 150 mm × 300 mm in a constant temperature and humidity chamber at 23 ° C. and 50% humidity with an applicator so as to have a thickness of 150 μm. With this point as a starting point, the surface condition of the coating film was confirmed by touching the finger, and the time (time) until the resin composition did not adhere to the finger was measured.

[Stain resistance]
The unsaturated polyester resin composition was applied to a glass plate of 150 mm × 300 mm in a constant temperature and humidity chamber at 23 ° C. and 50% humidity with an applicator so as to have a thickness of 150 μm. With this point as the starting point, a straight line of 5 cm was drawn on the coating film 24 hours later using a black felt-tip pen. Then, the black line was wiped off with a non-woven fabric sufficiently impregnated with acetone. If there is a trace of a black line, it is judged as "bad", and if there is no trace of a black line, it is judged as "good".

[Pencil hardness]
The unsaturated polyester resin composition was applied to a glass plate of 150 mm × 300 mm in a constant temperature and humidity chamber at 23 ° C. and 50% humidity with an applicator so as to have a thickness of 150 μm. From this point in time, 24 hours later, the pencil hardness of the coating film was measured based on JIS K5600-5-4: 1999 [scratch hardness (pencil method)].

[Storage stability]
The test was carried out using the mixture before the addition of the radical polymerization initiator (F) in the preparation of the unsaturated polyester resin composition. 100 g of the mixture is poured into a colorless and transparent flat-bottomed glass tube with a total length of 110 mm and an inner diameter of 35 mm to a height of 90 mm from the bottom, and the rest is filled with air to prepare a sample for measurement, stored in a constant temperature bath at 30 ° C., and not every day. The fluidity of the saturated polyester resin composition was visually observed and the number of days until gelation was measured. "Gelification" refers to a state in which the unsaturated polyester resin composition has no fluidity, and when the glass tube is turned upside down, the bubbles in the upper part of the glass tube do not move and continue to exist in the lower part.

(3) Preparation and Evaluation of Unsaturated Polyester Resin Composition [Examples 1 to 5, Comparative Examples 1 to 4]
Using a planetary mixer, a mixture of unsaturated polyester resin (A) and ethylenically unsaturated monomer (B) with the composition shown in Table 1, metal soap (C), bidentate ligand compound (D), Polysiloxane (E) and acetamide (H) were charged at 25 ° C. and mixed for 3 minutes, then the radical polymerization initiator (F) was added and mixed at 25 ° C. for 10 seconds to form an unsaturated polyester resin composition. Was prepared. Table 1 shows the evaluation results of the unsaturated polyester resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4.

The surfaces of Examples 1 to 5 described above were dried within 1 hour after molding, and the stain resistance and pencil hardness were also good. On the other hand, in Comparative Examples 1, 2 and 4, the time required for surface drying was long and the stain resistance was also poor. Comparative Example 3 did not cure.

According to the above configuration, the amount of residual styrene in the cured product is small, and the effect of excellent surface drying property and stain resistance is obtained. The unsaturated polyester resin composition can be suitably used for applications such as decorative boards that require quick curing and stain resistance.

Claims (12)

It has a coordination bond with the unsaturated polyester resin (A), the ethylenically unsaturated monomer (B), the metal soap (C), and the central metal contained in the metal soap (C), and is amide. An unsaturated polyester resin composition comprising a bidentate ligand compound (D) and a polysiloxane (E) having no bond. The first aspect of claim 1, wherein the metal soap (C) is 0.001 to 10 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). Unsaturated polyester resin composition. Claimed that the bidentate ligand compound (D) is 0.001 to 5 parts by mass with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). Item 2. The unsaturated polyester resin composition according to Item 1 or 2. Claims 1 to 3 in which the polysiloxane (E) is 0.001 to 1 part by mass with respect to a total of 100 parts by mass of the unsaturated polyester resin (A) and the ethylenically unsaturated monomer (B). The unsaturated polyester resin composition according to any one of the above. The unsaturated polyester resin composition according to any one of claims 1 to 4, wherein the central metal contained in the metal soap (C) is at least one selected from iron, cobalt, manganese and copper. The unsaturated polyester resin composition according to any one of claims 1 to 5, wherein the bidentate ligand compound (D) is at least one selected from β-diketone and α-ketolactone. The unsaturated polyester resin composition according to any one of claims 1 to 6, wherein the bidentate ligand compound (D) is an α-acetyl lactone. The unsaturated polyester resin composition according to any one of claims 1 to 7, wherein the polysiloxane (E) has a weight average molecular weight of 3,000 to 20,000. The unsaturated polyester resin composition according to any one of claims 1 to 8, further comprising a radical polymerization initiator (F). The cured product of the unsaturated polyester resin composition according to any one of claims 1 to 9. A composite material containing the unsaturated polyester resin composition according to any one of claims 1 to 9 and at least one selected from a fiber reinforcing material, a filler and an aggregate. The cured product of the composite material according to claim 11.