JP2023018923A - Resin composition and fiber-reinforced plastic composite pipe - Google Patents

Abstract

[Problem] To provide a resin composition that can suppress the decrease in curability caused by the addition of an ultraviolet absorber. [Solution] A resin composition comprising an unsaturated polyester resin (A), one or more ultraviolet absorbers (B) selected from the group consisting of compounds having a triazine skeleton, compounds having a benzophenone skeleton, and compounds having a cyanoacrylate skeleton, and a curing accelerator (E), the curing accelerator (E) containing a metal soap (E1), and the content of the ultraviolet absorber (B) per 100 parts by mass of the unsaturated polyester resin (A) is 1 to 5 parts by mass. [Selected Figure] None

Description

TECHNICAL FIELD The present invention relates to a resin composition and a fiber-reinforced plastic composite pipe.

Fiber reinforced plastic (FRP), which is a cured composite material containing a curable resin and reinforcing fibers, is used in various fields such as agriculture, sewerage, construction, and transportation. Examples of moldings containing FRP (FRP moldings) include FRP composite pipes and the like.
Unsaturated polyester resins are among the resins used in fiber reinforced plastics (FRP). When FRP is used outdoors, the resin of FRP suffers from photodegradation and hydrolysis due to ultraviolet rays, resulting in thinning and cracking, which makes it difficult to maintain the strength of FRP.

As a means for improving the weather resistance (discoloration resistance due to sunlight) of FRP molded products, there is a method of applying a weather-resistant paint to the outermost surface of FRP molded products to form a coating film. When a coating film of a weather-resistant paint is formed on the outermost surface of an FRP molded product, there is a problem that if the coating film is peeled off by flying objects, deterioration of the FRP progresses from the peeled-off portion.
To address these problems, there is a method of blending weather resistant additives such as UV absorbers and light stabilizers into the FRP resin (Patent Document 1).

JP 2017-206630 A

According to the findings of the present inventors, the addition of an ultraviolet absorber may reduce the curability of the resin. For example, problems such as slowing of the reaction rate of the curing reaction and insufficient progress of curing may occur.
An object of the present invention is to provide a resin composition capable of suppressing deterioration in curability due to the addition of an ultraviolet absorber.

The inventors of the present invention have found that when the resin composition contains a metal soap as a reaction accelerator, the curability tends to be lowered by the addition of the ultraviolet absorber. Then, the present inventors have found that such a decrease in curability can be suppressed by using a specific ultraviolet absorber, and have completed the present invention.

The present invention has the following aspects.
<1>
An unsaturated polyester resin (A), one or more UV absorbers (B) selected from the group consisting of compounds having a triazine skeleton, compounds having a benzophenone skeleton, and compounds having a cyanoacrylate skeleton (B), and a curing accelerator ( E), wherein the curing accelerator (E) contains a metal soap (E1), and the content of the ultraviolet absorber (B) is 1 to 1 with respect to 100 parts by mass of the unsaturated polyester resin (A). The resin composition, which is 5 parts by mass.
<2>
The resin composition of <1>, further comprising a light stabilizer (D).
<3>
The resin composition of <2>, wherein the content of the light stabilizer (D) is 0.01 to 1 part by mass with respect to 100 parts by mass of the unsaturated polyester resin (A).
<4>
Cylindrical, having, in order from the inner surface, an inner protective layer, an inner fiber reinforced resin layer, a resin mortar layer, an outer fiber reinforced resin layer, and an outer protective layer,
The outer fiber-reinforced resin layer is made of one or more selected from the group consisting of reinforcing fibers, unsaturated polyester resin (A), a compound having a triazine skeleton, a compound having a benzophenone skeleton, and a compound having a cyanoacrylate skeleton. It contains an ultraviolet absorber (B) and a curing accelerator (E), the curing accelerator (E) contains a metal soap (E1), and the unsaturated polyester resin (A) is 100 parts by mass. A fiber-reinforced plastic composite pipe containing 1 to 5 parts by mass of the absorbent (B).
<5>
The outer surface protective layer contains the unsaturated polyester resin (A), the ultraviolet absorber (B), and the curing accelerator (E), and the curing accelerator (E) contains the metal soap (E1). The fiber-reinforced plastic composite pipe of <4>, wherein the content of the ultraviolet absorber (B) is 1 to 5 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (A).
<6>
The fiber-reinforced plastic composite pipe of <5>, the outer surface of which is coated with a weather-resistant paint.

According to the resin composition of the present invention, deterioration of curability due to addition of an ultraviolet absorber can be suppressed.

1 is a perspective view showing one embodiment of a fiber-reinforced plastic composite pipe of the present invention; FIG. 4 is a graph showing the results of heat curing tests in Examples and Comparative Examples.

The following term definitions apply throughout the specification and claims.
A numerical range represented by "-" includes the numerical values at both ends of the numerical range.
(Meth)acryl is a general term for acryl and methacryl. The same applies to (meth)acrylate, (meth)acryloyl, (meth)acryloyloxy and (meth)acrylamide.

(resin composition)
The resin composition of the present invention comprises an unsaturated polyester resin (A) (hereinafter also referred to as "(A) component"), an ultraviolet absorber (B) (hereinafter also referred to as "(B) component"), and a curing Accelerator (E) (hereinafter also referred to as "component (E)").
Furthermore, it is preferable that a light stabilizer (D) (hereinafter also referred to as "(D) component") is included.

<Unsaturated polyester resin (A)>
By containing the component (A), the resin composition is cured to form a molded article.
The (A) component contains an unsaturated polyester (a1) and a polymerizable unsaturated monomer (a2).

The unsaturated polyester (a1) preferably uses a saturated dibasic acid (a11), an unsaturated dibasic acid (a12), and a glycol (a13) as raw materials.

The saturated dibasic acid (a11) is a dibasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, or adipic acid that does not contain non-conjugated double bonds between carbon atoms in one molecule. As for the saturated dibasic acid (a11), one type may be used alone, or two or more types may be used in combination.
The unsaturated dibasic acid (a12) is a dibasic acid containing one or more non-conjugated double bonds between carbon atoms in one molecule such as maleic anhydride or fumaric acid. As for the unsaturated dibasic acid (a12), one type may be used alone, or two or more types may be used in combination.

Glycol (a13) is an alkylene glycol such as ethylene glycol or propylene glycol, a polyoxyalkylene glycol such as dialkylene glycol or trialkylene glycol, or a bisphenol such as bisphenol A or bisphenol F having two hydroxyl groups in one molecule. is a diol containing groups. Glycol (a13) may be used alone or in combination of two or more, as required.

The unsaturated polyester (a1) further has one or two non-conjugated double bonds between carbon atoms in one molecule, which are not included in either the unsaturated dibasic acid (a12) or the glycol (a13). A monomer (a14) can be used as a raw material. Examples of such monomer (a14) include, but are not limited to, styrene, propylene, dicyclopentadiene, and (meth)acrylic acid alkyl esters. As for the monomer (a14), one type may be used alone, or two or more types may be used in combination.

The method for synthesizing the unsaturated polyester (a1) is not particularly limited, and the saturated dibasic acid (a11), the unsaturated dibasic acid (a12) and the glycol (a13), and optionally the monomer (a14) are charged simultaneously. , a synthetic method of condensing, and the like.

Component (A) is an ortho-unsaturated polyester resin, an iso-unsaturated polyester resin, a tere-unsaturated ester resin, or a bis-unsaturated polyester, depending on the type of saturated dibasic acid (a11) or the type of glycol (a13). It may be classified as a resin.

The polymerizable unsaturated monomer (a2) is not particularly limited, and those conventionally used for unsaturated polyester resins can be used.
Examples of polymerizable unsaturated monomers (a2) include styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinyl acetate, diarylphthalate, triarylcia Nurate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (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-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether ( meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate , dipropylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monobutyl ether (meth) acrylate, dipropylene glycol monohexyl ether (meth) acrylate, dipropylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol di(meth) ) acrylate, dipropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth) ) acrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis[4-(methacryloxyethoxy)phenyl]propane, 2,2-bis[4-(methacryloxydiethoxy)phenyl]propane , 2, 2- Bis[4-(methacryloxypolyethoxy)phenyl]propane, tetraethylene glycol diacrylate, bisphenol A ethylene oxide addition (n=2) diacrylate, isocyanuric acid ethylene oxide addition (n=3) diacrylate and pentaerythritol diacrylate monostearate and the like.
The polymerizable unsaturated monomers (a2) may be used singly or in combination of two or more as necessary.

The number average molecular weight of component (A) is not particularly limited, but is preferably 400 to 1,500, more preferably 400 to 1,200, and even more preferably 400 to 1,000. When the number average molecular weight of the component (A) is within the above range, the fluidity of the resin composition is good, and moldability is further improved.
The number average molecular weight is a value measured by GPC (gel permeation chromatography) analysis.

The contents of the unsaturated polyester (a1) and the polymerizable unsaturated monomer (a2) in the component (A) are not particularly limited, but the unsaturated polyester (a1) and the polymerizable unsaturated monomer (a2) 100 parts by mass, the unsaturated polyester (a1) is preferably 80 to 60 parts by mass, and the balance is preferably the polymerizable unsaturated monomer (a2). That is, the preferred range of the mass ratio represented by (a1)/{(a1)+(a2)} is 0.6 to 0.8. Within this range, component (A) has better shrinkability, physical properties and moldability.

The component (A) may be mixed with the compound used in the synthesis of the unsaturated polyester (a1) and a compound other than the polymerizable unsaturated monomer (a2) to the extent that the effect of the present invention is not lost. good.

The content of component (A) relative to the total mass of the resin composition is preferably 90.0 to 99.9% by mass, more preferably 95.0 to 99.9% by mass. When it is at least the lower limit of the above range, the strength of a molded article (hereinafter also referred to as "resin molded article") that is a cured product of the resin composition is further enhanced. When it is at most the upper limit, the content of additive components other than the component (A) can be increased. For example, by increasing the content of the component (B), the weather resistance can be further improved.

From the viewpoint of high physical properties and corrosion resistance, it is preferable that the component (A) contains an isounsaturated polyester resin.
Examples of commercially available iso-unsaturated polyester resins include iso-unsaturated polyester resins (manufactured by Japan U-Pica Co., Ltd.).
The content of the isounsaturated polyester resin is preferably 60 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, relative to the total mass of component (A).

<Ultraviolet absorber (B)>
Component (B) includes a compound having a triazine skeleton (hereinafter also referred to as a "triazine compound"), a compound having a benzophenone skeleton (hereinafter also referred to as a "benzophenone compound"), and a compound having a cyanoacrylate skeleton (hereinafter referred to as It is one or more selected from the group consisting of (also referred to as "cyanoacrylate compound").
Triazine-based compounds, benzophenone-based compounds, and cyanoacrylate-based compounds may be compounds known as UV absorbers.
By adding the (B) component to the resin composition containing the (A) component and the (E) component, it is possible to prevent deterioration of the curability of the resin composition while imparting UV absorbing power.
Since none of the triazine-based compound, benzophenone-based compound, and cyanoacrylate-based compound reacts with the metal soap (E1) described below, it is thought that the addition of the ultraviolet absorber can prevent deterioration in curability.

Specific examples include the following.
[Triazine-based compound]
Triazine is a compound represented by the following formula (b1).

The “compound having a triazine skeleton” is a compound represented by the formula (b1) or a compound in which some or all of the hydrogen atoms of the compound of the formula (b1) are substituted with other substituents.
Examples of substituents include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a methoxyphenyl group, a hydroxymethoxyphenyl group, and the like.

Specific examples of triazine compounds include 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4 -ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4 -butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2 -hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4- Diphenyl-6-[2-hydroxy-4-(1-isooctyloxycarbonylethoxy)]-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)- Examples include 1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, and the like.
Commercially available products include LA-46 (manufactured by ADEKA) and EVERSORB40 (manufactured by Eiko Kagaku).

[Benzophenone compound]
Benzophenone is a compound represented by the following formula (b2).

A "compound having a benzophenone skeleton" is a compound represented by the formula (b2) or a compound in which some or all of the hydrogen atoms of the compound of the formula (b2) are substituted with other substituents.
Examples of substituents include a hydroxy group, an alkyl group, an alkoxy group, a sulfone group, and an alkylamino group.

Specific examples of benzophenone compounds include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2,4-dihydroxybenzophenone. , 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone etc. can be exemplified.
Commercially available products include 1413 (manufactured by ADEKA), EVERSORB11 (manufactured by Eiko Chemical Co., Ltd.), EVERSORB12 (manufactured by Eiko Chemical Co., Ltd.), Uvinal 3049 (manufactured by BASF), Uvinal 3050 (manufactured by BASF), JF-51 (Johoku Chemical Kogyo Co., Ltd.) and the like can be exemplified.

[Cyanoacrylate compound]
The α-cyanoacrylate is a compound in which one of the hydrogen atoms bonded to the α-position carbon of an acrylate ester is substituted with a CN group, preferably a compound represented by the formula (b3).
_CH2 =C(CN)COOR (b3)
In formula (b3), R represents a linear or branched alkyl group having 2 to 6 carbon atoms.

A “compound having a cyanoacrylate skeleton” is α-cyanoacrylate or a compound in which some or all of the hydrogen atoms of α-cyanoacrylate are substituted with other substituents.
Preferred are compounds represented by the formula (b3) or compounds in which some or all of the hydrogen atoms in the compound of the formula (b3) are substituted with other substituents.
A benzyl group can be exemplified as a substituent.

Specific examples of cyanoacrylate compounds include 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, ethyl 2-cyano-3,3-diphenylacrylate, 2-cyano-3,3-diphenylacrylate 2 -ethylhexyl, 2,2-bis{[(2-cyano-3,3-diphenylacryloyl)oxy]methyl}propane-1,3-diyl=bis(2-cyano-3,3-diphenylacrylate), etc. I can give an example.
Commercially available products include Uvinal 3035 (manufactured by BASF), Uvinal 3039 (manufactured by BASF), and Uvinal 3030 (manufactured by BASF).

The content of component (B) in the resin composition is 1 to 5 parts by mass, preferably 1 to 4 parts by mass, more preferably 1 to 3 parts by mass, per 100 parts by mass of component (A). When it is at least the lower limit of the above range, the weather resistance of the cured resin molding can be further improved. When it is equal to or less than the upper limit, the strength of the cured resin molding can be increased.

<Other UV absorbers (C)>
The resin composition may contain an ultraviolet absorber (C) other than the component (B) (hereinafter also referred to as "component (C)") within a range that does not impair the effects of the present invention.
As component (C), a known ultraviolet absorber that does not correspond to any of triazine-based compounds, benzophenone-based compounds, and cyanoacrylate-based compounds can be used.
Examples thereof include compounds having a benzotriazole skeleton (hereinafter also referred to as "benzotriazole compounds").
Specific examples include the following.

[Benzotriazole compound]
Benzotriazole is a compound represented by the following formula (c1) or a compound represented by the following formula (c2).

The "compound having a benzotriazole skeleton" means a compound represented by formula (c1) or (c2), or a compound of formula (c1) or a compound of formula (c2) in which some or all of the hydrogen atoms are It is a compound substituted with other substituents.
Substituents include hydroxyphenyl group, 3-t-butyl-2-hydroxy-5-methylphenyl group, 2-hydroxy-5-octylphenyl group, 2-hydroxy-5-methylphenyl group, 2-hydroxy-3 ,5-di(1,1dimethylbenzyl)phenyl group and the like.

Examples of benzotriazole compounds include 2-(3'-t-butyl-2'hydroxy-5'-methylphenyl)5-chlorobenzotriazole, 3-(2H-benzotriazol-2-yl)-4- Hydroxyphenethyl methacrylate (CAS: 153175-43-0), 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy -5′-t-octylphenyl)benzotriazole, 2-(5-chloro-2H-benzotriazol-2-lyl)-6-t-butyl-4-methylphenol and the like.
Commercially available products include EVERSORB73 (manufactured by Eiko Chemical Co., Ltd.), Vanaresin UVA-5080 (manufactured by Shin-Nakamura Chemical Co., Ltd.), JF-79 (manufactured by Johoku Chemical Co., Ltd.), JF-83 (manufactured by Johoku Chemical Co., Ltd.), and Adekastab LA. -36 (manufactured by ADEKA) and the like can be exemplified.

The content of component (C) in the resin composition is preferably less than 1 part by mass with respect to 100 parts by mass of component (A), more preferably 0.1 part by mass or less, and further preferably 0.01 part by mass or less. preferable. Zero is particularly preferred. When it is at most the above upper limit, the curability of the resin composition is less likely to decrease.
The total content of components (B) and (C) is preferably 1 to 5 parts by mass, preferably 1 to 4 parts by mass, more preferably 1 to 3 parts by mass, relative to 100 parts by mass of component (A). preferable.

<Light stabilizer (D)>
By adding the component (D) to the resin composition, the weather resistance of the resin molding can be further enhanced.
UV absorbers absorb UV rays to improve weather resistance, while light stabilizers react with radicals generated by UV irradiation to prevent degradation reactions caused by radicals and improve weather resistance. .
As the component (D), a hindered amine light stabilizer (D1) (hereinafter also referred to as "(D1) component") is preferable. The component (D1) may be used alone or in combination of two or more.
Component (D) may contain one or more light stabilizers other than component (D1). As other light stabilizers, known light stabilizers can be used.

[(D1) Component]
The (D1) component is a compound having a hindered amine structure.
A compound having a hindered amine structure is a compound represented by the following formula (d1) or a compound in which some or all of the hydrogen atoms in the following formula (d1) are substituted with other substituents.

Examples of the component (D1) include a compound having one hindered amine structure, a compound having two hindered amine structures, a compound having three hindered amine structures, a compound having four hindered amine structures, and a polymer having a hindered amine structure.
Examples of (D1) component include compounds having a 2,2,6,6-tetramethylpiperidine skeleton.
Types of the component (D1) include NH type, NR type and N-OR type. In the present invention, the component (D1) may be of any type, but the N-OR type is preferred from the viewpoint of compatibility and acid-basicity.
Specific examples of the component (D1) include bis(2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis( 2,2,6,6-tetramethyl-4-piperidyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4 -piperidyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)carbonate, bis(1,2, 2,6,6-pentamethyl-4-piperidyl)oxalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)malonate, bis(1,2,2,6,6-pentamethyl-4- piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N,N'-bis (2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide, 1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidyl)tolylene-2,4 -dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate and the like.

When the resin composition contains component (D), the content of component (D) with respect to 100 parts by mass of component (A) is preferably 0.01 to 1 part by mass, and 0.05 to 0.3 parts by mass. more preferred. When it is at least the lower limit of the above range, the effect of improving weather resistance is excellent. If it is at most the upper limit, poor curing is unlikely to occur during the molding reaction, and the effect of improving weather resistance is likely to be obtained.
The content of component (D1) relative to component (D) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass. 100% by weight is particularly preferred.

<(E) Component>
The (E) component contains a metal soap (E1). The metal soap (E1) may be used alone or in combination of two or more.
The component (E) may contain one or more curing accelerators other than the metal soap (E1).

Examples of the metal soap (E1) include vanadyl octenoate, copper naphthenate, barium naphthenate, cobalt naphthenate and cobalt octoate.

Other curing accelerators include Li ₃ [Co(NO ₂ ) ₆ ], Li ₃ [Co(NO ₂ ) ₅ Cl], Li ₃ [Co(NO ₂ ) ₅ Br], Li ₃ [Co(NO ₂ ) ₄ Cl ₂ ], Li ₃ [Co(NO ₂ ) ₄ Br ₂ ], Na ₃ [Co(NO ₂ ) ₆ ], Na ₃ [Co(NO ₂ ) ₅ Cl], Na ₃ [Co(NO ₂ ) _5Br ], _Na3 [ _Co ( _NO2 ) _4Cl2 ], _Na3 [Co( _NO2 ) _{4Br2 ]} , K3 _[ Co( _NO2 ) ₆ ], K3 _[ Co( _NO2 ) ₅ Cl], K ₃ [Co(NO ₂ ) ₅ Br], K ₃ [Co(NO ₂ ) ₄ Cl ₂ ] and K ₃ [Co(NO ₂ ) ₄ Br ₂ ], vanadyl acetyl acetate, cobalt metal chelate compounds such as acetylacetate and iron acetylacetonate, and N,N-dimethylamino-p-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, methylhydroxyethylaniline, N,N-dimethyl- p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, 4-N,N-dimethylaminobenzaldehyde, 4-N,N-bis(2-hydroxyethyl)aminobenzaldehyde, 4-methylhydroxy Amines such as ethylaminobenzaldehyde, N,N-bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine and diethanolaniline can be exemplified.

The content of component (E) per 100 parts by mass of component (A) is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass. If it is at least the lower limit of the above range, the curing time can be sufficiently shortened, and it is easy to suppress the influence of poor curing due to the influence of environmental changes. If it is equal to or less than the upper limit, it is easy to suppress effective shrinkage (cracking) due to a rapid heat generation temperature rise.

<Curing agent (G)>
The resin composition preferably contains a curing agent (G). The coexistence of the curing accelerator (E) and the curing agent (G) accelerates the curing reaction.
The curing agent (G) is not particularly limited, but an organic peroxide catalyst is preferred. Organic peroxide catalysts include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, 1,1-bis(t-butylperoxy)-3 , 3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, millihydroperoxide, acetylperoxide, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, isobutylperoxide, 3,3,5-trimethylhexanoyl peroxide and lauryl peroxide, etc. Examples include organic peroxides and azo polymerization initiators such as azobisisobutyronitrile and azobiscarbonamide.
The curing agent (G) may be used alone or in combination of two or more.
The content when the resin composition contains the curing agent (G) is not particularly limited, but is preferably 0.1 to 4 parts by mass, and 0.3 to 3 parts by mass, relative to 100 parts by mass of component (A). part is more preferred.

<Other ingredients>
The resin composition of the present invention may contain components other than the above components (A) to (E) and curing agent (G). Other components include antioxidants, polymerization inhibitors, fillers, pigments, viscosity reducing agents, antioxidants, plasticizers, flame retardants, stabilizers, reinforcing agents, and the like.

Antioxidants include phenolic antioxidants, phosphoric acid antioxidants, aromatic amine antioxidants (primary antioxidants), sulfur antioxidants (secondary antioxidants), thioether antioxidants. An inhibitor and the like can be exemplified.

Examples of polymerization inhibitors include, but are not limited to, hydroquinone, toluhydroquinone, trimethylhydroquinone, tertiarybutylhydroquinone, ditertiarybutylhydroquinone, tertiarybutylcatechol, methoxyhydroquinone, benzoquinone, tertiarybutylquinone and phenothiazine.
The polymerization inhibitor may be used singly or in combination of two or more.
Containing a polymerization inhibitor suppresses the reaction between the unsaturated polyester (a1) and the polymerizable unsaturated monomer (a2), thereby increasing safety.
When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 0.1 parts by mass per 100 parts by mass of component (A).

<Method for producing resin composition>
The method for producing the resin composition of the present invention is not particularly limited. For example, a method of adding the curing agent (G) to a preliminary mixture containing all components other than the curing agent (G) and mixing them to produce a resin composition is preferred.
When using two or more kinds of ultraviolet absorbers, a mixture obtained by mixing them in advance may be used.
When an ultraviolet absorber and a light stabilizer are used in combination, a mixture obtained by mixing them in advance may be used.

(resin molding)
The resin molded body is obtained by curing the resin composition of the present invention and shaping it into an arbitrary shape.
Examples of resin moldings include resin parts of FRP, resin parts of fiber-reinforced plastic composite pipes, manholes, drainage basins, building material blocks, pavement blocks, lids, pipe materials, moldings for civil engineering and construction such as repair materials, and artificial marble. moldings, landscape moldings, chairs, benches, C.I. C. There are boxes (for information communication power underground burial), information-related molded products, power-related molded products, etc.

<Method for manufacturing resin molding>
A resin molding having a specific shape can be produced by molding the resin composition and curing it by heating.
The method for producing the resin molding is not particularly limited, but examples thereof include cast molding, centrifugal molding, compression molding and continuous molding.

In the cast molding method, a resin composition is poured into a mold and cured by heating.
In the centrifugal molding method, a resin composition is poured into a cylindrical mold, the mold is rotated, and the resin composition is formed into a uniform thickness by the centrifugal force, and cured by heating.
In the compression molding method, the resin composition is poured into a mating mold, compressed with a press, and cured by heating.
In the cast molding method, the centrifugal molding method and the compression molding method, reinforcing fibers may be placed in a mold, the reinforcing fibers may be impregnated with a resin composition, and cured to form an FRP. Examples of reinforcing fibers include glass fibers, carbon fibers, and boron fibers. The thickness (diameter) of the reinforcing fibers is, for example, 5 to 30 μm. The reinforcing fibers may be in the form of a bundle or sheet aligned in one direction, or may be in the form of plain weave or twill weave.

In the continuous molding method, while winding the resin composition around a rotating mandrel, the resin composition is sent forward at a constant speed and passed through a curing furnace, where it is heated and cured. Before and after the resin composition is wound, the reinforcing fiber may be wound, and the resin composition impregnated in the wound fiber may be cured to form an FRP.

The curing temperature of the resin composition is not particularly limited, but is preferably 50°C or higher, more preferably 50 to 70°C, and even more preferably 55 to 65°C.
The curing time of the resin composition is not particularly limited, but is preferably 6 hours or longer, more preferably 12 hours or longer, and still more preferably 24 to 48 hours.

(Fiber-reinforced plastic composite pipe)
An embodiment of the fiber-reinforced plastic composite pipe (FRPM pipe) of the present invention will be described with reference to FIG.
The FRPM pipe 1 of FIG. 1 has a cylindrical shape extending in the pipe axis O direction, and includes an annular or cylindrical resin mortar layer 4, an inner fiber reinforced resin layer 3 located on the inner peripheral surface of the resin mortar layer 4, a resin An outer fiber reinforced resin layer 5 positioned on the outer peripheral surface of the mortar layer 4, an inner protective layer 2 positioned on the inner peripheral surface of the inner fiber reinforced resin layer 3, and an outer surface protection positioned on the outer peripheral surface of the outer fiber reinforced resin layer 5. layer 6;
That is, the FRPM pipe 1 has an inner protective layer 2, an inner fiber reinforced resin layer 3, a resin mortar layer 4, an outer fiber reinforced resin layer 5, and an outer protective layer 6 in order from the inner circumference. Either one of the inner fiber-reinforced resin layer 3 and the outer fiber-reinforced resin layer 5 may be provided, but it is preferable to have both. Neither the inner surface protective layer 2 nor the outer surface protective layer 6 may be provided, but it is preferable to have one or both of them.
Note that the FRPM pipe is not limited to a cylindrical shape, and may be a square tube shape such as a square tube shape.

In this embodiment, the inner fiber reinforced resin layer 3 consists of a first inner fiber reinforced resin layer 3a in which fibers extend in the circumferential direction and a second inner fiber reinforced resin layer 3b in which fibers extend in the axial direction. have However, the present invention is not limited to this, and the inner fiber reinforced resin layer 3 may be composed of one layer. In this case, the reinforcing fibers forming the inner fiber-reinforced resin layer 3 may be woven fabric.

In this embodiment, the outer fiber reinforced resin layer 5 includes a first outer fiber reinforced resin layer 5a in which fibers extend in the circumferential direction and a second outer fiber reinforced resin layer 5b in which fibers extend in the axial direction. have However, the present invention is not limited to this, and the outer fiber reinforced resin layer 5 may be composed of one layer. In this case, the reinforcing fibers forming the outer fiber-reinforced resin layer 5 may be woven fabric.

The resin composition that forms the inner surface protective layer 2 may be a conventionally known resin composition containing a thermosetting resin (such as a composition containing an iso-unsaturated polyester resin and a curing agent), or the resin of the present invention. It may be a composition.

As the inner fiber-reinforced resin layer 3, a combination of reinforcing fibers and a cured product of a resin composition can be exemplified. This resin composition is the same as the resin composition forming the inner surface protective layer 2 .

The resin mortar layer 4 is a hardened resin concrete composition. A resin concrete composition can be exemplified by, for example, a mixture of resin mortar and aggregate.
Examples of resin mortar include thermosetting resins such as unsaturated polyester resins.
Examples of the aggregate include silica sand, gravel, crushed stone, cobblestone, blast-furnace slag aggregate, artificial lightweight aggregate, and the like, which have conventionally been incorporated in resin concrete compositions. The average particle size of aggregate is, for example, 0.1 to 10 mm.
The amount of aggregate in the resin concrete is, for example, 60 to 90 parts by mass with respect to 100 parts by mass of resin mortar.
The resin concrete composition may contain additives such as a polymerization inhibitor, a curing agent, and a curing accelerator.

As the outer fiber-reinforced resin layer 5, a combination of reinforcing fibers and a resin composition can be exemplified. This resin composition is the same as the resin composition forming the inner surface protective layer 2 . Among them, the resin composition of the present invention is preferable as the resin composition forming the outer surface fiber reinforced resin layer 5 . By using the resin composition of the present invention, the weather resistance of the outer fiber-reinforced resin layer 5 can be improved, and the weather resistance of the FRPM pipe can be improved.

The resin composition forming the outer protective layer 6 is the same as the resin composition forming the inner protective layer 2 . Among them, the resin composition of the present invention is preferable as the resin composition forming the outer surface protective layer 6 . By forming the outer surface protective layer 6 with the resin composition of the present invention, the weather resistance of the resin molding can be improved, and the weather resistance of the FRPM pipe can be improved.

The inner diameter R of the FRPM pipe 1 can be appropriately determined according to the application of the FRPM pipe 1 .
The length of the FRPM pipe 1 in the direction of the pipe axis O1 can be determined as appropriate according to the application of the FRPM pipe 1 .
The thickness of each layer constituting the FRPM pipe 1 can be appropriately determined in relation to the inner diameter R, the length in the direction of the pipe axis O1, the strength required for the FRPM pipe 1, and the like.

<Method for manufacturing FRPM pipe>
The manufacturing method of the FRPM tube 1 is not particularly limited, and conventionally known manufacturing methods such as a filament winding method, a centrifugal molding method, a pultrusion method and a hand layup method can be used.
In the filament winding method, the core tube is rotated and sent at a constant speed, and the materials of the inner protective layer 2, the inner fiber reinforced resin layer 3, the resin mortar layer 4, the outer fiber reinforced resin layer 5, and the outer protective layer 6 are sequentially wound, This is a manufacturing method in which FRPM pipes are continuously manufactured by successive heat curing. According to these methods, FRPM pipes of various sizes can be manufactured by changing the size of the core tube.

In addition, as the method for manufacturing the FRPM pipe 1, the method for manufacturing the FRPM pipe described in [0016] to [0019] of JP-A-2001-205711, [0020] to [0028] in JP-A-2001-205712. ] or the FRPM pipe manufacturing method described in [0009] to [0019] of JP-A-10-193467.
That is, a resin composition that forms an inner surface protective layer 2 on the surface of the wound steel belt while spirally winding an endless steel belt around the peripheral surface of a cylindrical mold that rotates about the tube axis; The reinforcing fiber, the resin composition for FRP, the resin concrete composition, the reinforcing fiber, the resin composition for FRP, and the resin composition forming the outer surface protective layer 6 are supplied in this order, and each resin composition The material is cured to continuously form the FRPM tube 1 . The steel belt is advanced by the rotation of the cylindrical die, from the end of the cylindrical die, through the interior of the die and back to the beginning of the die.
Therefore, the FRPM pipe 1 extends in the axial direction of the cylindrical mold. A product of the FRPM tube 1 is obtained by cutting the elongated FRPM tube 1 to an arbitrary length.
According to this manufacturing method, the inner diameter R of the FRPM pipe 1 can be adjusted by changing the outer diameter of the mold.

The FRPM tube of the present invention is not limited to the embodiments described above. The outer surface of the FRPM pipe of the present invention may be coated with a weather resistant paint in order to further improve weather resistance. That is, the FRPM pipe of the present invention may have a coating layer of weather resistant paint on the outermost surface.
In general, the outermost layer is coated to prevent deterioration of the constituent base materials of structures, pipes, transportation equipment, and the like used outdoors. By coating the component with a coating film, it is possible to suppress the effects of deterioration factors such as ultraviolet rays, moisture, temperature, and adhesion of foreign matter on the component. Examples of weather-resistant paints include fluorine-based paints, silicone-based paints, and acrylic-based paints. Weather resistant paints include top coats that are coated on the surface of FRP products for outdoor use. From the viewpoint of increasing the adhesion to the FRPM pipe, fluorine-based paints and acrylic-based paints are more suitable as the weather-resistant paint.
Examples of the coating method include spray coating, brush coating, roller coating, and the like. Among them, as the coating method, spray coating is preferable in consideration of the stability of the film thickness and the finish.
By having a coating layer of a weather-resistant paint on the outer surface, the penetration of ultraviolet rays and moisture into the resin composition constituting the FRPM pipe can be further reduced, and the weather resistance can be further improved.
The coating amount of the weather-resistant paint is, for example, preferably 80-300 g/cm ² , more preferably 200-260 g/cm ² .

According to the resin composition of the present invention, as shown in the examples below, a specific ultraviolet absorber (B) is added as an ultraviolet absorber to the resin composition containing the components (A) and (E1). By doing so, it is possible to impart ultraviolet absorption ability while suppressing deterioration in curability due to the addition of the ultraviolet absorber. The weather resistance of the resin molded article can be enhanced by imparting ultraviolet absorption ability.
The resin composition of the present invention is particularly suitable as a resin composition for FRP.

Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited to the examples described later, and various modifications are possible as long as the gist of the present invention is not changed. be.

(Raw materials used)
<Unsaturated polyester resin (A)>
(A-1): Iso-unsaturated polyester resin (manufactured by Japan U-Pica Co., Ltd.).
<Ultraviolet absorber (B)>
(B-1): An ultraviolet absorber having a triazine skeleton, ADEKA product name “LA-46”.
<Other UV absorbers (C)>
(C-1): UV absorber having a benzotriazole skeleton, product name of Eikoh Kagaku Co., Ltd. "EVERSORB73".
<Light stabilizer (D)>
(D1-1): a hindered amine light stabilizer having an N-OR functional group, Eikoh Kagaku Co., Ltd. product name "EVERSORB95".
<Curing accelerator (E)>
(E1-1): cobalt naphthenate <curing agent (G)>
(G-1): Organic peroxide catalyst, product name of NOF Corporation "Permec N"

In each of the following examples, a resin composition was produced with the formulation shown in Table 1.
<Example 1>
The (B) component, the (A) component and the (E) component were kneaded in a mixer, and the curing agent (G) was added to the resulting kneaded product and mixed to obtain a resin composition.
<Example 2>
The (B) component and the (D) component were mixed in advance. The resulting mixture, components (A), and components (E) were kneaded in a mixer, and a curing agent (G) was added to the resulting kneaded product and mixed to obtain a resin composition.
<Comparative Example 1>
The components (B), (C) and (D) were mixed in advance. The resulting mixture, components (A), and components (E) were kneaded in a mixer, and a curing agent (G) was added to the resulting kneaded product and mixed to obtain a resin composition.
<Comparative Example 2>
The components (A) and (E) were kneaded in a mixer, and the curing agent (G) was added to the resulting kneaded product and mixed to obtain a resin composition.

The resin composition obtained in each example was subjected to a heat curing test by the following method to evaluate curability. The results are shown in FIG. The horizontal axis in FIG. 2 indicates the elapsed time (minutes) from the start of heating, and the vertical axis indicates the temperature (° C.) of the resin composition. Table 2 shows the maximum temperature reaching time (min), maximum temperature (°C), and reaction rate (°C/min) based on the results in FIG.

<Heat curing test>
A resin composition that cures by an exothermic reaction is placed in a test tube and heated in an oil bath. , the temperature change was measured in the process of cooling down to the same temperature as the oil bath by radiating heat.
Specifically, 25 g of the resin composition at 30°C was put into a test tube. The depth from the bottom of the test tube to the upper surface of the resin composition was 70 mm. A K-type thermocouple was set in the test tube at a position 10 mm above the bottom of the test tube. This test tube was heated in an oil bath at 60° C., and the change in temperature of the resin composition in the test tube over time was measured.
The time from the start of heating in the oil bath until reaching the maximum temperature (maximum temperature reaching time), the maximum temperature, and the temperature at the start of heating were recorded, and the reaction rate was determined by the following formula (I). A high maximum temperature is an index of sufficient progress of the curing reaction.
Reaction rate (unit: °C/min) = (maximum temperature (°C) - temperature at the start of heating (°C))/time to reach maximum temperature (min) (I)

Comparative Example 2 is a blank test consisting only of component (A), component (E1) and curing agent (G).
As shown in the results of FIG. 2 and Table 2, Examples 1 and 2 exhibited curability (maximum temperature, reaction rate) equivalent to that of Comparative Example 2, despite the addition of component (B). .

1 fiber-reinforced plastic composite pipe 2 inner protective layer 3 inner fiber-reinforced resin layer 3a first inner fiber-reinforced resin layer 3b second inner fiber-reinforced resin layer 4 resin mortar layer 5 outer fiber-reinforced resin layer 5a first outer fiber Reinforced resin layer 5b Second outer fiber reinforced resin layer 6 Outer protective layer

Claims (6)

an unsaturated polyester resin (A);
one or more UV absorbers (B) selected from the group consisting of compounds having a triazine skeleton, compounds having a benzophenone skeleton, and compounds having a cyanoacrylate skeleton;
and a curing accelerator (E),
The curing accelerator (E) contains a metal soap (E1),
A resin composition in which the content of the ultraviolet absorber (B) is 1 to 5 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (A). Furthermore, the resin composition of Claim 1 containing a light stabilizer (D). 3. The resin composition according to claim 2, wherein the content of said light stabilizer (D) is 0.01 to 1 part by mass with respect to 100 parts by mass of said unsaturated polyester resin (A). Cylindrical, having, in order from the inner surface, an inner protective layer, an inner fiber reinforced resin layer, a resin mortar layer, an outer fiber reinforced resin layer, and an outer protective layer,
The outer fiber-reinforced resin layer is made of one or more selected from the group consisting of reinforcing fibers, unsaturated polyester resin (A), a compound having a triazine skeleton, a compound having a benzophenone skeleton, and a compound having a cyanoacrylate skeleton. It contains an ultraviolet absorber (B) and a curing accelerator (E), the curing accelerator (E) contains a metal soap (E1), and the unsaturated polyester resin (A) is 100 parts by mass. A fiber-reinforced plastic composite pipe containing 1 to 5 parts by mass of the absorbent (B). The outer surface protective layer contains the unsaturated polyester resin (A), the ultraviolet absorber (B), and the curing accelerator (E), and the curing accelerator (E) contains the metal soap (E1). 5. The fiber-reinforced plastic composite pipe according to claim 4, wherein the content of said ultraviolet absorber (B) is 1 to 5 parts by mass with respect to 100 parts by mass of said unsaturated polyester resin (A). 6. The fiber-reinforced plastic composite pipe according to claim 5, wherein the outer surface is coated with a weather resistant paint.

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