Fiber Reinforced Plastic Composite Pipe

Abstract

To provide a resin composition capable of suppressing a decrease in curability due to addition of an ultraviolet absorber.SOLUTION: The resin composition contains: an unsaturated polyester resin (A); one or more ultraviolet absorbers (B) selected from the group consisting of a compound having a triazine skeleton, a compound having a benzophenone skeleton, and a compound having a cyanoacrylate skeleton; and a curing accelerator (E). The curing accelerator (E) contains a metal soap (E1). The content of the ultraviolet absorbers (B) is 1-5 pts.mass based on 100 pts.mass of the unsaturated polyester resin (A).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition and a fiber-reinforced plastic composite pipe. [Background technology]

[0002] Fiber-reinforced plastics (FRP), made by curing composite materials containing curable resin and reinforcing fibers, are used in a variety of fields, including agriculture, sewage systems, construction, and transportation. Examples of molded products containing FRP (FRP molded products) include FRP composite pipes. Unsaturated polyester resin is used in fiber reinforced plastics (FRP). When FRP is used outdoors, the resin in FRP is subject to photodegradation and hydrolysis due to ultraviolet rays, which can cause thinning and cracks, making it difficult to maintain the strength of the FRP.

[0003] One method for improving the weather resistance (resistance to discoloration due to sunlight) of FRP molded products is to apply a weather-resistant paint to the outermost surface of the FRP molded product to form a coating. When a weather-resistant paint coating is formed on the outermost surface of an FRP molded product, if the coating is peeled off by a flying object, the problem is that deterioration of the FRP will progress from the peeled off point. To address these problems, there is a method of blending weather resistance additives such as ultraviolet absorbers and light stabilizers into the resin of FRP (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-206630 A Summary of the Invention [Problem to be solved by the invention]

[0005] According to the findings of the present inventors, the addition of an ultraviolet absorber may reduce the curability of the resin, for example, the reaction rate of the curing reaction may slow down, curing may not proceed sufficiently, and other problems may occur. An object of the present invention is to provide a resin composition capable of suppressing a decrease in curability caused by the addition of an ultraviolet absorber. [Means for solving the problem]

[0006] The present inventors have found that when a resin composition contains a metal soap as a reaction accelerator, the addition of an ultraviolet absorber tends to cause a decrease in curability, and have discovered that the use of a specific ultraviolet absorber can suppress such a decrease in curability, thereby arriving at the present invention.

[0007] The present invention has the following aspects. <1> 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 a content of the ultraviolet absorber (B) being 1 to 5 parts by mass per 100 parts by mass of the unsaturated polyester resin (A). <2> Further, the composition contains a light stabilizer (D). <1> A resin composition. <3> The content of the light stabilizer (D) is 0.01 to 1 part by mass relative to 100 parts by mass of the unsaturated polyester resin (A). <2> A resin composition. <4> It is cylindrical and has, 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 fiber-reinforced plastic composite pipe has an outer fiber-reinforced resin layer comprising reinforcing fibers, 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 a content of the ultraviolet absorber (B) being 1 to 5 parts by mass per 100 parts by mass of the unsaturated polyester resin (A). <5> the outer surface protective layer contains the unsaturated polyester resin (A), the ultraviolet absorber (B), and the curing accelerator (E), the curing accelerator (E) contains the metal soap (E1), and the content of the ultraviolet absorber (B) is 1 to 5 parts by mass per 100 parts by mass of the unsaturated polyester resin (A); <4> Fiber reinforced plastic composite pipe. <6> The exterior is coated with weather-resistant paint. <5> Fiber reinforced plastic composite pipe. Effect of the Invention

[0008] According to the resin composition of the present invention, it is possible to suppress the decrease in curability caused by the addition of an ultraviolet absorber. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a perspective view showing one embodiment of a fiber-reinforced plastic composite pipe of the present invention. [Diagram 2] 1 is a graph showing the results of a heat curing test in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The following definitions of terms apply throughout the specification and claims. Numerical ranges expressed using "~" include both ends of the range. (Meth)acrylic is a general term for acrylic and methacrylic. The same applies to (meth)acrylate, (meth)acryloyl, (meth)acryloyloxy, and (meth)acrylamide.

[0011] (Resin composition) The resin composition of the present invention contains an unsaturated polyester resin (A) (hereinafter also referred to as "component (A)"), an ultraviolet absorber (B) (hereinafter also referred to as "component (B)"), and a curing accelerator (E) (hereinafter also referred to as "component (E)"). It is preferable that the composition further contains a light stabilizer (D) (hereinafter, also referred to as "component (D)").

[0012] <Unsaturated polyester resin (A)> By containing the component (A), the resin composition cures to form a molded article. The component (A) contains an unsaturated polyester (a1) and a polymerizable unsaturated monomer (a2).

[0013] The unsaturated polyester (a1) is preferably prepared by using a saturated dibasic acid (a11), an unsaturated dibasic acid (a12), and a glycol (a13) as raw materials.

[0014] The saturated dibasic acid (a11) is a dibasic acid that does not contain a non-conjugated double bond between carbon atoms in one molecule, such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, etc. The saturated dibasic acid (a11) may be used alone or in combination of two or more kinds, as necessary. The unsaturated dibasic acid (a12) is a dibasic acid containing one or more carbon-carbon non-conjugated double bonds in one molecule, such as maleic anhydride or fumaric acid. The unsaturated dibasic acid (a12) may be used alone or in combination of two or more kinds, as necessary.

[0015] The glycol (a13) is a diol containing two hydroxy groups in one molecule, such as an alkylene glycol, e.g., ethylene glycol or propylene glycol, a polyoxyalkylene glycol, e.g., dialkylene glycol or trialkylene glycol, or a bisphenol, e.g., bisphenol A or bisphenol F. The glycol (a13) may be used alone or in combination of two or more kinds, as necessary.

[0016] The unsaturated polyester (a1) can further use, as a raw material, a monomer (a14) having one or two carbon atom non-conjugated double bonds in one molecule, which is not included in either the unsaturated dibasic acid (a12) or the glycol (a13). Examples of such a monomer (a14) include, but are not limited to, styrene, propylene, dicyclopentadiene, and (meth)acrylic acid alkyl esters. The monomer (a14) may be used alone or in combination of two or more kinds, as necessary.

[0017] The method for synthesizing the unsaturated polyester (a1) is not particularly limited, and may be, for example, a method in which a saturated dibasic acid (a11), an unsaturated dibasic acid (a12), a glycol (a13), and, if desired, a monomer (a14) are simultaneously charged and condensed.

[0018] The component (A) may be classified into ortho-unsaturated polyester resins, iso-unsaturated polyester resins, tere-unsaturated ester resins, or bis-unsaturated polyester resins, depending on the type of saturated dibasic acid (a11) or the type of glycol (a13).

[0019] The polymerizable unsaturated monomer (a2) is not particularly limited, and any monomer that has been conventionally used in unsaturated polyester resins can be used. Examples of the polymerizable unsaturated monomer (a2) include styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinyl acetate, diaryl phthalate, triaryl cyanurate, 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, and sucrose. Tearyl, 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 Sil ether (meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polytetramethylene glycol dimethacrylate, 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 adduct (n=2) diacrylate, isocyanuric acid ethylene oxide adduct (n=3) diacrylate, and pentaerythritol diacrylate monostearate, etc. The polymerizable unsaturated monomer (a2) may be used alone or in combination of two or more kinds, as required.

[0020] The number average molecular weight of component (A) is not particularly limited, but is preferably 400 to 1500, more preferably 400 to 1200, and even more preferably 400 to 1000. When the number average molecular weight of component (A) is within the above range, the resin composition has good fluidity and better moldability. The number average molecular weight is a value measured by GPC (gel permeation chromatography) analysis.

[0021] In the (A) component, the content of the unsaturated polyester (a1) and the polymerizable unsaturated monomer (a2) is not particularly limited, but it is preferable that the unsaturated polyester (a1) is 80 to 60 parts by mass, and the polymerizable unsaturated monomer (a2) is the remainder, with the total amount of the unsaturated polyester (a1) and the polymerizable unsaturated monomer (a2) being 100 parts by mass. That is, the preferred range of the mass ratio represented by (a1) / {(a1)+(a2)} is 0.6 to 0.8. Within this range, the shrinkability, physical properties, and moldability of the (A) component are improved.

[0022] The component (A) may contain compounds other than the compound used in the synthesis of the unsaturated polyester (a1) and the polymerizable unsaturated monomer (a2) as long as the effects of the present invention are not lost.

[0023] The content ratio of the (A) component to the total mass of the resin composition is preferably 90.0 to 99.9 mass%, more preferably 95.0 to 99.9 mass%. When it is equal to or more than the lower limit of the above range, the strength of the molded product (hereinafter also referred to as "resin molded product") which is a cured product of the resin composition can be further increased. When it is equal to or less than the upper limit, the content of additive components other than the (A) component can be increased. For example, the content of the (B) component can be increased to further improve weather resistance.

[0024] From the standpoint of high physical properties and corrosion resistance, it is preferable that the component (A) contains an isounsaturated polyester resin. An example of a commercially available iso-unsaturated polyester resin is iso-unsaturated polyester resin (manufactured by Nippon U-Pica Corporation). The content of the isounsaturated polyester resin relative to the total mass of the component (A) is preferably from 60 to 100 mass %, more preferably from 90 to 100 mass %, and even more preferably from 95 to 100 mass %.

[0025] <Ultraviolet absorber (B)> The (B) component is at least one selected from the group consisting of compounds having a triazine skeleton (hereinafter also referred to as "triazine-based compounds"), compounds having a benzophenone skeleton (hereinafter also referred to as "benzophenone-based compounds"), and compounds having a cyanoacrylate skeleton (hereinafter also referred to as "cyanoacrylate-based compounds"). As the triazine-based compound, the benzophenone-based compound, and the cyanoacrylate-based compound, compounds known as ultraviolet absorbents can be used. By adding the component (B) to a resin composition containing the components (A) and (E), it is possible to impart ultraviolet absorbing ability to the resin composition while preventing a decrease in the curability of the resin composition. It is believed that the triazine-based compounds, benzophenone-based compounds and cyanoacrylate-based compounds do not react with the metal soap (E1) described below, and therefore the decrease in curability caused by the addition of an ultraviolet absorber can be prevented.

[0026] Specific examples include the following: [Triazine compounds] Triazine is a compound represented by the following formula (b1).

[0027] [ka]

[0028] The "compound having a triazine skeleton" refers to a compound represented by formula (b1) or a compound in which some or all of the hydrogen atoms of the compound represented by formula (b1) have been substituted with other substituents. Examples of the substituent include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a methoxyphenyl group, and a hydroxymethoxyphenyl group.

[0029] 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, and 2,4-diphenyl Examples include 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)-1,3,5-triazine, and 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine. Examples of commercially available products include LA-46 (manufactured by ADEKA Corporation) and EVERSORB40 (manufactured by Eiko Kagaku Co., Ltd.).

[0030] [Benzophenone compounds] Benzophenone is a compound represented by the following formula (b2).

[0031] [ka]

[0032] The "compound having a benzophenone skeleton" refers to a compound represented by formula (b2) or a compound in which some or all of the hydrogen atoms of the compound represented by formula (b2) have been substituted with other substituents. Examples of the substituent include a hydroxy group, an alkyl group, an alkoxy group, a sulfone group, and an alkylamino group.

[0033] Specific examples of benzophenone compounds include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone. Examples of commercially available products include 1413 (manufactured by ADEKA), EVERSORB 11 (manufactured by Eikoh Chemical Industry Co., Ltd.), EVERSORB 12 (manufactured by Eikoh Chemical Industry Co., Ltd.), Uvinal 3049 (manufactured by BASF), Uvinal 3050 (manufactured by BASF), and JF-51 (manufactured by Johoku Chemical Industry Co., Ltd.).

[0034] [Cyanoacrylate compounds] An α-cyanoacrylate is a compound in which one of the hydrogen atoms bonded to the carbon at the α-position of an acrylic ester is substituted with a CN group, and is preferably a compound represented by formula (b3). CH2 = C(CN)COOR (b3) In formula (b3), R represents a linear or branched alkyl group having 2 to 6 carbon atoms.

[0035] The term "compound having a cyanoacrylate skeleton" refers to an α-cyanoacrylate or a compound in which some or all of the hydrogen atoms of an α-cyanoacrylate have been substituted with other substituents. Preferably, it is a compound represented by formula (b3) or a compound in which some or all of the hydrogen atoms of the compound represented by formula (b3) have been substituted with other substituents. An example of the substituent is a benzyl group.

[0036] Specific examples of cyanoacrylate compounds include 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2,2-bis{[(2-cyano-3,3-diphenylacryloyl)oxy]methyl}propane-1,3-diyl=bis(2-cyano-3,3-diphenylacrylate), and the like. Examples of commercially available products include Uvinal 3035 (manufactured by BASF), Uvinal 3039 (manufactured by BASF), and Uvinal 3030 (manufactured by BASF).

[0037] The content of the (B) component in the resin composition is 1 to 5 parts by mass, preferably 1 to 4 parts by mass, and more preferably 1 to 3 parts by mass, per 100 parts by mass of the (A) component. When the content is equal to or more than the lower limit of the above range, the weather resistance of the cured resin molding can be further improved. When the content is equal to or less than the upper limit, the strength of the cured resin molding can be increased.

[0038] <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)") as long as the effects of the present invention are not impaired. As the component (C), a known ultraviolet absorber that does not fall into the category of a triazine-based compound, a benzophenone-based compound, or a cyanoacrylate-based compound can be used. For example, compounds having a benzotriazole skeleton (hereinafter also referred to as "benzotriazole-based compounds") can be mentioned. Specific examples include the following:

[0039] [Benzotriazole compounds] Benzotriazole is a compound represented by the following formula (c1) or a compound represented by the following formula (c2).

[0040] [ka]

[0041] The "compound having a benzotriazole skeleton" refers to a compound represented by formula (c1) or (c2), or a compound in which some or all of the hydrogen atoms of the compound of formula (c1) or formula (c2) have been substituted with other substituents. Examples of the substituent include a hydroxyphenyl group, a 3-t-butyl-2-hydroxy-5-methylphenyl group, a 2-hydroxy-5-octylphenyl group, a 2-hydroxy-5-methylphenyl group, and a 2-hydroxy-3,5-di(1,1 dimethylbenzyl)phenyl group.

[0042] 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, and 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol. Examples of commercially available products include EVERSORB73 (manufactured by Nagamitsu Chemical Co., Ltd.), Vanalesin 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 Adeka STAB LA-36 (manufactured by ADEKA Corporation).

[0043] The content of the (C) component in the resin composition is preferably less than 1 part by mass, more preferably 0.1 parts by mass or less, and even more preferably 0.01 parts by mass or less, per 100 parts by mass of the (A) component. Zero is particularly preferred. If it is less than the upper limit, the curability of the resin composition is unlikely to decrease. The total content of the components (B) and (C) is preferably 1 to 5 parts by mass, more preferably 1 to 4 parts by mass, and even more preferably 1 to 3 parts by mass, per 100 parts by mass of the component (A).

[0044] <Light stabilizer (D)> By adding the component (D) to the resin composition, the weather resistance of the resin molded article can be further improved. While UV absorbers improve weather resistance by absorbing UV rays, light stabilizers react with radicals generated by UV irradiation, thereby preventing degradation reactions caused by radicals and improving weather resistance. The component (D) is preferably a hindered amine type light stabilizer (D1) (hereinafter also referred to as "component (D1)"). The component (D1) may be one type or a combination of two or more types. The component (D) may contain one or more light stabilizers other than the component (D1). As the other light stabilizer, known light stabilizers can be used.

[0045] [Component (D1)] The component (D1) is a compound having a hindered amine structure. The 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) have been substituted with other substituents.

[0046] [ka]

[0047] 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. An example of the component (D1) is a compound having a 2,2,6,6-tetramethylpiperidine skeleton. The type of component (D1) is NH type, NR type, or N-OR type. In the present invention, the component (D1) may be any type, but is preferably N-OR type from the viewpoints 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.

[0048] When the resin composition contains the (D) component, the content of the (D) component per 100 parts by mass of the (A) component is preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.3 parts by mass. When the content is equal to or more than the lower limit of the above range, the weather resistance is improved. When the content is equal to or less than the upper limit, curing failure is unlikely to occur during the molding reaction, and the weather resistance improvement effect is easily obtained. The content of the component (D1) relative to the component (D) is preferably 50 to 100 mass %, more preferably 80 to 100 mass %, further preferably 90 to 100 mass %, and particularly preferably 100 mass %.

[0049] <(E) component> The component (E) contains a metal soap (E1). The metal soap (E1) may be one type or a combination of two or more types. The component (E) may contain one or more curing accelerators other than the metal soap (E1).

[0050] Examples of the metal soap (E1) include vanadyl octenate, copper naphthenate, barium naphthenate, cobalt naphthenate, and cobalt octenate.

[0051] Other hardening accelerators include cobalt compounds such as Li3[Co(NO2)6], Li3[Co(NO2)5Cl], Li3[Co(NO2)5Br], Li3[Co(NO2)4Cl2], Li3[Co(NO2)4Br2], Na3[Co(NO2)6], Na3[Co(NO2)5Cl], Na3[Co(NO2)5Br], Na3[Co(NO2)4Cl2], Na3[Co(NO2)4Br2], K3[Co(NO2)6], K3[Co(NO2)5Cl], K3[Co(NO2)5Br], K3[Co(NO2)4Cl2] and K3[Co(NO2)4Br2], and metal chelate compounds such as vanadyl acetyl acetate, cobalt acetyl acetate and iron acetylacetonate. and amines such as 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-methylhydroxyethylaminobenzaldehyde, N,N-bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, and diethanolaniline.

[0052] The content of the (E) component per 100 parts by mass of the (A) component is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass. When the content is equal to or more than the lower limit of the above range, the curing time can be sufficiently shortened, and the influence of curing failure due to environmental changes can be easily suppressed. When the content is equal to or less than the upper limit, it is easy to suppress shrinkage (cracks) due to a sudden increase in heat generation temperature.

[0053] <Hardening agent (G)> The resin composition preferably contains a curing agent (G). When the curing accelerator (E) and the curing agent (G) coexist, the curing reaction is further accelerated. The curing agent (G) is not particularly limited, but is preferably an organic peroxide catalyst. Examples of the organic peroxide catalyst include organic peroxides such as benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 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, dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide and lauryl peroxide, and azo-based polymerization initiators such as azobisisobutyronitrile and azobiscarbonamide. The curing agent (G) may be used alone or in combination of two or more kinds. When the resin composition contains the curing agent (G), the content is not particularly limited, but is preferably 0.1 to 4 parts by mass, and more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the component (A).

[0054] <Other ingredients> The resin composition of the present invention may contain other components in addition to the above-mentioned components (A) to (E) and the curing agent (G). Examples of other components include antioxidants, polymerization inhibitors, fillers, pigments, viscosity reducers, antioxidants, plasticizers, flame retardants, stabilizers, reinforcing materials, etc.

[0055] Examples of the antioxidant include phenol-based antioxidants, phosphoric acid-based antioxidants, aromatic amine-based antioxidants (primary antioxidants), sulfur-based antioxidants (secondary antioxidants), and thioether-based antioxidants.

[0056] The polymerization inhibitor is not particularly limited, but examples thereof include hydroquinone, toluhydroquinone, trimethylhydroquinone, tertiary butylhydroquinone, ditertiary butylhydroquinone, tertiary butylcatechol, methoxyhydroquinone, benzoquinone, tertiary butylquinone, and phenothiazine. The polymerization inhibitor may be used alone or in combination of two or more kinds. By containing the polymerization inhibitor, the reaction between the unsaturated polyester (a1) and the polymerizable unsaturated monomer (a2) is suppressed, thereby improving 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 part by mass per 100 parts by mass of the component (A).

[0057] <Method of producing resin composition> The method for producing the resin composition of the present invention is not particularly limited. For example, a method for producing the resin composition is preferred in which the curing agent (G) is added to a premix containing all components other than the curing agent (G) and mixed to produce the resin composition. When two or more kinds of ultraviolet absorbents are used, they may be mixed in advance and used as a mixture. When an ultraviolet absorber and a light stabilizer are used in combination, a mixture of these may be used in advance.

[0058] (Resin molding) The resin molded article is obtained by curing the resin composition of the present invention and forming it into any desired shape. Examples of resin molded articles include the resin parts of FRP, the resin parts of fiber-reinforced plastic composite pipes, manholes, drainage manholes, building material blocks, paving blocks, covers, pipe materials, repair materials and other civil engineering and construction molded articles, artificial marble molded articles, landscape molded articles, chairs, benches, CC boxes (for underground burial of information and communication power) boxes, information-related molded articles, and power-related molded articles.

[0059] <Method of manufacturing resin molded body> The resin composition is molded and heated to cure, whereby a resin molded article having a specific shape can be produced. The method for producing the resin molded body is not particularly limited, but examples thereof include cast molding, centrifugal molding, compression molding, and continuous molding.

[0060] In the cast molding method, a resin composition is poured into a mold and heated to harden. In centrifugal molding, a resin composition is poured into a cylindrical mold, the mold is then rotated, and the centrifugal force causes the resin composition to be shaped to a uniform thickness, and the resin composition is then heated and cured. In the compression molding method, a resin composition is poured into a mold, compressed by a press, and heated to harden. In the cast molding method, centrifugal molding method, and compression molding method, reinforcing fibers may be placed in a mold, impregnated with a resin composition, and cured to form 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 a plain weave or twill weave.

[0061] In the continuous molding method, the resin composition is wound around a rotating mandrel, and the resin composition is passed through a curing furnace while being fed forward at a constant speed, where it is heated and cured. Before or after winding the resin composition, reinforcing fibers may be wound around the resin composition, and the resin composition impregnated into the wound fibers may be cured to form an FRP.

[0062] 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 more, more preferably 12 hours or more, and further preferably 24 to 48 hours.

[0063] (Fiber reinforced plastic composite pipe) With reference to FIG. 1, an embodiment of a fiber reinforced plastic composite pipe (FRPM pipe) of the present invention will be described. The FRPM pipe 1 in FIG. 1 is cylindrical and extends in the direction of the pipe axis O, and has an annular or tubular resin mortar layer 4, an inner surface fiber reinforced resin layer 3 located on the inner surface of the resin mortar layer 4, an outer surface fiber reinforced resin layer 5 located on the outer surface of the resin mortar layer 4, an inner surface protective layer 2 located on the inner surface of the inner surface fiber reinforced resin layer 3, and an outer surface protective layer 6 located on the outer surface of the outer surface of the outer fiber reinforced resin layer 5. That is, the FRPM pipe 1 has, in order from the inner periphery side, 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. It is sufficient to have only one of the inner fiber-reinforced resin layer 3 and the outer fiber-reinforced resin layer 5, but it is preferable to have both. It is not necessary to have either the inner protective layer 2 or the outer protective layer 6, but it is preferable to have one or both. The FRPM pipe is not limited to a cylindrical shape, but may be a rectangular pipe shape or other angular pipe shape.

[0064] In this embodiment, the inner surface fiber reinforced resin layer 3 has a first inner surface fiber reinforced resin layer 3a in which the fibers extend in the circumferential direction and a second inner surface fiber reinforced resin layer 3b in which the fibers extend in the axial direction. However, the present invention is not limited to this, and the inner surface fiber reinforced resin layer 3 may be composed of one layer. In this case, the reinforcing fibers constituting the inner surface fiber reinforced resin layer 3 may be woven.

[0065] In this embodiment, the outer fiber-reinforced resin layer 5 has a first outer fiber-reinforced resin layer 5a in which the fibers extend in the circumferential direction and a second outer fiber-reinforced resin layer 5b in which the fibers extend in the axial direction. 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 constituting the outer fiber-reinforced resin layer 5 may be woven.

[0066] The resin composition forming the inner surface protective layer 2 may be a conventionally known resin composition containing a thermosetting resin (such as a composition having an iso-based unsaturated polyester resin and a curing agent), or it may be the resin composition of the present invention.

[0067] The inner surface fiber-reinforced resin layer 3 may be, for example, a combination of reinforcing fibers and a cured product of a resin composition. This resin composition is the same as the resin composition forming the inner surface protective layer 2.

[0068] The resin mortar layer 4 is a hardened product of a resin concrete composition. The resin concrete composition can be, 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 those that have been conventionally mixed in resin concrete compositions, such as silica sand, gravel, crushed stone, boulders, blast furnace slag aggregate, artificial lightweight aggregate, etc. The average particle size of the aggregate is, for example, 0.1 to 10 mm. In the resin concrete, the amount of aggregate per 100 parts by mass of resin mortar is, for example, 60 to 90 parts by mass. The resin concrete composition may contain additives such as a polymerization inhibitor, a hardener, and a hardening accelerator.

[0069] An example of the outer fiber-reinforced resin layer 5 is a combination of reinforcing fibers and a resin composition. This resin composition 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 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.

[0070] 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 protective layer 6. By forming the outer protective layer 6 from the resin composition of the present invention, the weather resistance of the resin molded body is improved, and the weather resistance of the FRPM pipe can be improved.

[0071] The inner diameter R of the FRPM pipe 1 can be appropriately determined depending on the application of the FRPM pipe 1. The length of the FRPM pipe 1 in the pipe axis O1 direction can be determined appropriately depending on 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 pipe axis O1 direction, and the strength required for the FRPM pipe 1 and the like.

[0072] <Manufacturing method of FRPM pipe> The manufacturing method of the FRPM pipe 1 is not particularly limited, and examples thereof include conventionally known manufacturing methods such as the filament winding method, the centrifugal molding method, the draw molding method, or the hand lay-up method. The filament winding method is a manufacturing method in which a mandrel is rotated and fed at a constant speed, and the materials of the inner surface protective layer 2, the inner surface fiber-reinforced resin layer 3, the resin mortar layer 4, the outer surface fiber-reinforced resin layer 5, and the outer surface protective layer 6 are sequentially wound and sequentially heat-cured to continuously manufacture an FRPM pipe. According to these methods, FRPM pipes of various sizes can be manufactured by changing the size of the mandrel.

[0073] In addition, as the manufacturing method of the FRPM pipe 1, the manufacturing method of the FRPM pipe described in

[0016] to

[0019] of Japanese Patent Application Laid-Open No. 2001-205711, the manufacturing method of the FRPM pipe described in

[0020] to

[0028] of Japanese Patent Application Laid-Open No. 2001-205712, or the manufacturing method of the FRPM pipe described in

[0009] to

[0019] of Japanese Patent Application Laid-Open No. 10-193467 can also be mentioned. That is, while an endless steel belt is spirally wound around the peripheral surface of a cylindrical mold that rotates around the pipe axis, a resin composition for forming the inner surface protective layer 2, a reinforcing fiber, a resin composition for FRP, a resin concrete composition, a reinforcing fiber, a resin composition for FRP, and a resin composition for forming the outer surface protective layer 6 are supplied in this order to the surface of the wound steel belt, and each resin composition is cured to continuously form the FRPM pipe 1. The steel belt advances due to the rotation of the cylindrical mold and returns from the end of the cylindrical mold through the inside of the mold to the start of the mold. For this reason, the FRPM pipe 1 extends in the axial direction of the cylindrical mold. By cutting the extended FRPM pipe 1 to an arbitrary length, a product of the FRPM pipe 1 can be obtained. 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.

[0074] The FRPM pipe of the present invention is not limited to the above-mentioned embodiment. The FRPM pipe of the present invention may have an outer surface 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 a weather-resistant paint on the outermost surface. Generally, in order to prevent deterioration of the constituent base material of structures, piping, transportation equipment, etc. used outdoors, a paint is applied to the outermost layer. By covering with a paint coating, the influence of deterioration factors such as ultraviolet rays, moisture, temperature, and adhesion of foreign matter on the constituent parts can be suppressed. Examples of weather-resistant paints include fluorine-based paints, silicon-based paints, and acrylic-based paints. Other examples of weather-resistant paints include top coats that are applied to the surface of FRP products used outdoors. From the viewpoint of further improving adhesion with FRPM pipes, fluorine-based paints and acrylic paints are more suitable as weather-resistant paints. Examples of the coating method include spray coating, brush coating or roller coating, etc. Among these, spray coating is preferred in terms of the stability of the film thickness and the finished appearance. By having a weather-resistant paint coating layer on the outer surface, the transmission of ultraviolet rays and moisture to the resin composition that makes up the FRPM pipe is further reduced, further improving weather resistance. The amount of weather-resistant paint applied is, for example, 80 to 300 g / cm 2 is preferable, and 200 to 260 g / cm 2 is more preferred.

[0075] According to the resin composition of the present invention, as shown in the examples described later, by adding a specific ultraviolet absorber (B) as an ultraviolet absorber to a resin composition containing components (A) and (E1), it is possible to impart ultraviolet absorbing ability while suppressing the decrease in curability caused by the addition of the ultraviolet absorber. By imparting ultraviolet absorbing ability, the weather resistance of the resin molded article can be improved. The resin composition of the present invention is particularly suitable as a resin composition for FRP. EXAMPLES

[0076] Hereinafter, the present invention will be described in more detail with reference to examples. However, the technical scope of the present invention is not limited to the examples described below, and various modifications are possible as long as they do not change the gist of the present invention.

[0077] (Raw materials used) <Unsaturated polyester resin (A)> (A-1): Iso-unsaturated polyester resin (manufactured by Japan U-Pica Corporation). <Ultraviolet absorber (B)> (B-1): UV absorber having a triazine structure, ADEKA product name "LA-46". <Other UV absorbers (C)> (C-1): An ultraviolet absorber having a benzotriazole skeleton, Eiko Chemical Co., Ltd. product name "EVERSORB73". <Light stabilizer (D)> (D1-1): Hindered amine type light stabilizer with N-OR functional group, Eiko Chemical Co., Ltd. product name "EVERSORB95". <Curing accelerator (E)> (E1-1): Cobalt naphthenate <Hardening agent (G)> (G-1): Organic peroxide catalyst, NOF Corp. product name "Permec N"

[0078] In each of the following examples, a resin composition was produced according to the formulation shown in Table 1. <Example 1> The (B), (A) and (E) components were kneaded together in a mixer, and the curing agent (G) was added to the resulting kneaded mixture and mixed to obtain a resin composition. <Example 2> Components (B) and (D) were mixed in advance. The resulting mixture was kneaded with components (A) and (E) in a mixer, and the curing agent (G) was added to the resulting mixture and mixed to obtain a resin composition. <Comparative Example 1> Components (B), (C), and (D) were mixed in advance. The resulting mixture was kneaded with components (A) and (E) in a mixer, and the curing agent (G) was added to the resulting mixture and mixed to obtain a resin composition. <Comparative Example 2> The components (A) and (E) were kneaded together in a mixer, and the curing agent (G) was added to the resulting kneaded mixture and mixed to obtain a resin composition.

[0079] A heat curing test was carried out for the resin composition obtained in each example by the method described below, and the curability was evaluated. The results are shown in Figure 2. The horizontal axis of Figure 2 shows the time (minutes) elapsed from the start of heating, and the vertical axis shows the temperature (°C) of the resin composition. Table 2 shows the time (minutes) to reach the maximum temperature, the maximum temperature (°C), and the reaction rate (°C / min) based on the results of Figure 2.

[0080] <Heat curing test> A resin composition that cures by an exothermic reaction was placed in a test tube and heated in an oil bath. As the curing process progressed, the temperature of the resin composition rose, became higher than the temperature of the oil bath, and after reaching its maximum temperature, it released heat and cooled to the same temperature as the oil bath. The temperature change was measured during this process. Specifically, 25 g of the resin composition at 30°C was placed in a test tube. The depth from the bottom of the test tube to the top 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. The test tube was heated in an oil bath at 60°C, and the change over time in the temperature of the resin composition in the test tube was measured. The time from the start of heating in the oil bath until the maximum temperature was reached (time to reach maximum temperature), the maximum temperature, and the temperature at the start of heating were recorded, and the reaction rate was calculated using the following formula (I). A high maximum temperature is an indicator that the curing reaction has progressed sufficiently. Reaction rate (unit: °C / min) = (maximum temperature (°C) - temperature at start of heating (°C)) / time to reach maximum temperature (min) (I)

[0081] [Table 1]

[0082] [Table 2]

[0083] Comparative Example 2 is a blank test consisting of only the component (A), the component (E1), and the curing agent (G). As shown in the results of FIG. 2 and Table 2, Examples 1 and 2 exhibited the same curability (maximum temperature, reaction rate) as Comparative Example 2, despite the addition of component (B). [Explanation of symbols]

[0084] 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

[Claim 1] It is cylindrical and has, 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 surface fiber reinforced resin layer includes reinforcing fibers, an unsaturated polyester resin (A), an ultraviolet absorber (B) which is a compound having a triazine skeleton, and a curing accelerator (E), the curing accelerator (E) includes a metal soap (E1), and the content of the ultraviolet absorber (B) is 1 to 5 parts by mass relative to 100 parts by mass of the unsaturated polyester resin (A), the outer surface protective layer contains the unsaturated polyester resin (A), the ultraviolet absorber (B), and the curing accelerator (E), the curing accelerator (E) contains the metal soap (E1), and the content of the ultraviolet absorber (B) is 1 to 5 parts by mass per 100 parts by mass of the unsaturated polyester resin (A), A fiber-reinforced plastic composite pipe whose outer surface is coated with weather-resistant paint.

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