JPH01308433A - Coated fiber-reinforced resin molding, its production and coating composition used for its production - Google Patents
Coated fiber-reinforced resin molding, its production and coating composition used for its productionInfo
- Publication number
- JPH01308433A JPH01308433A JP13849888A JP13849888A JPH01308433A JP H01308433 A JPH01308433 A JP H01308433A JP 13849888 A JP13849888 A JP 13849888A JP 13849888 A JP13849888 A JP 13849888A JP H01308433 A JPH01308433 A JP H01308433A
- Authority
- JP
- Japan
- Prior art keywords
- reinforced resin
- copolymer
- fluorine
- fiber
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 30
- 239000011347 resin Substances 0.000 title claims abstract description 30
- 238000000465 moulding Methods 0.000 title claims abstract description 14
- 239000008199 coating composition Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 47
- 239000011737 fluorine Substances 0.000 claims description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 46
- 229920006243 acrylic copolymer Polymers 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000003973 paint Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 239000005056 polyisocyanate Substances 0.000 abstract description 5
- 229920001228 polyisocyanate Polymers 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 229920003180 amino resin Polymers 0.000 abstract 1
- -1 polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer Polymers 0.000 description 18
- 239000000203 mixture Substances 0.000 description 7
- 239000006082 mold release agent Substances 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical group FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- IZLFSDDOEKWVLD-UHFFFAOYSA-N 2-chloro-1,1,3,4,4,5,6,6,6-nonafluorohex-1-ene Chemical compound FC(C(F)(F)F)C(C(C(=C(F)F)Cl)F)(F)F IZLFSDDOEKWVLD-UHFFFAOYSA-N 0.000 description 1
- ZXABMDQSAABDMG-UHFFFAOYSA-N 3-ethenoxyprop-1-ene Chemical compound C=CCOC=C ZXABMDQSAABDMG-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IEAIASZSACRBLE-UHFFFAOYSA-N FC(=C(C(C(CCF)(F)F)F)Cl)F Chemical compound FC(=C(C(C(CCF)(F)F)F)Cl)F IEAIASZSACRBLE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- UGIOKXCGSSCHDE-UHFFFAOYSA-N [2-hydroxy-4-(2-hydroxyethyl)phenyl]-phenylmethanone Chemical compound OC1=CC(CCO)=CC=C1C(=O)C1=CC=CC=C1 UGIOKXCGSSCHDE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、塗膜を有する繊維強化樹脂成形品、その製造
方法およびその製造に使用する塗料組成物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fiber-reinforced resin molded article having a coating film, a method for producing the same, and a coating composition used for producing the same.
［従来の技術］
従来、繊維強化樹脂成形品は、軽量、高強度、種々な形
状に成形可能であるなどの利点を生かし、内、外装材、
各種設備機器などの建設分野、タンクなどの容器、船舶
、自動車、電気機器、スポーツ用品など広範囲な分野で
利用されている。これら繊維強化樹脂成形品は、意匠性
、耐久性などを向上させるため各種塗料の塗装がされて
きている。[Conventional technology] Conventionally, fiber-reinforced resin molded products have been used for interior, exterior,
It is used in a wide range of fields, including the construction field for various equipment, containers such as tanks, ships, automobiles, electrical equipment, and sporting goods. These fiber-reinforced resin molded products have been coated with various paints to improve their design and durability.
また、耐候性の優れた塗料として、硬化反応性部位を有
する溶剤可溶性の含フッ素共重合体を必須成分とする塗
料組成物が知られている。Moreover, as a coating material with excellent weather resistance, a coating composition containing as an essential component a solvent-soluble fluorine-containing copolymer having a curing reactive site is known.
例えば特開昭５７−３４１０７号、特開昭５８−１３６
６６２号など。For example, JP-A-57-34107, JP-A-58-136
No. 662 etc.
この様な含フッ素共重合体を必須成分とする塗料組成物
を繊維強化樹脂成形品に塗装することも試みられておる
が、一般に成形後、スプレー塗装により塗装するため、
塗料の損失が極めて大きいという問題点があった。Attempts have also been made to coat fiber-reinforced resin molded products with coating compositions containing such fluorine-containing copolymers as an essential component, but since the coating is generally done by spray painting after molding,
There was a problem in that the loss of paint was extremely large.
［発明の解決しようとする問題点］
また、塗料の損失を少なくし、また均一な塗膜を付与す
る方法として、あらかじめ塗料を塗布した成形用型を用
いて繊維強化樹脂を成形する方法も知られている。しか
しながら、この方法を用いて前述の含フッ素共重合体を
必須成分とする塗料を塗装した場合には、成形後スプレ
ー塗装した場合に比べて塗膜の密着性が極めて低いとい
う問題点があった。[Problems to be solved by the invention] In addition, a method of molding fiber-reinforced resin using a mold coated with paint in advance is also known as a method of reducing loss of paint and providing a uniform coating film. It is being However, when using this method to apply a paint containing the aforementioned fluorine-containing copolymer as an essential component, there was a problem in that the adhesion of the paint film was extremely low compared to when spray painting was performed after molding. .
［問題点を解決するための手段］
本発明は前述の問題点を解決すべくなされたものであり
、
（１）フルオロオレフィンに基づくフッ素含有量が１０
重量％以上であり、硬化反応性部位を有し。[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems. (1) The fluorine content based on the fluoroolefin is 10
% by weight or more, and has a curing reactive site.
テトラヒドロフラン中３０℃で測定される固有粘度が０
．０２〜４．０ ｄｉ／ｇである溶剤可溶性含フッ素共
重合体、スチレンに基づく重合した単位を１０重量％以
上有するアクリル系共重合体、および、硬化剤に基づく
硬化塗膜を有する繊維強化樹脂成形品。Intrinsic viscosity measured at 30°C in tetrahydrofuran is 0.
．． 02 to 4.0 di/g, a solvent-soluble fluorine-containing copolymer, an acrylic copolymer having 10% by weight or more of polymerized units based on styrene, and a fiber reinforced resin having a cured coating film based on a curing agent. Molding.
（２）フルオロオレフィンに基づくフッ素含有量が１０
重量％以上であり、硬化反応性部位を有し、テトラヒド
ロフラン中３０℃で測定される固有粘度が０．０２〜４
．０ ｄｌ／ｇである溶剤可溶性含フッ素共重合体、ス
チレンに基づく重合した単位を１０重量％以上有するア
クリル系共重合体、および硬化剤を含む塗料をあらかじ
め内面に塗布した繊維強化樹脂成形品の製造方法。(2) Fluorine content based on fluoroolefins is 10
% by weight or more, has a curing reactive site, and has an intrinsic viscosity of 0.02 to 4 as measured at 30°C in tetrahydrofuran.
．． 0 dl/g of a solvent-soluble fluorine-containing copolymer, an acrylic copolymer containing 10% by weight or more of styrene-based polymerized units, and a fiber-reinforced resin molded product whose inner surface is coated with a paint containing a curing agent in advance. Production method.
（３）フルオロオレフィンに基づくフッ素含有量が１０
重量％以上であり、硬化反応性部位を有し、テトラヒド
ロフラン中３０℃で測定される固有粘度が０．０２〜４
．０ ｄｉ／ｇである溶剤可溶性含フッ素共重合体、ス
チレンに基づく重合した単位を１０重量％以上有するア
クリル系共重合体、および硬化剤を含んでなる繊維強化
樹脂被覆用塗料組成物。(3) Fluorine content based on fluoroolefins is 10
% by weight or more, has a curing reactive site, and has an intrinsic viscosity of 0.02 to 4 as measured at 30°C in tetrahydrofuran.
．． A coating composition for coating fiber-reinforced resin, comprising a solvent-soluble fluorine-containing copolymer having a molecular weight of 0 di/g, an acrylic copolymer having 10% by weight or more of polymerized units based on styrene, and a curing agent.
を提供するものである。It provides:
本発明において、硬化反応性部位を有する溶剤可溶性含
フッ素共重合体としては１種々の含フッ素重合体が採用
されるが、ポリテトラフルオロエチレン、テトラフルオ
ロエチレン−ヘキサフルオロプロピレン共重合体、テト
ラフルオロエチレン−パーフルオロ（アルキルビニルエ
ーテル）共重合体などの溶剤に不溶性の含フッ素重合体
は、紫外線吸収剤、硬化剤との均一混合が難しく好まし
くない、好ましい溶剤可溶性含フッ素共重合体としては
、フルオロオレフィンおよびエチレン性不飽和化合物の
共重合体を挙げることができる。ここで、フルオロオレ
フィンとしては、テトラフルオロエチレン、クロロトリ
フルオロエチレン、トリフルオロエチレン、フッ化ビニ
リデン、ヘキサフルオロプロピレン、ペンタフルオロプ
ロピレンなどの炭素数２〜４程度のフルオロオレフィン
が好ましい、特に、テトラフルオロエチレン、クロロト
リフルオロエチレン、フッ化ビニリデンまたはヘキサフ
ルオロプロピレンが好ましく採用される。エチレン性不
飽和化合物としては、上記フルオロオレフィンと共重合
可能なものが採用される。かかるエチレン性不飽和化合
物としては、オレフィン類、ビニルエーテル類、ビニル
エステル類、アリルエーテル類、アリルエステル類、ア
クリロイル基含有化合物、メタクリロイル基含有化合物
などが例示される。特に、フルオロオレフィン類との共
重合性に優れ、また、共重合された共重合体が溶剤に対
する溶解性が優れる点から、オレフィン類、ビニルエー
テル類、ビニルエステル類、アリルエーテル類、アリル
エステル類が好ましく採用される。In the present invention, as the solvent-soluble fluorine-containing copolymer having a curing-reactive site, one of various fluorine-containing polymers is employed, including polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, Fluorine-containing polymers that are insoluble in solvents, such as ethylene-perfluoro(alkyl vinyl ether) copolymers, are difficult to mix uniformly with ultraviolet absorbers and curing agents, which is undesirable. Mention may be made of copolymers of olefins and ethylenically unsaturated compounds. Here, as the fluoroolefins, fluoroolefins having about 2 to 4 carbon atoms such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, and pentafluoropropylene are preferable, especially tetrafluoroethylene. Ethylene, chlorotrifluoroethylene, vinylidene fluoride or hexafluoropropylene are preferably employed. As the ethylenically unsaturated compound, one that is copolymerizable with the above-mentioned fluoroolefins is employed. Examples of such ethylenically unsaturated compounds include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acryloyl group-containing compounds, methacryloyl group-containing compounds, and the like. In particular, olefins, vinyl ethers, vinyl esters, allyl ethers, and allyl esters have excellent copolymerizability with fluoroolefins, and the copolymer has excellent solubility in solvents. Preferably adopted.
かかるエチレン性不飽和化合物としては、炭素数ｌＮ１
３程度の直鎖状９分岐状あるいは脂環状のアルキル基を
有する化合物が好ましく採用される。アルキル基の炭素
数があまりに大きいものは、硬化物の耐候性を低下させ
る傾向があり、好ましいとは言えない、また、エチレン
性不飽和化合物は、炭素に結合した水素の一部または全
部がフッ素に置換されたものであってもよい。Such ethylenically unsaturated compounds have a carbon number lN1
A compound having about 3 linear, 9-branched or alicyclic alkyl groups is preferably employed. If the number of carbon atoms in the alkyl group is too large, it tends to reduce the weather resistance of the cured product, so it is not desirable.In addition, ethylenically unsaturated compounds have fluorine in which some or all of the hydrogens bonded to carbon are fluorine. It may be replaced with .
また、本発明における含フッ素共重合体はフルオロオレ
フィンおよびエチレン性不飽和化合物がそれぞれ単独で
、または二種類以上の混合で共重合されているものであ
ってもよい。Further, the fluorine-containing copolymer in the present invention may be a copolymer of a fluoroolefin and an ethylenically unsaturated compound, each singly or as a mixture of two or more.
本発明における含フッ素共重合体は、硬化反応性部位を
有する。ここで、硬化反応性部位とは、それ自身同志ま
たは、硬化剤あるいは紫外線吸収剤と反応して、含フッ
素共重合体間に橋かけ構造を形成し、組成物を硬化体に
転化させることの可能な部位である。かかる硬化反応性
部位としては、水酸基、カルボン酸基、酸アミド基、ア
ミノ基、メルカプト基などの活性水素含有基、エポキシ
基、不飽和基、ヨウ素、臭素などの活性ハロゲン含有基
、加水分解可能なシリル基などが例示される。中でも、
後述する硬化剤との反応性が優れる点から活性水素基含
有基またはエポキシ基が好ましく採用される。The fluorine-containing copolymer in the present invention has a curing reactive site. Here, the curing-reactive site refers to a site that reacts with itself or with a curing agent or an ultraviolet absorber to form a bridge structure between fluorine-containing copolymers and convert the composition into a cured product. This is a possible part. Such curing reactive sites include active hydrogen-containing groups such as hydroxyl groups, carboxylic acid groups, acid amide groups, amino groups, and mercapto groups, epoxy groups, unsaturated groups, active halogen-containing groups such as iodine and bromine, and hydrolyzable groups. Examples include silyl groups. Among them,
An active hydrogen group-containing group or an epoxy group is preferably employed because of its excellent reactivity with the curing agent described below.
かかる硬化反応性部位の導入方法としては、硬化反応性
部位を有するモノマーを共重合させる、含フッ素共重合
体の一部を硬化反応性部位に変換させる。含フッ素共重
合体に硬化反応性部位を有するまたは硬化反応性部位を
与える化合物を反応させるなどの方法が例示される。こ
こで、硬化反応性部位を有するモノマーとしては、ヒド
ロキシアルキルビニルエーテル、ヒドロキシアルキルア
リルエーテル、ヒドロキシアルキルビニルエステル、ヒ
ドロキシアルキルビニルエステル、ヒドロキシアルキル
アリルエステル、グリシジルビニルエーテル、グリシジ
ルアリルエーテル、アミノアルキルビニルエーテル、ア
ミノアルキルアリルエーテル、アミノアルキルビニルエ
ステル、アミノアルキルアリルエステル、アクリル酸、
メタクリル酸、アリルビニルエーテルなどが例示される
。含フッ素共重合体の一部を硬化反応性部位に変換させ
る方法としては、重合後加水分解可能なエステル結合を
有するモノマーを共重合させた後、加水分解してカルボ
ン酸基または水酸基に変換せしめる方法などがある。ま
た、含フッ素共重合体に化合物を反応させて硬化部位を
導入する方法としては、水酸基を有する含フッ素共重合
体に多価カルボン酸無水物を反応させてカルボン酸基を
導入する方法、水酸基を有する含フッ素共重合体にイソ
シアナート基含有アクリロイル化合物またはメタクリロ
イル化合物あるいは、アクリル酸クロライドなどの化合
物を反応させて不飽和基を導入する方法、エポキシ基を
有する含フッ素共重合体に、多価カルボン酸無水物を反
応させて本酸基とカルボン酸基を、フェノールを反応さ
せて水酸基を導入する方法などが例示される。As a method for introducing such a curing-reactive site, a monomer having a curing-reactive site is copolymerized, and a part of the fluorine-containing copolymer is converted into a curing-reactive site. Examples include a method in which a fluorine-containing copolymer is reacted with a compound that has a curing reactive site or provides a curing reactive site. Here, the monomers having a curing reactive site include hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyalkyl vinyl ester, hydroxyalkyl vinyl ester, hydroxyalkyl allyl ester, glycidyl vinyl ether, glycidyl allyl ether, aminoalkyl vinyl ether, aminoalkyl Allyl ether, aminoalkyl vinyl ester, aminoalkyl allyl ester, acrylic acid,
Examples include methacrylic acid and allyl vinyl ether. A method for converting a part of the fluorine-containing copolymer into a curing reactive site is to copolymerize a monomer having an ester bond that can be hydrolyzed after polymerization, and then hydrolyze it to convert it into a carboxylic acid group or a hydroxyl group. There are methods. In addition, methods for introducing a curing site by reacting a compound into a fluorine-containing copolymer include a method in which a polyhydric carboxylic acid anhydride is reacted with a fluorine-containing copolymer having a hydroxyl group to introduce a carboxylic acid group; A method of introducing an unsaturated group into a fluorine-containing copolymer having an epoxy group by reacting an isocyanate group-containing acryloyl compound or methacryloyl compound or a compound such as acrylic acid chloride; Examples include a method of reacting a carboxylic acid anhydride to introduce the present acid group and a carboxylic acid group, and a method of reacting a phenol to introduce a hydroxyl group.
本発明における含フッ素共重合体は、フッ素含有量が１
０重量％以上、特に、フルオロオレフィン単位に基づく
フッ素含有量が１０重量％以上のものであることが好ま
しい、フッ素含有量が低いものは、それ自身の耐候性が
低いため、硬化物の表面部分の耐候性が悪くなることが
あり、好ましくない、特に、フルオロオレフィンが３０
〜７０モル％の割合で共重合された含フッ素共重合体が
好ましい、フルオロオレフィンの共重合割合があまりに
多くなると溶剤に対する溶解性が低下し、塗料用として
組成物を用いる場合に作業性が低下する、また硬化剤お
よび紫外線吸収剤の混合作業性が低下することがあり、
好ましいとはいえなくなる。また、硬化反応性部位を有
する繰り返し単位が２〜４０モル％程度の割合で含まれ
ていることが好ましい、硬化反応性部位の量が少なすぎ
ると機械的性質を示す硬化体を与えることができず、ま
た、多すぎると、硬化体が硬くなって可撓性がなく、脆
いものとなってしまい、塗料用などの用途に適さなくな
るため好ましくない。The fluorine-containing copolymer in the present invention has a fluorine content of 1
It is preferable that the fluorine content is 0% by weight or more, especially 10% by weight or more based on fluoroolefin units.Those with a low fluorine content have low weather resistance themselves, so the surface portion of the cured product The weather resistance of
A fluorine-containing copolymer copolymerized at a ratio of ~70 mol% is preferred; if the copolymerization ratio of fluoroolefin is too high, the solubility in solvents will decrease, and workability will decrease when the composition is used as a paint. Also, the mixing workability of the curing agent and ultraviolet absorber may decrease.
It is no longer desirable. Further, it is preferable that the repeating unit having a curing reactive site is contained in a proportion of about 2 to 40 mol%; if the amount of the curing reactive site is too small, a cured product exhibiting mechanical properties cannot be obtained. On the other hand, if the amount is too large, the cured product becomes hard, inflexible, and brittle, making it unsuitable for applications such as paints.
また、本発明における含フッ素共重合体は、テトラヒド
ロフラン中３０℃で測定される固有粘度（以下、単に［
η］ということがある）が、０．０２〜４．０ ｄｌ／
ｇであるものが、塗料用など被覆用に用いる場合に作業
性、硬化物の物性が優れることから好ましい。In addition, the fluorine-containing copolymer in the present invention has an intrinsic viscosity (hereinafter simply [
η]) is 0.02 to 4.0 dl/
When used for coatings such as paints, it is preferable to use the compound having the formula g, since the workability and physical properties of the cured product are excellent.
本発明におけるアクリル系共重合体は、スチレンに基づ
く重合した単位を１０重量％以上含有する。スチレンに
基づく重合した単位を含有しないあるいは少なすぎる場
合には、塗膜の密着性が低下し好ましくない、好ましく
はスチレンに基づく重合した単位を３０重量％以上含有
するものであるが、あまり、スチレンに基づく重合した
単位の大きなアクリル系共重合体を採用すると、成形品
の耐候性が低くなり好ましくない、好ましくは５０重量
％以下程度含有するアクリル系共重合体である。また、
アクリル系共重合体は、スチレンの他に、アクリロイル
化合物またはメタアクリロイル化合物が共重合したもの
である。かかるアクリロイル化合物またはメタアクリロ
イル化合物としては、アクリル酸アルキルエステル、メ
タアクリル酸アルキルエステルなどが例示される。また
、アクリル系共重合体としては、前記含フッ素共重合体
と同様の硬化反応性部位を有しているものが強靭な塗膜
が得られるため好ましい、かかる硬化反応性部位の導入
方法としては、含フッ素共重合体に硬化部位を導入した
時と同様に、硬化反応性部位を有するモノマーを共重合
させる。アクリル系共重合体の一部を硬化反応性部位に
変換させる。アクリル系共重合体に硬化反応性部位を有
するまたは硬化反応性部位を与える化合物を反応させる
などの方法が採用可能である。The acrylic copolymer in the present invention contains 10% by weight or more of polymerized units based on styrene. If it does not contain styrene-based polymerized units or if it is too small, the adhesion of the coating film will deteriorate, which is undesirable.It is preferable to contain 30% by weight or more of styrene-based polymerized units. If an acrylic copolymer having a large polymerized unit based on the above is employed, the weather resistance of the molded article will deteriorate, which is undesirable.Preferably, the acrylic copolymer contains about 50% by weight or less. Also,
The acrylic copolymer is a copolymer of an acryloyl compound or a methacryloyl compound in addition to styrene. Examples of such acryloyl compounds or methacryloyl compounds include acrylic acid alkyl esters and methacrylic acid alkyl esters. Furthermore, as the acrylic copolymer, it is preferable to use one having a curing reactive site similar to that of the fluorine-containing copolymer because a tough coating film can be obtained.As for the method of introducing such a curing reactive site, , a monomer having a curing reactive site is copolymerized in the same way as when a curing site is introduced into a fluorine-containing copolymer. A portion of the acrylic copolymer is converted into a curing reactive site. A method can be adopted in which the acrylic copolymer is reacted with a compound that has a curing reactive site or provides a curing reactive site.
本発明において、硬化剤としては、前記含フッ素共重合
体の硬化反応性部位と反応し得る基を有する化合物であ
って、含フッ素共重合体と反応して良好な硬化体を与え
るものが採用される。かかる硬化剤としてはポリイソシ
アナート系、アミノブラスト、多塩基酸無水物金属アル
コキシドなどを挙げることができる。ポリイソシアナー
ト系としては、ヘキサメチレンジイソシアナートなどの
ポリイソシアナート化合物。In the present invention, the curing agent used is a compound having a group capable of reacting with the curing reactive site of the fluorine-containing copolymer, which reacts with the fluorine-containing copolymer to give a good cured product. be done. Examples of such curing agents include polyisocyanate, aminoblast, polybasic acid anhydride metal alkoxide, and the like. Examples of polyisocyanate compounds include hexamethylene diisocyanate and other polyisocyanate compounds.
メチルシリルトリイソシアナートなどのシリルイソシア
ナート化合物や、これらの部分縮合物、多量体や、イソ
シアナート基をフェノールなどのブロック化剤でブロッ
クしたブロックポリイソシアナート化合物などが例示さ
れる。特に無黄変タイプのものが好ましく採用される。Examples include silyl isocyanate compounds such as methylsilyl triisocyanate, partial condensates and polymers thereof, and blocked polyisocyanate compounds in which isocyanate groups are blocked with a blocking agent such as phenol. In particular, a non-yellowing type is preferably employed.
アミノブラストとしては、メラミン樹脂、グアナミン樹
脂、尿素樹脂などが採用される。中でもメタノール、エ
タノール、プロパツール、ブクノールなどの低級アルコ
ールの一種または二種以上により少なくとも部分的にエ
ーテル化されたメラミンが好ましく採用される。多塩基
酸無水物としては、無水フタル酸、無水ピロメリット酸
などの芳香族多価カルボン酸無水物や無水マレイン酸、
無ホコハク酸などの脂肪族多価カルボン酸無水物などが
例示される。As the aminoblast, melamine resin, guanamine resin, urea resin, etc. are used. Among them, melamine that has been at least partially etherified with one or more lower alcohols such as methanol, ethanol, propatool, and buknol is preferably employed. Examples of polybasic acid anhydrides include aromatic polycarboxylic acid anhydrides such as phthalic anhydride and pyromellitic anhydride, maleic anhydride,
Examples include aliphatic polycarboxylic acid anhydrides such as anophosuccinic acid.
本発明において、含フッ素共重合体、アクリル系共重合
体および硬化剤の配合量は、特に限定されず、目的、用
途に応じて適宜選定可能であるが、塗膜形成成分中含フ
ッ素共重合体が１０重量％以上、アクリル系共重合体が
２０重量％以上含まれていることが耐候性および塗膜の
密着性の優れた繊維強化樹脂成形品が得られるため好ま
しい、特に、含フッ素共重合体が５０重量％以上含まれ
るものが耐候性に優れ、また、アクリル系共重合体が３
０重量％以上含まれるものが塗膜の密着性が優れるため
好ましい、また、硬化剤は、含フッ素共重合体とアクリ
ル系共重合体の合計量に対して５〜２００重量％程度の
量が通常採用される。In the present invention, the blending amounts of the fluorine-containing copolymer, acrylic copolymer, and curing agent are not particularly limited, and can be appropriately selected depending on the purpose and use. It is preferable to contain 10% by weight or more of the copolymer and 20% by weight or more of the acrylic copolymer because a fiber-reinforced resin molded product with excellent weather resistance and coating adhesion can be obtained. In particular, fluorine-containing copolymer Those containing 50% by weight or more of a polymer have excellent weather resistance, and those containing 3% or more of an acrylic copolymer have excellent weather resistance.
It is preferable that the curing agent is contained in an amount of 0% by weight or more because the adhesion of the coating film is excellent.Also, the amount of the curing agent is about 5 to 200% by weight based on the total amount of the fluorine-containing copolymer and the acrylic copolymer. Usually adopted.
本発明における塗料組成物は、上記含フッ素共重合体、
アクリル系共重合体および硬化剤の他に溶剤、光安定剤
０着色剤、硬化触媒、レベリング剤、滑剤、粘度調整剤
１分散安定剤、ゲル化防止剤などが添加されていてもよ
い６本発明において、繊維強化樹脂成形品は、前述の塗
料組成物をあらかじめ内面に塗布した成形用型を用いて
成形される。成形用型に塗料用組成物を塗布するに当り
、成形用型からの離脱を容易ならしめるために離型剤が
塗布されていることが好ましい、離型剤としては、フッ
素系離型剤、シリコーン系離型剤、ポリビニルアルコー
ル系離型剤、金属石けん、酸アミドなどを利用すること
ができる。The coating composition in the present invention comprises the above-mentioned fluorine-containing copolymer,
In addition to the acrylic copolymer and curing agent, a solvent, a light stabilizer, a coloring agent, a curing catalyst, a leveling agent, a lubricant, a viscosity modifier, a dispersion stabilizer, an anti-gelling agent, etc. may be added.6 In the invention, the fiber-reinforced resin molded article is molded using a mold whose inner surface is coated with the above-mentioned coating composition in advance. When applying the coating composition to a mold, it is preferable that a mold release agent is applied to make it easy to separate from the mold. Examples of the mold release agent include a fluorine-based mold release agent, Silicone mold release agents, polyvinyl alcohol mold release agents, metal soaps, acid amides, etc. can be used.
また、本発明において、塗料用組成物を繊維強化樹脂成
形用型内面に塗布するに際しては、スプレー塗装など従
来一般に用いられる方法が採用可能である。また、成形
用型内面に塗布された塗料を乾燥あるいは硬化せしめた
後、繊維強化樹脂の成形を行うことが好ましい、乾燥あ
るいは硬化を行なわずに繊維強化樹脂の成形を行うと、
塗膜のむらが生じ、耐気候性が低下することがあり好ま
しくない、また硬化を行う場合には、完全に硬化させて
しまわない方が塗膜の密着性の優れた成形品が得られる
ため好ましい。Furthermore, in the present invention, when applying the coating composition to the inner surface of the fiber-reinforced resin molding mold, conventionally commonly used methods such as spray coating can be employed. In addition, it is preferable to mold the fiber-reinforced resin after drying or curing the paint applied to the inner surface of the mold.If the fiber-reinforced resin is molded without drying or curing,
This is undesirable as it may cause unevenness in the coating film and reduce weather resistance.Also, when curing, it is preferable not to completely cure the product as this will result in a molded product with excellent adhesion of the coating film. .
繊維強化樹脂の成形に当っては、従来周知の成形法、例
えば、射出成形、トランスファー成形、圧縮成形、引き
抜き成形、フィラメントワインディング成形、ハンドレ
イアップ成形、インジェクションモールド成形などの方
法が採用可能である。In molding the fiber-reinforced resin, conventionally known molding methods such as injection molding, transfer molding, compression molding, pultrusion molding, filament winding molding, hand lay-up molding, and injection molding can be employed. .
また、本発明において使用される繊維強化樹脂も従来周
知のものを採用することができる。Furthermore, conventionally known fiber reinforced resins can be used as the fiber reinforced resin used in the present invention.
例えば、強化繊維として、炭素繊維、ガラス繊維などの
無機繊維、アラミド繊維などの有機繊維などを含む不飽
和ポリエステル樹脂、ビニルエステル、エポキシｔｄ脂
など広範なものが、採用可能である。For example, a wide variety of reinforcing fibers can be employed, including inorganic fibers such as carbon fibers and glass fibers, organic fibers such as aramid fibers, unsaturated polyester resins, vinyl esters, and epoxy TD resins.
また、本発明の繊維強化樹脂成形品は、特定の含フッ素
共重合体、アクリル系共重合体および硬化剤に基づく硬
化樹脂が一体的に形成されているため、極めて耐候性が
優れ、美粧性が長期にわたって持続されるという優れた
ものである。In addition, the fiber-reinforced resin molded product of the present invention has extremely excellent weather resistance and cosmetic properties because the cured resin based on a specific fluorine-containing copolymer, acrylic copolymer, and curing agent is integrally formed. It is an excellent product that lasts for a long time.
［実施例］
実施例１〜４．比較例１
第１表に示す配合の組成物を、キシレン、イソブチルケ
トン混合溶媒２００重量部、ミネラルスピリット４０重
量部に溶かした塗料組成物を、シリコーン系離型剤を塗
布した金型に塗布し、８０℃で１０分間乾燥、予備硬化
を行なった。この金型を用いて、ガラス繊維を含む不飽
和ポリエステル樹脂を常圧、温度１２０’Ｃにて３０分
間で熱硬化させた後、冷却して、金型から成形品をとり
出した。[Example] Examples 1 to 4. Comparative Example 1 A coating composition in which the composition shown in Table 1 was dissolved in 200 parts by weight of a mixed solvent of xylene and isobutyl ketone and 40 parts by weight of mineral spirit was applied to a mold coated with a silicone mold release agent. , and was dried and precured at 80° C. for 10 minutes. Using this mold, an unsaturated polyester resin containing glass fibers was thermally cured at normal pressure and a temperature of 120'C for 30 minutes, then cooled and the molded product was taken out from the mold.
この成形品の塗膜の密着性（セロテープゴバン目剥離試
験）、耐候性（サンシャインウェザ−オーメーター２０
００時間後の光沢保持率）。The adhesion of the coating film of this molded product (Cello tape goblin peeling test), weather resistance (Sunshine Weather-Ohmeter 20
Gloss retention rate after 00 hours).
型からの脱型性を第２表に示した。Table 2 shows the removability from the mold.
第１表 （重量部）なお硬化剤は、
ヘキサメチレンジイソシア゛ナート環状三量体、硬化触
媒は、ジプチル錫ジラウレート、紫外線吸収剤１は、２
−ヒドロキシ−４−才クトキシベンゾフェノン、紫外線
吸収剤２は、２−ヒドロキシ−４−ヒドロキシエチルベ
ンゾフェノン、着色剤は、ルチル型酸化チタン粉末であ
り、含フッ素共重合体Ａ−１〜Ａ−４゜アクリル系共重
合体Ｂ−１，８−２は、次に示す共重合体組成を有する
。ものである。Table 1 (parts by weight) The curing agent is
Hexamethylene diisocyanate cyclic trimer, curing catalyst: diptyltin dilaurate, ultraviolet absorber 1: 2
-Hydroxy-4-hydroxybenzophenone, UV absorber 2 is 2-hydroxy-4-hydroxyethylbenzophenone, colorant is rutile titanium oxide powder, and fluorine-containing copolymers A-1 to A-4 The acrylic copolymers B-1 and 8-2 have the following copolymer composition. It is something.
含フッ素共重合体組成 （重量％）なお、Ａ−４は
、ヒドロキシブチルビニルエーテルに基づく水酸基の１
０％を無水コハク酸を反応させてカルボン酸基に変性し
たものである。Fluorine-containing copolymer composition (wt%) A-4 is one of the hydroxyl groups based on hydroxybutyl vinyl ether.
0% was modified into carboxylic acid groups by reacting with succinic anhydride.
アクリル系共重合体組成 （重量％）第２表
［発明の効果〕
本発明によれば、耐候性に優れ、塗膜の密着性の優れた
繊維樹脂成形品を、塗料の損失な（、効率的に製造する
ことができる。また、かかる繊維強化樹脂成形品は、耐
候性に優れ、長期にわたって美粧性が保持されるもので
ある。Acrylic copolymer composition (wt%) Table 2 [Effects of the invention] According to the present invention, fiber resin molded products with excellent weather resistance and excellent paint film adhesion can be produced without loss of paint (and efficiency). Furthermore, such fiber-reinforced resin molded products have excellent weather resistance and retain their cosmetic properties over a long period of time.
Claims (3)
重量％以上であり、硬化反応性部位を有し、テトラヒド
ロフラン中３０℃で測定される固有粘度が０．０２〜４
．０ｄｌ／ｇである溶剤可溶性含フッ素共重合体、スチ
レンに基づく重合した単位を１０重量％以上有するアク
リル系共重合体、および、硬化剤に基づく硬化塗膜を有
する繊維強化樹脂成形品。(1) Fluorine content based on fluoroolefins is 10
% by weight or more, has a curing reactive site, and has an intrinsic viscosity of 0.02 to 4 as measured at 30°C in tetrahydrofuran.
．． A fiber-reinforced resin molded article having a solvent-soluble fluorine-containing copolymer having a concentration of 0 dl/g, an acrylic copolymer having 10% by weight or more of polymerized units based on styrene, and a cured coating film based on a curing agent.
重量％以上であり、硬化反応性部位を有し、テトラヒド
ロフラン中３０℃で測定される固有粘度が０．０２〜４
．０ｄｌ／ｇである溶剤可溶性フッ素共重合体、スチレ
ンに基づく重合した単位を１０重量％以上有するアクリ
ル系共重合体、および硬化剤を含む塗料をあらかじめ内
面に塗布した繊維強化樹脂成形用型を用いて繊維強化樹
脂材料を成形することを特徴とする塗膜を有する繊維強
化樹脂成形品の製造方法。(2) Fluorine content based on fluoroolefins is 10
% by weight or more, has a curing reactive site, and has an intrinsic viscosity of 0.02 to 4 as measured at 30°C in tetrahydrofuran.
．． Using a fiber-reinforced resin mold whose inner surface is pre-coated with a paint containing a solvent-soluble fluorine copolymer with a concentration of 0 dl/g, an acrylic copolymer containing 10% by weight or more of styrene-based polymerized units, and a curing agent. 1. A method for producing a fiber-reinforced resin molded product having a coating film, the method comprising molding a fiber-reinforced resin material using a coating film.
重量％以上であり、硬化反応性部位を有し、テトラヒド
ロフラン中３０℃で測定される固有粘度が０．０２〜４
．０ｄｌ／ｇである溶剤可溶性含フッ素共重合体、スチ
レンに基づく重合した単位を１０重量％以上有するアク
リル系共重合体、および硬化剤を含んでなる繊維強化樹
脂被覆用塗料組成物。(3) Fluorine content based on fluoroolefins is 10
% by weight or more, has a curing reactive site, and has an intrinsic viscosity of 0.02 to 4 as measured at 30°C in tetrahydrofuran.
．． A coating composition for coating fiber-reinforced resin, comprising a solvent-soluble fluorine-containing copolymer having a concentration of 0 dl/g, an acrylic copolymer having 10% by weight or more of polymerized units based on styrene, and a curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63138498A JP2858415B2 (en) | 1988-06-07 | 1988-06-07 | Fiber-reinforced resin molded article having cured coating film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63138498A JP2858415B2 (en) | 1988-06-07 | 1988-06-07 | Fiber-reinforced resin molded article having cured coating film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01308433A true JPH01308433A (en) | 1989-12-13 |
| JP2858415B2 JP2858415B2 (en) | 1999-02-17 |
Family
ID=15223525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63138498A Expired - Fee Related JP2858415B2 (en) | 1988-06-07 | 1988-06-07 | Fiber-reinforced resin molded article having cured coating film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2858415B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59101359A (en) * | 1982-12-02 | 1984-06-11 | 日本発条株式会社 | Fiber reinforced plastic board and its manufacture |
| JPS6245635A (en) * | 1985-08-23 | 1987-02-27 | Idemitsu Petrochem Co Ltd | Plastic molding and its production |
| JPS62212471A (en) * | 1986-03-13 | 1987-09-18 | Dainippon Ink & Chem Inc | Paint resin composition |
-
1988
- 1988-06-07 JP JP63138498A patent/JP2858415B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59101359A (en) * | 1982-12-02 | 1984-06-11 | 日本発条株式会社 | Fiber reinforced plastic board and its manufacture |
| JPS6245635A (en) * | 1985-08-23 | 1987-02-27 | Idemitsu Petrochem Co Ltd | Plastic molding and its production |
| JPS62212471A (en) * | 1986-03-13 | 1987-09-18 | Dainippon Ink & Chem Inc | Paint resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2858415B2 (en) | 1999-02-17 |
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