JP5115428B2 - Antifouling FRP molded product and method for producing the same - Google Patents
Antifouling FRP molded product and method for producing the same Download PDFInfo
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- JP5115428B2 JP5115428B2 JP2008247567A JP2008247567A JP5115428B2 JP 5115428 B2 JP5115428 B2 JP 5115428B2 JP 2008247567 A JP2008247567 A JP 2008247567A JP 2008247567 A JP2008247567 A JP 2008247567A JP 5115428 B2 JP5115428 B2 JP 5115428B2
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- 230000003373 anti-fouling effect Effects 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920005989 resin Polymers 0.000 claims description 162
- 239000011347 resin Substances 0.000 claims description 162
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 84
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 239000011941 photocatalyst Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 34
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims description 22
- 239000011159 matrix material Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
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- 150000002736 metal compounds Chemical class 0.000 claims description 16
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
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- 229940077441 fluorapatite Drugs 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 238000001746 injection moulding Methods 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
- Catalysts (AREA)
Description
本発明は、防汚性を向上したＦＲＰ成形品に関し、特に屋外で使用するＦＲＰ成形品、例えば鉄道用の高欄や道路などに設けられるＦＲＰ製防音壁の防汚性向上技術に関する。 The present invention relates to an FRP molded product with improved antifouling properties, and more particularly to a technology for improving antifouling properties of FRP molded products used outdoors, for example, FRP soundproof walls provided on railings, roads, and the like.
防汚性を向上させる技術として、基材表面に酸化チタン等の光触媒粒子を分散させた光触媒層を設けた製品が近年多数商品化されている。光触媒には２つの機能があり、有機物を分解する酸化還元機能と、超親水化の２つの機能があることはよく知られている。前者の機能を利用した抗菌機能を持った製品、前者と後者の両方の機能を利用した防汚機能を持った製品等が代表的である。 As a technique for improving the antifouling property, many products having a photocatalyst layer in which photocatalyst particles such as titanium oxide are dispersed on the surface of a base material have been commercialized in recent years. It is well known that the photocatalyst has two functions, that is, a redox function for decomposing organic substances and a superhydrophilic function. Representative products include antibacterial products using the former function, and antifouling products using both the former and latter functions.
近年の超親水化技術の課題として触媒活性、効果の持続性、触媒粒子の基材に対する接着強度の向上があり、超親水性に限らず光触媒に伴う課題として可視光活性、暗所微弱光活性の増加、基材劣化防止があり、これらに対する技術開発が行われている。 Recent superhydrophilization technology issues include catalytic activity, sustained effect, and improved adhesion strength of catalyst particles to the substrate. Not only superhydrophilicity, but also issues associated with photocatalysts are visible light activity and low-light activity in the dark. And the prevention of deterioration of the base material.
例えば、防汚性を微弱な紫外線で長期間維持するために、超親水効果の持続性、光触媒微弱光活性を向上させる技術が特許文献１、特許文献２に記載されている。 For example, in order to maintain antifouling property for a long time with weak ultraviolet rays, Patent Document 1 and Patent Document 2 describe techniques for improving the sustainability of the superhydrophilic effect and the photocatalytic weak light activity.
特許文献１に記載の技術は基材表面に光触媒層を有する光触媒構造体において、光触媒層表面の少なくとも一部を、極めて薄く（０．２〜１００ｎｍ）他の金属化合物で覆うことにより、光触媒作用による親水性を向上させる技術である。ここで金属化合物の薄膜としては、ケイ素、ジルコニウム、アルミニウム、ニオビウム、タンタラム及びゲルマニウムからなる群から選ばれる一種若しくは二種以上の金属の酸化物、水酸化物又はそれらの混合物からなる薄膜である。また、光触媒層の膜厚は親水性、コスト、透明性から０．０１〜１０μｍと非常に薄い。 In the photocatalyst structure having a photocatalyst layer on the surface of a substrate, the technique described in Patent Document 1 covers at least a part of the surface of the photocatalyst layer with a very thin (0.2 to 100 nm) other metal compound, thereby photocatalytic action. This is a technique for improving the hydrophilicity due to. Here, the thin film of the metal compound is a thin film made of an oxide, a hydroxide or a mixture of one or more metals selected from the group consisting of silicon, zirconium, aluminum, niobium, tantalum and germanium. Moreover, the film thickness of a photocatalyst layer is as very thin as 0.01-10 micrometers from hydrophilic property, cost, and transparency.
このような親水性向上の原理としては以下のメカニズムが考えられている。すなわち、光触媒作用によって生成した正孔と電子は通常は大部分が再結合して消失してしまうが、その中の一部は表面に拡散して近傍の酸素や水分などと反応し活性酸素を生成する。その活性酸素が金属化合物に結合している有機残基や吸着されている水やガス成分などと反応して金属化合物表面に多くの水酸基（ＯＨ基）を生成させる。これらの水酸基が大気中の水分を捕捉し、多数の水分子を表面に物理吸着させて吸着水層を形成し、超親水性を発現する。 The following mechanism is considered as a principle of such hydrophilic improvement. That is, most of the holes and electrons generated by photocatalysis usually recombine and disappear, but some of them diffuse to the surface and react with nearby oxygen, moisture, etc. to react with active oxygen. Generate. The active oxygen reacts with an organic residue bonded to the metal compound, adsorbed water, a gas component, or the like to generate many hydroxyl groups (OH groups) on the surface of the metal compound. These hydroxyl groups capture moisture in the atmosphere, and a large number of water molecules are physically adsorbed on the surface to form an adsorbed water layer, thereby exhibiting super hydrophilicity.
特許文献１の基材表面の光触媒層、金属化合物薄膜は、親水性を得るための薄膜層であり、ＦＲＰ成形品の表面に設けられる数百μｍの厚みを持つゲルコート樹脂層のように基材自体の紫外線劣化を何十年間といった長期的に防止する保護層としての機能はない。 The photocatalyst layer and the metal compound thin film on the surface of the base material of Patent Document 1 are thin film layers for obtaining hydrophilicity, and the base material is a gel coat resin layer having a thickness of several hundreds μm provided on the surface of the FRP molded product. It does not function as a protective layer that prevents its own UV degradation for a long period of time, such as decades.
特許文献２に記載の技術は光触媒性酸化物とアモルファス酸化物（水ガラス、無定形酸化チタン、水酸化チタン、無定形アルミナ、水酸化アルミニウムなど）を含有する表面層を基材表面に設ける技術である。特許文献２に記載の表面層は防曇、防汚のみを目的とした層であり、表面層の膜厚は光の干渉による表面層の発色防止、部材の透明度確保、耐摩耗性向上のために、０．２μｍ以下が好ましいとしており、本技術においてもＦＲＰ成形品のゲルコート樹脂層のように基材自体の紫外線劣化防止機能はない。 The technique described in Patent Document 2 is a technique in which a surface layer containing a photocatalytic oxide and an amorphous oxide (water glass, amorphous titanium oxide, titanium hydroxide, amorphous alumina, aluminum hydroxide, etc.) is provided on the substrate surface. It is. The surface layer described in Patent Document 2 is a layer intended only for antifogging and antifouling, and the film thickness of the surface layer is for preventing coloration of the surface layer due to light interference, ensuring transparency of the member, and improving wear resistance. In addition, 0.2 μm or less is preferable, and even in the present technology, there is no UV deterioration preventing function of the base material itself unlike the gel coat resin layer of the FRP molded product.
一方、光触媒を表面に担持する樹脂材料を製造するために、樹脂中に光触媒粒子を単体で分散すると、光触媒粒子に接触している樹脂を酸化分解するため、これを防止する技術が特許文献３に記載がある。 On the other hand, in order to produce a resin material carrying a photocatalyst on the surface, when photocatalyst particles are dispersed alone in the resin, the resin in contact with the photocatalyst particles is oxidatively decomposed. There is a description.
特許文献３に記載の技術は、樹脂ベース成分と、フッ素アパタイトを主成分とする無機多孔質体中に光触媒を含浸させてなる微粒子とを含み、該微粒子が樹脂ベース成分の表面に析出するように担持させる技術である。 The technique described in Patent Document 3 includes a resin base component and fine particles obtained by impregnating a photocatalyst into an inorganic porous material mainly composed of fluorapatite, and the fine particles are deposited on the surface of the resin base component. This is a technology to be carried on
特許文献３に記載の方法は、光触媒による酸化分解反応による担持樹脂の酸化分解による減肉が問題となる場合は有効であるが、ＦＲＰ成形品表面のゲルコート樹脂層のように製品の耐久期間を考慮しても光触媒を担持する樹脂の酸化分解速度に対して十分な樹脂膜厚を有する場合は、メリットがない。
本発明の課題は、上記従来技術の問題点を解決しようとするものであり、光触媒層表面を金属化合物薄膜で覆うことなく、親水化を向上させることができ、光触媒粒子を担持する樹脂材料の分解による破壊、減肉が製品の耐久性に悪影響を与えないＦＲＰ成形品を安価に提供することにある。 An object of the present invention is to solve the above-mentioned problems of the prior art, and it is possible to improve hydrophilicity without covering the surface of the photocatalyst layer with a metal compound thin film, and the resin material supporting the photocatalyst particles. An object of the present invention is to provide an inexpensive FRP molded product in which destruction and thinning due to decomposition do not adversely affect the durability of the product.
上記課題を解決するために、本発明は以下の構成を採用する。すなわち、
（１）少なくとも表面の一部がゲルコート樹脂層で覆われたＦＲＰ成形品であって、前記ゲルコート樹脂層の厚みが１００μｍ〜１，０００μｍであるとともに、少なくともルチル型酸化チタンを含む光触媒粒子が練混された前記ゲルコート樹脂層の表面を研磨処理することにより前記光触媒粒子が露出されてなることを特徴とする防汚性ＦＲＰ成形品。
（２）前記ゲルコート樹脂層の前記ルチル型酸化チタン含有量が０．１〜２０重量％であることであることを特徴とする（１）に記載の防汚性ＦＲＰ成形品。
（３）前記ゲルコート樹脂層の膜厚方向内側よりも表面側の方が、前記ルチル型酸化チタンの濃度が高いことを特徴とする（１）または（２）に記載の防汚性ＦＲＰ成形品。
（４）前記ゲルコート樹脂層が金属化合物として水酸化アルミニウムおよび／または二酸化珪素（ＳｉＯ２）を含み、前記水酸化アルミニウムおよび／または二酸化珪素の一部が前記ゲルコート樹脂層表面に露出していることを特徴とする（１）〜（３）のいずれかに記載の防汚性ＦＲＰ成形品。
（５）前記ゲルコート樹脂層の前記水酸化アルミ含有量が１０〜４０重量％であることを特徴とする（４）に記載の防汚性ＦＲＰ成形品。
（６）前記ゲルコート樹脂層の前記二酸化珪素（ＳｉＯ２）含有量が０．１〜１０重量％であることを特徴とする（４）に記載の防汚性ＦＲＰ成形品。
（７）前記ゲルコート樹脂層表面の算術平均表面粗さが０．１μｍ〜１０μｍであることを特徴とする（１）〜（６）のいずれかに記載の防汚性ＦＲＰ成形品。
（８）前記防汚性ＦＲＰ成形品が防音壁であることを特徴とする（１）〜（７）のいずれかに記載の防汚性ＦＲＰ成形品。
（９）少なくともルチル型酸化チタンを含む光触媒粒子を練混させた未硬化ゲルコート樹脂を成形型に吹き付け、その上から補強繊維基材を積層し、未硬化マトリクス樹脂を含浸させ、ゲルコート樹脂およびマトリクス樹脂を硬化させた後、成形型から脱型する工程と、脱型した成形品表面に一体化されたゲルコート樹脂層表面を機械研磨することにより、前記光触媒粒子の一部をゲルコート樹脂層表面に露出させる工程を含むことを特徴とする防汚性ＦＲＰ成形品の製造方法。
（１０）少なくともルチル型酸化チタンを含む光触媒粒子と、金属化合物として水酸化アルミニウムおよび／または二酸化珪素（ＳｉＯ２）を含む未硬化ゲルコート樹脂を成形型に吹き付け、その上から補強繊維基材を積層し、未硬化マトリクス樹脂を含浸させ、前記未硬化ゲルコート樹脂および前記未硬化マトリクス樹脂の硬化後、成形型から脱型する工程と、脱型した成形品表面に一体化されたゲルコート樹脂層表面を機械研磨することにより、前記光触媒粒子の一部、前記水酸化アルミニウムの一部および／または前記二酸化珪素（ＳｉＯ２）の一部をゲルコート樹脂層表面に露出させる工程を含むことを特徴とする防汚性ＦＲＰ成形品の製造方法。
（１１）算術平均表面粗さが０．１μｍ〜１０μｍとなるように機械研磨することを特徴とする（９）または（１０）に記載のＦＲＰ成形品の製造方法。
In order to solve the above problems, the present invention employs the following configuration. That is,
(1) An FRP molded article in which at least a part of the surface is covered with a gel coat resin layer, wherein the gel coat resin layer has a thickness of 100 μm to 1,000 μm, and photocatalyst particles containing at least rutile titanium oxide are kneaded. An antifouling FRP molded article, wherein the photocatalyst particles are exposed by polishing the surface of the mixed gel coat resin layer.
(2) The antifouling FRP molded product according to (1), wherein the rutile-type titanium oxide content of the gel coat resin layer is 0.1 to 20% by weight.
(3) The antifouling FRP molded product according to (1) or (2), wherein the concentration of the rutile titanium oxide is higher on the surface side than on the inner side in the film thickness direction of the gel coat resin layer. .
(4) The gel coat resin layer contains aluminum hydroxide and / or silicon dioxide (SiO 2 ) as a metal compound, and a part of the aluminum hydroxide and / or silicon dioxide is exposed on the surface of the gel coat resin layer. The antifouling FRP molded product according to any one of (1) to (3).
(5) The antifouling FRP molded product according to (4), wherein the content of the aluminum hydroxide in the gel coat resin layer is 10 to 40% by weight.
(6) The antifouling FRP molded product according to (4), wherein the content of the silicon dioxide (SiO 2 ) in the gel coat resin layer is 0.1 to 10% by weight.
(7) The antifouling FRP molded product according to any one of (1) to (6), wherein the arithmetic average surface roughness of the surface of the gel coat resin layer is 0.1 μm to 10 μm.
(8) The antifouling FRP molded product according to any one of (1) to (7), wherein the antifouling FRP molded product is a soundproof wall.
(9) An uncured gel coat resin in which photocatalyst particles containing at least rutile-type titanium oxide are kneaded is sprayed on a mold, a reinforcing fiber base material is laminated thereon, and impregnated with an uncured matrix resin, and the gel coat resin and matrix After the resin is cured, a part of the photocatalyst particles is formed on the surface of the gel coat resin layer by mechanically polishing the surface of the gel coat resin layer integrated with the step of removing the mold from the mold and the molded product thus removed. The manufacturing method of the antifouling FRP molded product characterized by including the process to expose.
(10) A photocatalyst particle containing at least rutile-type titanium oxide and an uncured gel coat resin containing aluminum hydroxide and / or silicon dioxide (SiO 2 ) as a metal compound are sprayed on a mold, and a reinforcing fiber base material is laminated thereon. And a step of removing the mold from the mold after the uncured matrix resin is impregnated, and curing the uncured gel coat resin and the uncured matrix resin, and the surface of the gel coat resin layer integrated on the surface of the molded product that has been removed. And a step of exposing a part of the photocatalyst particles, a part of the aluminum hydroxide and / or a part of the silicon dioxide (SiO 2 ) to the surface of the gel coat resin layer by mechanical polishing. Manufacturing method of dirty FRP molded product.
(11) The method for producing an FRP molded product according to (9) or (10), wherein mechanical polishing is performed so that the arithmetic average surface roughness is 0.1 μm to 10 μm.
本発明によれば、表面の親水性を長期間維持することができ、長期間の防汚性、耐久性に優れるＦＲＰ成形品を安価に得ることができる。特に、光触媒層表面を金属化合物薄膜で覆うことなく、親水化を向上させることができ、光触媒粒子を担持する樹脂材料の分解による破壊、減肉が製品の耐久性に悪影響を与えないＦＲＰ成形品を安価に提供するができる。 According to the present invention, the hydrophilicity of the surface can be maintained for a long period of time, and an FRP molded product excellent in long-term antifouling properties and durability can be obtained at a low cost. In particular, it is possible to improve hydrophilicity without covering the surface of the photocatalyst layer with a metal compound thin film, and FRP molded products in which destruction and thinning due to decomposition of the resin material supporting the photocatalyst particles do not adversely affect the durability of the product. Can be provided at low cost.
具体的には、本発明のＦＲＰ成形品はＦＲＰスキン材と、該ＦＲＰスキン材の少なくとも表面の一部に一体化されたゲルコート樹脂で構成されており、該ゲルコート樹脂が光触媒活性の低いルチル型結晶を含有するルチル型酸化チタンを含み、前記ルチル型酸化チタンの一部をゲルコート樹脂層表面に露出させた構造とすることにより、ゲルコート樹脂の分解がほとんどない長期耐久性、長期親水性に優れた防汚性ＦＲＰ成形品を得ることができる。また、前記ルチル型酸化チタンを含む光触媒層であるゲルコート樹脂層に金属化合物として水酸化アルミニウムを分散させることにより、親水性を更に向上させた防汚性ＦＲＰ成形品を安価に得ることができる。光触媒層表面を金属化合物薄膜で覆う構造に対し、安価に製造することが可能である。 Specifically, the FRP molded product of the present invention is composed of an FRP skin material and a gel coat resin integrated with at least a part of the surface of the FRP skin material, and the gel coat resin has a low photocatalytic activity. It has excellent long-term durability and long-term hydrophilicity with almost no decomposition of the gel coat resin by including a rutile-type titanium oxide containing crystals and a structure in which a part of the rutile-type titanium oxide is exposed on the surface of the gel coat resin layer. An antifouling FRP molded product can be obtained. Further, by dispersing aluminum hydroxide as a metal compound in the gel coat resin layer, which is a photocatalyst layer containing rutile-type titanium oxide, an antifouling FRP molded product with improved hydrophilicity can be obtained at low cost. It can be manufactured at low cost for a structure in which the surface of the photocatalyst layer is covered with a metal compound thin film.
以下、本発明の最良の実施形態の例を、図面を参照しながら説明する。なお、本発明が、図面に記載された態様に限定される訳ではない。 Hereinafter, examples of the best mode of the present invention will be described with reference to the drawings. In addition, this invention is not necessarily limited to the aspect described in drawing.
図１は、本発明の一実施態様に係わるＦＲＰ成形品の断面図の一部を示す。 FIG. 1 shows a part of a sectional view of an FRP molded product according to an embodiment of the present invention.
図１に示すように、ＦＲＰ成形品１は、ＦＲＰスキン材２の少なくとも表面の一部がゲルコート樹脂層３で覆われており、ゲルコート樹脂層３が光触媒としてルチル型酸化チタン５を含んでおり、ルチル型酸化チタン５の一部がゲルコート樹脂層３の表面に露出している。
光触媒としてルチル型酸化チタン５がゲルコート樹脂層３の表面に露出することにより、光励起による親水性を発現することができ、セルフクリーニング効果による防汚機能を得ることができる。
As shown in FIG. 1, in the FRP molded product 1, at least a part of the surface of the FRP skin material 2 is covered with a gel coat resin layer 3, and the gel coat resin layer 3 includes rutile titanium oxide 5 as a photocatalyst. A part of the rutile titanium oxide 5 is exposed on the surface of the gel coat resin layer 3.
When the rutile titanium oxide 5 is exposed as a photocatalyst on the surface of the gel coat resin layer 3, hydrophilicity due to photoexcitation can be expressed, and an antifouling function due to a self-cleaning effect can be obtained.
図２は、本発明の別の実施態様に係わるＦＲＰ成形品の断面図の一部を示す。 FIG. 2 shows a part of a sectional view of an FRP molded product according to another embodiment of the present invention.
図２に示すように、ＦＲＰ成形品１はＦＲＰスキン材２の少なくとも表面の一部がゲルコート樹脂層３で覆われており、ゲルコート樹脂層３が光触媒としてルチル型酸化チタン５および金属化合物として水酸化アルミニウム６を含んでおり、ルチル型酸化チタン５の一部および水酸化アルミニウム６の一部がゲルコート樹脂層３の表面に露出している。 As shown in FIG. 2, in the FRP molded article 1, at least a part of the surface of the FRP skin material 2 is covered with a gel coat resin layer 3, and the gel coat resin layer 3 is water as a rutile titanium oxide 5 and a metal compound as a photocatalyst. Aluminum oxide 6 is included, and part of rutile titanium oxide 5 and part of aluminum hydroxide 6 are exposed on the surface of gel coat resin layer 3.
図３は、本発明のさらに別の実施態様に係わるＦＲＰ成形品の断面図の一部を示す。 FIG. 3 shows a part of a cross-sectional view of an FRP molded product according to still another embodiment of the present invention.
図３に示すように、ＦＲＰ成形品１はＦＲＰスキン材２の少なくとも表面の一部がゲルコート樹脂層３で覆われており、ゲルコート樹脂層３が光触媒としてルチル型酸化チタン５、金属化合物として水酸化アルミニウム６、および二酸化珪素７を含んでおり、ルチル型酸化チタン５の一部、水酸化アルミニウム６の一部、および二酸化珪素７の一部がゲルコート樹脂層３表面に露出している。 As shown in FIG. 3, in the FRP molded product 1, at least a part of the surface of the FRP skin material 2 is covered with a gel coat resin layer 3, and the gel coat resin layer 3 is a rutile type titanium oxide 5 as a photocatalyst and water as a metal compound. Aluminum oxide 6 and silicon dioxide 7 are included, and part of rutile titanium oxide 5, part of aluminum hydroxide 6, and part of silicon dioxide 7 are exposed on the surface of gel coat resin layer 3.
ＦＲＰスキン材２のマトリクス樹脂としては、エポキシ樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、フェノール樹脂などの熱硬化性樹脂が好適である。鉄道用の高欄や道路などに設けられるＦＲＰ製防音壁として使用する場合は、これらの樹脂中に層状化合物（例えば、マイカ、二硫化モリブデン、窒化硼素など）や針状化合物（例えば、ゾノトライト、チタン酸カリ、炭素繊維など）、粒状および板状化合物（例えば、フェライト、タルク、クレーなど）などの制振剤を添加することができる。制振剤を添加することによって、無機物結晶同士あるいは無機物とマトリクス樹脂との相互運動による摩擦熱への変換がなされ、上記フィラーを充填することによって弾性率と密度が増大し、振動物体の運動エネルギーを消散させて、パネルの振動を軽減することができる。かかる制振剤は、その添加量に比例し制振効果が大きくなるが、添加量がマトリクス樹脂の全体積の５体積％より小さいとその制振効果が小さくなることがあり、７０体積％を越えるとマトリクス樹脂の補強繊維への含浸性が悪化することが問題があるため、添加量はマトリクス樹脂の全体積の５〜７０体積％含まれていることが好ましく、より好ましくは１０〜５０体積％である。 The matrix resin of the FRP skin material 2 is preferably a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, or a phenol resin. When used as an FRP sound barrier provided on railings or roads for railways, layered compounds (for example, mica, molybdenum disulfide, boron nitride, etc.) and acicular compounds (for example, zonotlite, titanium) are used in these resins. Damping agents such as acid potash, carbon fibers, etc.), granular and plate-like compounds (eg, ferrite, talc, clay, etc.) can be added. By adding a damping agent, conversion to frictional heat is achieved by the mutual movement of inorganic crystals or between inorganic and matrix resin. Filling the filler increases the elastic modulus and density, and the kinetic energy of the vibrating object. Can be dissipated to reduce panel vibration. Such a vibration damping agent increases the vibration damping effect in proportion to the amount of addition, but if the amount added is less than 5% by volume of the total volume of the matrix resin, the vibration damping effect may be reduced. If exceeding, there is a problem that the impregnation property of the matrix resin into the reinforcing fiber is deteriorated. Therefore, the addition amount is preferably included in an amount of 5 to 70% by volume, more preferably 10 to 50% by volume of the total volume of the matrix resin. %.
また、上記のマトリクス樹脂中に難燃剤を添加して、難燃性を向上させることができる。フェノール樹脂はそれ自体で難燃性に優れており、かつ安価であるため好ましく使用される。かかる難燃剤は、使用するマトリクス樹脂によって適宜選定することができ、テトラブロモビスフェノールＡ、ヘキサブロモベンゼン等の臭素系難燃剤の他、トリフェニルホスフェート、クレジルフェニルホスフェート、芳香族リン酸エステル、芳香族縮合リン酸エステル、ポリリン酸塩類、赤リン系等のリン系難燃剤や三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム等の無機系難燃剤を使用することができる。塩素系難燃剤も使用可能であるが、燃焼時の有害物質発生の問題から環境面を考慮した上での使用が望ましい。難燃剤の種類によりその難燃効果は異なるが、添加量がマトリクス樹脂の全重量の０．１重量％未満では難燃効果がほとんどなく、５０重量％以上では耐熱性、耐光性の低下や機械物性の低下を引き起こすことがあるため、添加量は０．１〜５０重量％であることが好ましく、より好ましくは０．３〜４０重量％である。 Moreover, a flame retardant can be added in said matrix resin, and a flame retardance can be improved. Phenol resin itself is excellent in flame retardancy and is preferably used because it is inexpensive. Such a flame retardant can be appropriately selected depending on the matrix resin to be used. In addition to brominated flame retardants such as tetrabromobisphenol A and hexabromobenzene, triphenyl phosphate, cresyl phenyl phosphate, aromatic phosphate ester, aromatic It is possible to use phosphorus-based flame retardants such as group condensed phosphates, polyphosphates, red phosphorus, and inorganic flame retardants such as antimony trioxide, antimony tetroxide, antimony pentoxide, aluminum hydroxide, and magnesium hydroxide. it can. Chlorine flame retardants can also be used, but it is desirable to use them in consideration of the environment from the problem of generation of harmful substances during combustion. The flame retardant effect varies depending on the type of flame retardant, but if the added amount is less than 0.1% by weight of the total weight of the matrix resin, there is almost no flame retardant effect, and if it is 50% by weight or more, the heat resistance and light resistance are reduced. Since the physical properties may be lowered, the addition amount is preferably 0.1 to 50% by weight, more preferably 0.3 to 40% by weight.
なお、上記これらの添加物は、取り付ける箇所つまり、火災による延焼を防ぐところ、振動伝播が著しいところなどの状況に合わせて、両方またはいずれか一方を適宜選択すればよい。 In addition, the above-mentioned additives may be appropriately selected in accordance with a situation such as a place to be attached, that is, a place where fire spread due to fire is prevented and a place where vibration propagation is remarkable.
前記ＦＲＰスキン材２の補強繊維基材としては、用途、使用条件に応じて適宜、ガラス繊維や炭素繊維などからなる無機繊維や、アラミド繊維、ナイロン繊維あるいはポリエステル繊維などの有機繊維などを用いることができる。また、用いられる繊維の形態としては、例えば、繊維長が１〜３ｍｍである短繊維やマット、連続繊維からなるクロス、ストランドなどを好適に用いることができる。 As the reinforcing fiber base material of the FRP skin material 2, an inorganic fiber made of glass fiber or carbon fiber, or an organic fiber such as aramid fiber, nylon fiber, or polyester fiber, or the like is appropriately used depending on the application and use conditions. Can do. Moreover, as a form of the fiber to be used, for example, a short fiber or mat having a fiber length of 1 to 3 mm, a cloth made of continuous fiber, a strand, or the like can be preferably used.
ここで、軽量で高強度のＦＲＰを得るためには、炭素繊維が最も好ましいが、コストとのバランスを取るため、ガラス繊維／炭素繊維のハイブリッド、あるいはガラス繊維のものも好ましい。 Here, in order to obtain light weight and high strength FRP, carbon fiber is most preferable, but in order to balance with cost, a glass fiber / carbon fiber hybrid or glass fiber is also preferable.
炭素繊維を入れることにより、振動減衰性が向上するため、特に鉄道高架橋での使用に適している。さらに用いる炭素繊維の種類は、炭素繊維の高い強度および弾性率を考えると、どんなものでも良いが、より低コスト化のためには、いわゆるラージ・トウの炭素繊維を用いるのが最も好ましい。例えば、炭素繊維糸１本のフィラメント数が通常の１０，０００本未満のものではなく、１０，０００〜３００，０００本の範囲、より好ましくは５０，０００〜１５０，０００本の範囲にあるトウ状の炭素繊維フィラメント糸を使用するほうが樹脂の含浸性、補強繊維基材としての取り扱い性、さらには補強繊維基材の経済性おいて、より優れるため、好ましい。また、必要に応じて、あるいは要求される機械特性などに応じて、補強繊維の層を複数層に積層して補強繊維基材を形成し、その補強繊維基材に樹脂を含浸する。積層する補強繊維層には、一方向に引き揃えた繊維層や織物層を適宜積層でき、その繊維配向方向も、要求される強度の方向に応じて適宜選択できる。 Incorporation of carbon fiber improves vibration damping and is particularly suitable for use in railway viaducts. Further, any carbon fiber may be used in consideration of the high strength and elastic modulus of the carbon fiber, but it is most preferable to use a so-called large tow carbon fiber for further cost reduction. For example, the number of filaments of one carbon fiber yarn is not less than the usual 10,000, but is in the range of 10,000 to 300,000, more preferably in the range of 50,000 to 150,000. It is preferable to use a carbon fiber filament thread in the form of a resin because it is more excellent in resin impregnation property, handling property as a reinforcing fiber substrate, and economics of the reinforcing fiber substrate. Further, if necessary or according to required mechanical properties, a reinforcing fiber base is formed by laminating a plurality of layers of reinforcing fibers, and the reinforcing fiber base is impregnated with a resin. In the reinforcing fiber layer to be laminated, a fiber layer or a woven fabric layer arranged in one direction can be appropriately laminated, and the fiber orientation direction can also be appropriately selected according to the required strength direction.
ゲルコート樹脂層３は不飽和ポリエステル樹脂、ビニルエステル樹脂、エポキシ樹脂、フェノール樹脂等が好適に使用できる。 As the gel coat resin layer 3, an unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, or the like can be suitably used.
ゲルコート樹脂層３の膜厚は１００μｍ〜１，０００μｍの範囲であることが好ましく、より好ましくは３００μｍ〜７００μｍである。不飽和ポリエステル未硬化ゲルコート樹脂に対し、光触媒としてルチル型酸化チタン５を５〜１０重量％混入して硬化させたゲルコート樹脂層３に、東京地方の３０年間に相当する紫外線量を照射した後のゲルコート樹脂層３の酸化分解による減肉量は２０μｍであった。ゲルコート樹脂の材質、紫外線量の地域差および一般的なＦＲＰ製品の耐久期間を考慮すると、ゲルコート樹脂層３の膜厚は１００μｍ以上であることが好ましい。１，０００μｍを越えるとゲルコート樹脂のコストが高くなり過ぎたり、樹脂収縮によるひび割れを発生させたりすることがある。 The film thickness of the gel coat resin layer 3 is preferably in the range of 100 μm to 1,000 μm, more preferably 300 μm to 700 μm. After irradiating the unsaturated polyester uncured gel coat resin with 5 to 10% by weight of rutile-type titanium oxide 5 as a photocatalyst and curing the gel coat resin layer 3 with an ultraviolet ray equivalent to 30 years in the Tokyo region. The thickness reduction due to oxidative decomposition of the gel coat resin layer 3 was 20 μm. Considering the material of the gel coat resin, the regional difference in the amount of ultraviolet rays, and the durability period of general FRP products, the film thickness of the gel coat resin layer 3 is preferably 100 μm or more. If it exceeds 1,000 μm, the cost of the gel coat resin may become too high, or cracks due to resin shrinkage may occur.
ゲルコート樹脂層３は様々な色に着色することが可能で、種々の無機顔料、有機顔料を未硬化ゲルコート樹脂に添加することができる。光触媒としてのルチル型酸化チタン５は白色無機顔料を兼ねるため、他の顔料との組み合わせにより、ゲルコート樹脂層３の着色を自由に調整することができる。 The gel coat resin layer 3 can be colored in various colors, and various inorganic pigments and organic pigments can be added to the uncured gel coat resin. Since the rutile titanium oxide 5 as a photocatalyst also serves as a white inorganic pigment, the coloring of the gel coat resin layer 3 can be freely adjusted by combining with other pigments.
光触媒としては、酸化チタンＴｉＯ２、チタン酸ストロンチウムＳｒＴｉＯ３、酸化タングステンＷＯ２、酸化亜鉛ＺｎＯ、硫化亜鉛ＺｎＳ、硫化カドミウムＣｄＳ、タンタル酸ナトリウムＮａＴａＯ３等が知られているが、励起電子と正孔の電荷分離が安定し、化学的な毒性が無く、安価に入手可能な酸化チタンが好ましい。光触媒特性を有する酸化チタンには、結晶構造によりアナターゼ型、ルチル型、ブルカイト型があるが、光触媒特性をもつのはアナターゼ型、ルチル型である。アナターゼ型は光触媒活性が最も高く、強い酸化分解反応、超親水性反応を呈する反面、担持材料が本発明の樹脂材料のような有機物の場合は、樹脂材料を酸化分解してしまうため好ましくない。ルチル型は白色顔料として利用されており、光触媒としてはアナターゼ型より光触媒活性が低く、酸化分解力は弱いが、親水性機能を持たせるには十分である。したがい、ゲルコート樹脂層３に混入する光触媒としてはルチル型酸化チタン５が最も好ましい。 Known photocatalysts include titanium oxide TiO 2 , strontium titanate SrTiO 3 , tungsten oxide WO 2 , zinc oxide ZnO, zinc sulfide ZnS, cadmium sulfide CdS, sodium tantalate NaTaO 3, etc., but excited electrons and holes It is preferable to use titanium oxide which has stable charge separation, is not chemically toxic and can be obtained at low cost. Titanium oxide having photocatalytic properties includes anatase type, rutile type, and brookite type depending on the crystal structure, but anatase type and rutile type have photocatalytic properties. The anatase type has the highest photocatalytic activity and exhibits a strong oxidative decomposition reaction and a superhydrophilic reaction. On the other hand, when the support material is an organic substance such as the resin material of the present invention, the resin material is oxidized and decomposed. The rutile type is used as a white pigment. As a photocatalyst, the photocatalytic activity is lower than that of the anatase type and the oxidative decomposition ability is weak, but it is sufficient to have a hydrophilic function. Therefore, rutile type titanium oxide 5 is most preferable as a photocatalyst mixed in the gel coat resin layer 3.
ルチル型酸化チタン５のゲルコート樹脂層３に対する含有量は０．１〜２０重量％であることが好ましい。０．１重量％以下ではルチル型酸化チタン５の光触媒機能を十分発揮することができない他、上述の着色調整範囲が小さくなり、色が限定される問題がある。２０重量％を越えると、未硬化ゲルコート樹脂が増粘し、作業性が低下したり、硬化後のゲルコート樹脂層の伸びが低下して、ひび割れが発生したりする等の問題がある。 The content of the rutile titanium oxide 5 with respect to the gel coat resin layer 3 is preferably 0.1 to 20% by weight. If it is 0.1% by weight or less, the photocatalytic function of the rutile-type titanium oxide 5 cannot be sufficiently exhibited, and the above-mentioned color adjustment range becomes small, and the color is limited. If it exceeds 20% by weight, the uncured gel coat resin will increase in viscosity and workability will decrease, and the elongation of the cured gel coat resin layer will decrease and cracks will occur.
ゲルコート樹脂層３にルチル型酸化チタン５および水酸化アルミニウム６を添加することにより、前述した原理によりゲルコート樹脂層３表面の親水性を向上させることができる。さらに、水酸化アルミニウム６は難燃剤としても機能するため、添加により難燃性能を付与することができる。 By adding rutile type titanium oxide 5 and aluminum hydroxide 6 to the gel coat resin layer 3, the hydrophilicity of the surface of the gel coat resin layer 3 can be improved according to the principle described above. Furthermore, since the aluminum hydroxide 6 also functions as a flame retardant, flame resistance can be imparted by addition.
水酸化アルミニウム６のゲルコート樹脂層３に対する含有量は１０〜４０重量％であることが好ましい。１０重量％未満では上述の親水性の向上機能を十分発揮できず、４０重量％を越えると、未硬化ゲルコート樹脂が増粘し、作業性が低下したり、硬化後のゲルコート樹脂層３の伸びが低下し、ひび割れが発生したりする等の問題がある。 The content of aluminum hydroxide 6 with respect to the gel coat resin layer 3 is preferably 10 to 40% by weight. If the amount is less than 10% by weight, the above-described hydrophilicity-improving function cannot be sufficiently exhibited. If the amount exceeds 40% by weight, the uncured gel coat resin is thickened and the workability is reduced, or the gel coat resin layer 3 is stretched after curing. There is a problem that the cracks are reduced and cracks are generated.
ゲルコート樹脂層３にルチル型酸化チタン５、水酸化アルミニウム６、および二酸化珪素７を添加することにより、同様の原理によりゲルコート樹脂層３表面の親水性を向上させることができる。さらに、二酸化珪素７は揺変剤としても機能するため、添加により揺変性を付与することができ、未硬化ゲルコート樹脂を成形型に吹き付ける際の液垂れを防止することができる。 By adding rutile type titanium oxide 5, aluminum hydroxide 6 and silicon dioxide 7 to the gel coat resin layer 3, the hydrophilicity of the surface of the gel coat resin layer 3 can be improved by the same principle. Furthermore, since silicon dioxide 7 also functions as a thixotropic agent, thixotropic properties can be imparted by addition, and dripping when uncured gel coat resin is sprayed onto the mold can be prevented.
二酸化珪素７のゲルコート樹脂層３に対する含有量は０．１〜１０重量％であることが好ましい。より好ましくは０．１〜５重量％である。０．１重量％未満では揺変性が小さく、未硬化ゲルコート樹脂を成形型に吹き付けた際、成形型鉛直面の垂れが発生し、均一な膜厚のゲルコート樹脂層３が得られないという問題がある。１０重量％を越えると、作業性が低下したり、硬化後のゲルコート樹脂層３の伸びが低下し、ひび割れが発生したりする等の問題がある。 It is preferable that content with respect to the gel coat resin layer 3 of the silicon dioxide 7 is 0.1 to 10 weight%. More preferably, it is 0.1 to 5% by weight. If it is less than 0.1% by weight, the thixotropic property is small, and when the uncured gel coat resin is sprayed on the mold, the vertical surface of the mold sags and the gel coat resin layer 3 having a uniform film thickness cannot be obtained. is there. When it exceeds 10% by weight, there are problems that workability is reduced, elongation of the gel coat resin layer 3 after curing is reduced, and cracks are generated.
上記においては、水酸化アルミニウム６の存在下において、さらに二酸化珪素７を付加する態様についてのみ説明したが、金属化合物として二酸化珪素等の揺変剤のみを添加することも好ましい。その他にも、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、サリシレート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、オギザニリド系紫外線吸収剤、ヒンダードアミン系紫外線吸収剤、Ｎｉ系紫外線吸収剤、ベンゾエート系紫外線吸収剤等に代表される光安定剤や、上記ＦＲＰスキン材２と同様の制振剤、難燃剤を添加することも好ましく、本発明の変形実施態様とすることができる。 In the above description, only the mode of adding silicon dioxide 7 in the presence of aluminum hydroxide 6 has been described, but it is also preferable to add only a thixotropic agent such as silicon dioxide as the metal compound. In addition, benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, Ni UV absorbers, benzoate It is also preferable to add a light stabilizer typified by an ultraviolet absorber or the like, a vibration damping agent similar to the FRP skin material 2, and a flame retardant, and this can be a modified embodiment of the present invention.
以下に本発明のＦＲＰ成形品１の製造方法の概略工程を説明する。 Below, the outline process of the manufacturing method of the FRP molded product 1 of this invention is demonstrated.
図４は、本発明の製造に係わる成形型の断面図を示す。 FIG. 4 shows a cross-sectional view of a mold for manufacturing according to the present invention.
まず、成形型８に離型剤を塗布した後、未硬化ゲルコート樹脂を成形型８に刷毛塗りもしくはスプレー塗布する。未硬化ゲルコート樹脂の硬化反応が進み、ゲル化した状態で、補強繊維基材を積層し、未硬化マトリクス樹脂を含浸させる。未硬化ゲルコート樹脂および未硬化マトリクス樹脂が完全硬化に近い状態まで硬化した後、成形型８から脱型し、ＦＲＰスキン材２とゲルコート樹脂層３が一体化された成形品を得る。 First, a mold release agent is applied to the mold 8, and then an uncured gel coat resin is applied to the mold 8 by brushing or spraying. The curing reaction of the uncured gel coat resin proceeds and the reinforcing fiber base material is laminated and impregnated with the uncured matrix resin in a gelled state. After the uncured gel coat resin and the uncured matrix resin are cured to a state almost completely cured, the mold is removed from the mold 8 to obtain a molded product in which the FRP skin material 2 and the gel coat resin layer 3 are integrated.
最後に、脱型したＦＲＰ成形品１の表面に一体化されたゲルコート樹脂層３の表面を機械研磨して目粗しすることにより、ゲルコート樹脂層３に含まれるルチル型酸化チタン５の一部、水酸化アルミニウム６の一部および／または二酸化珪素（ＳｉＯ２）７の一部をゲルコート樹脂層３の表面に露出させる。 Finally, a part of the rutile titanium oxide 5 contained in the gel coat resin layer 3 is obtained by mechanical polishing and roughening the surface of the gel coat resin layer 3 integrated with the surface of the demolded FRP molded product 1. Then, a part of aluminum hydroxide 6 and / or a part of silicon dioxide (SiO 2 ) 7 is exposed on the surface of the gel coat resin layer 3.
本発明に用いる成形型８は、脱型後ＦＲＰ成形品１の表面を研磨処理することから、成形型１の表面加工精度は特に限定されるものではない。前述したように、未硬化ゲルコート樹脂に前もって塗布する離型剤が残存しないように、平滑であることが望ましい。 Since the mold 8 used in the present invention polishes the surface of the FRP molded product 1 after demolding, the surface processing accuracy of the mold 1 is not particularly limited. As described above, it is desirable to be smooth so that the release agent applied in advance to the uncured gel coat resin does not remain.
本発明に係わるＦＲＰ成形品１の成形方法としては、成形型８に未硬化ゲルコート樹脂を塗布した後、ＦＲＰスキン材２を構成する補強繊維基材、マトリクス樹脂と一体化する成形法であれば、特に限定するものではない。 The molding method of the FRP molded product 1 according to the present invention is a molding method in which an uncured gel coat resin is applied to the molding die 8 and then integrated with the reinforcing fiber base material and the matrix resin constituting the FRP skin material 2. There is no particular limitation.
成形型８に未硬化ゲルコート樹脂を塗布した後、補強繊維基材を積層し、未硬化マトリクス樹脂を補強繊維基材に含浸し、硬化させる成形法（ハンドレイアップ法、スプレーアップ法、レジントランスファーモールディング法、レジンインジェクションモールディング法、ＳＣＲＩＭＰ法、ＶＡＲＩ法、ＲＩＶ法等）、成形型８に未硬化ゲルコート樹脂を塗布した後、半硬化状態のマトリクス樹脂を含浸させた補強繊維基材を積層し、硬化させる成形法（オートクレーブ法、ＳＭＣ法、ＢＭＣ法等）が好ましい。 A molding method (hand lay-up method, spray-up method, resin transfer) in which an uncured gel coat resin is applied to the mold 8 and then a reinforcing fiber base material is laminated and the reinforcing fiber base material is impregnated and cured. Molding method, resin injection molding method, SCRIMP method, VARI method, RIV method, etc.), after applying uncured gel coat resin to molding die 8, laminating a reinforcing fiber base impregnated with a semi-cured matrix resin, A curing method (autoclave method, SMC method, BMC method, etc.) for curing is preferred.
なお、引き抜き成形等の連続成形しようとした場合には、ゲルコート表面が未硬化となるため、ゲルコート樹脂にパラフィンを添加し、表面に偏析させることによって空気遮断し、表面まで硬化させるトップコート処理が必要となる。このようなトップコートでは、後述するようにゲルコート樹脂層３の内部でルチル型酸化チタン５等を表面近傍に高濃度に分布させることが困難となる。このため、ゲルコート樹脂層３が下面に塗布できるような、バッチ処理による成形型を用いることが好ましい。 In addition, when continuous molding such as pultrusion molding is attempted, the gel coat surface becomes uncured, so paraffin is added to the gel coat resin, and the surface is segregated on the surface to block air and cure to the surface. Necessary. In such a top coat, it becomes difficult to distribute the rutile type titanium oxide 5 and the like in a high concentration in the vicinity of the surface inside the gel coat resin layer 3 as described later. For this reason, it is preferable to use the shaping | molding die by a batch process so that the gel coat resin layer 3 can be apply | coated to a lower surface.
また、ルチル型酸化チタン５の比重は未硬化ゲルコート樹脂の比重の約３倍であるため、上述の成形法で成形型８に未硬化ゲルコート樹脂を吹き付けた後、硬化するまでの時間内にルチル型酸化チタン５はゲルコート樹脂層３内の成形型表面側の濃度が高くなるように分布する。このような分布が形成されることで、成形型８から脱型して得られたＦＲＰ成形品１の表面に存在するゲルコート樹脂層３の表面側においてルチル型酸化チタン５の濃度が高くなるため、光触媒機能を発揮するのに好都合となる。 In addition, since the specific gravity of the rutile titanium oxide 5 is about three times the specific gravity of the uncured gel coat resin, the rutile type titanium oxide 5 has a rutile within the time until it is cured after the uncured gel coat resin is sprayed on the mold 8 by the molding method described above. The mold titanium oxide 5 is distributed so that the concentration on the surface side of the mold in the gel coat resin layer 3 is increased. By forming such a distribution, the concentration of the rutile type titanium oxide 5 is increased on the surface side of the gel coat resin layer 3 existing on the surface of the FRP molded product 1 obtained by demolding from the mold 8. It is convenient to exert a photocatalytic function.
上述のＦＲＰ成形法では、成形型８から脱型したままではルチル型酸化チタン５がゲルコート樹脂層３の表面には露出しないため、ルチル型酸化チタン５は無機顔料として機能するのみであり、光触媒機能を得ることができない。本発明のＦＲＰ成形品１は、成形型８から脱型した後、ゲルコート樹脂層３の表面を機械研磨することにより、ルチル型酸化チタン５を表面に露出させ、光触媒機能を得ることができる。 In the above-described FRP molding method, the rutile titanium oxide 5 is not exposed on the surface of the gel coat resin layer 3 as it is removed from the mold 8, so that the rutile titanium oxide 5 only functions as an inorganic pigment and is a photocatalyst. Can't get function. After the FRP molded product 1 of the present invention is removed from the mold 8, the surface of the gel coat resin layer 3 is mechanically polished to expose the rutile titanium oxide 5 on the surface, thereby obtaining a photocatalytic function.
本発明ではゲルコート樹脂層３の表面にルチル型酸化チタン５を露出させるためにゲルコート樹脂層３を研磨処理する。研磨処理としては機械研磨が好ましく、具体的な機械研磨方法としては、サンドブラスト、サンドペーパー、砥石等、特に限定するものではない。 In the present invention, the gel coat resin layer 3 is polished to expose the rutile titanium oxide 5 on the surface of the gel coat resin layer 3. The polishing treatment is preferably mechanical polishing, and the specific mechanical polishing method is not particularly limited, such as sandblasting, sandpaper, and a grindstone.
機械研磨後のゲルコート樹脂層３の算術平均表面粗さ（ＪＩＳ Ｂ ０６５１（２００１））は０．１μｍ〜１０μｍであることが好ましい。算術平均表面粗さが０．１μｍより小さいとゲルコート樹脂層３表面と水滴との接触角が大きくなり、親水性が低下して汚れが付着しやすくなる。１０μｍを越えると、親水性の低下はみられないが、機械研磨作業に手間がかかることがある。 The arithmetic average surface roughness (JIS B 0651 (2001)) of the gel coat resin layer 3 after mechanical polishing is preferably 0.1 μm to 10 μm. When the arithmetic average surface roughness is less than 0.1 μm, the contact angle between the surface of the gel coat resin layer 3 and the water droplets is increased, the hydrophilicity is lowered, and dirt is easily attached. When the thickness exceeds 10 μm, no decrease in hydrophilicity is observed, but the mechanical polishing work may be troublesome.
以上の本発明の防音壁の実施例について説明する。 Examples of the above-described soundproof wall of the present invention will be described.
図４に本発明のＦＲＰ成形品１の製造工程の一例を示す。 FIG. 4 shows an example of the manufacturing process of the FRP molded product 1 of the present invention.
まず、ゲルコート樹脂層３としてルチル型酸化チタン５を７重量％、水酸化アルミニウム６を２０重量％、二酸化珪素７を３重量％含有するように配合された未硬化ゲルコート樹脂を離型処理された成形型８に吹き付けた。 First, an uncured gel coat resin blended so as to contain 7% by weight of rutile type titanium oxide 5, 20% by weight of aluminum hydroxide 6 and 3% by weight of silicon dioxide 7 as a gel coat resin layer 3 was subjected to a release treatment. The mold 8 was sprayed.
次に、ゲルコート樹脂がゲル化した状態で、ＦＲＰスキン材２を構成する補強繊維基材としてガラスチョップドストランドマット基材、ガラス０°／９０°／ガラスチョップドストランドマット基材、炭素繊維基材を積層し、不飽和ポリエステル樹脂を含浸させた。その後、成形型８を硬化炉で６０℃で２時間硬化させた後、成形型８から脱型し、ＦＲＰスキン材２の表面がゲルコート樹脂層３で覆われたＦＲＰ成形品を得た。 Next, a glass chopped strand mat substrate, a glass 0 ° / 90 ° / glass chopped strand mat substrate, and a carbon fiber substrate are used as the reinforcing fiber substrate constituting the FRP skin material 2 in a state where the gel coat resin is gelled. Laminated and impregnated with unsaturated polyester resin. Thereafter, the mold 8 was cured at 60 ° C. for 2 hours in a curing furnace, and then removed from the mold 8 to obtain an FRP molded product in which the surface of the FRP skin material 2 was covered with the gel coat resin layer 3.
得られたＦＲＰ成形品のゲルコート樹脂層３の表面を住友３Ｍ株式会社製スコッチブライト（登録商標）８４４８にて機械研磨により目粗しを行い、ルチル型酸化チタン５の一部、水酸化アルミニウム６の一部および二酸化珪素７の一部がゲルコート樹脂層３の表面に露出したＦＲＰ成形品Ａを得た。 The surface of the gel coat resin layer 3 of the obtained FRP molded product is roughened by mechanical polishing with Scotch Bright (registered trademark) 8448 manufactured by Sumitomo 3M Co., Ltd., and a part of the rutile titanium oxide 5, aluminum hydroxide 6 An FRP molded product A in which a part of the silicon dioxide 7 and a part of the silicon dioxide 7 were exposed on the surface of the gel coat resin layer 3 was obtained.
防汚性の比較テストのために、同様の方法で成形を行い、成形型から脱型したまま、ゲルコート樹脂層表面の機械研磨をおこなっていない成形品Ｂを得た。 For a comparison test of antifouling properties, molding was performed in the same manner, and a molded product B in which the gel coat resin layer surface was not mechanically polished was obtained while being removed from the mold.
このようにして得られたＦＲＰ成形品Ａ、ＦＲＰ成形品Ｂをゲルコート樹脂層が鉛直方向となるように屋外に１２ヶ月間放置し、ゲルコート樹脂層表面の汚染度合いを目視評価した。 The FRP molded product A and the FRP molded product B thus obtained were left outdoors for 12 months so that the gel coat resin layer was in the vertical direction, and the degree of contamination on the surface of the gel coat resin layer was visually evaluated.
図５に示すように、ゲルコート樹脂層表面を研磨していないＦＲＰ成形品Ｂは雨水の道筋に沿った黒色の汚染物質の付着が見られるのに対し、本発明のＦＲＰ成形品Ａは汚染物質の付着が見られなかった。 As shown in FIG. 5, the FRP molded product B in which the surface of the gel coat resin layer is not polished shows adhesion of black contaminants along the rainwater path, whereas the FRP molded product A of the present invention is contaminated with contaminants. The adhesion of was not seen.
本発明は、防汚性が必要なＦＲＰ成形品に適用できる。鉄道用の防音壁や高欄、道路などに設けられる防音壁、建材、冷却塔筐体、遊具、ボートなどの屋外で使用されるＦＲＰ成形品の他、屋内で使用されるＦＲＰ成形品にも利用できる。 The present invention can be applied to FRP molded products that require antifouling properties. Used for soundproof walls for railroads, railings, road walls, building materials, cooling tower housings, playground equipment, FRP molded products used outdoors such as boats, and FRP molded products used indoors it can.
１：ＦＲＰ成形品
２：ＦＲＰスキン材
３：ゲルコート樹脂層
４：ゲルコートベース樹脂
５：ルチル型酸化チタン
６：水酸化アルミニウム
７：二酸化珪素
８：成形型
1: FRP molded product 2: FRP skin material 3: Gel coat resin layer 4: Gel coat base resin 5: Rutile titanium oxide 6: Aluminum hydroxide 7: Silicon dioxide 8: Mold
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