TW201026497A - Functional panel - Google Patents
Functional panel Download PDFInfo
- Publication number
- TW201026497A TW201026497A TW098125136A TW98125136A TW201026497A TW 201026497 A TW201026497 A TW 201026497A TW 098125136 A TW098125136 A TW 098125136A TW 98125136 A TW98125136 A TW 98125136A TW 201026497 A TW201026497 A TW 201026497A
- Authority
- TW
- Taiwan
- Prior art keywords
- acrylate
- meth
- photopolymerizable
- functional panel
- monomer
- Prior art date
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- 239000000178 monomer Substances 0.000 claims abstract description 60
- 239000011342 resin composition Substances 0.000 claims abstract description 31
- 239000010410 layer Substances 0.000 claims abstract description 27
- 239000011247 coating layer Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 67
- -1 isodecyl (decyl) acrylate Chemical compound 0.000 claims description 66
- 239000000126 substance Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 17
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 9
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- ZLWGPFAPFZOSIO-UHFFFAOYSA-N 3,3-bis(1H-inden-1-yl)prop-2-enoic acid Chemical compound C1(C=CC2=CC=CC=C12)C(=CC(=O)O)C1C=CC2=CC=CC=C12 ZLWGPFAPFZOSIO-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- WJMQOVJVBXJQGM-UHFFFAOYSA-N C(CCCCCCCCC)C(=CC(=O)OCCCCCCCCCO)CCCCCCCCCC Chemical compound C(CCCCCCCCC)C(=CC(=O)OCCCCCCCCCO)CCCCCCCCCC WJMQOVJVBXJQGM-UHFFFAOYSA-N 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IBPADELTPKRSCQ-UHFFFAOYSA-N 9h-fluoren-1-yl prop-2-enoate Chemical compound C1C2=CC=CC=C2C2=C1C(OC(=O)C=C)=CC=C2 IBPADELTPKRSCQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
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- BGKZULDOBMANRY-UHFFFAOYSA-N sulfanyl prop-2-enoate Chemical compound SOC(=O)C=C BGKZULDOBMANRY-UHFFFAOYSA-N 0.000 description 3
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- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- DAWJJMYZJQJLPZ-UHFFFAOYSA-N 2-sulfanylprop-2-enoic acid Chemical compound OC(=O)C(S)=C DAWJJMYZJQJLPZ-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
- E04F13/18—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements of organic plastics with or without reinforcements or filling materials or with an outer layer of organic plastics with or without reinforcements or filling materials; plastic tiles
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- C—CHEMISTRY; METALLURGY
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
Description
201026497 六、發明說明： 【發明所屬之技術領域】 本發明係關於藉由利用含有特定的光聚合性 硬化性樹脂組成物來提高耐藥品性及财染色性之= 板》 功能性面 【先前技術】 作為建築材料使用< χ力能性面板剌 面、地板或天花板的壁面所設置之建材，配2揭的壁 而:皮賦予隔音效果或濕度調節性等各種功能：點 =材時，要求需具傷可抵抗在更嚴苛=以環 防水性、耐濕性等各種特性。 用衣i兄下之 了-平第U·2。112號公報)中揭示 紫外線料ΐ 表面的下塗膜上，再進一步形成由 ❹ 妬。、” ’丙烯酸酯樹脂塗料所形成的上塗膜之装錦 产用逮ΐ文獻中記载了將該裝飾板作為如上所述之有水環 ^、於、_而使用時具有良好的抗溫水性、硬度特性、厚實 a Μ染性等’且不料發生膨脹㈣落等情況。 ^方面，近年來在住宅内的壁面，特別是浴室、洗 色i或蔚房使用含有酸等強刺激性的清潔劑或染髮劑等染 ΛΙ·機會增加’因這些藥劑附著而造成不只是壁面會產 化是A劣化，亦會引起變色或染色。毋須贅言變質或劣 希望發生的現象’且一但產生變色便無法回復到原 201026497 來的顏色’此外染色發生時，隨著時間增加要回復到原來. =顏色越發_亦為林望變色錢色現象發生的原因。’ 於此種地點之功能性面板被要求為一種可抗清潔劑或 =色劑的使用，且不會產生變質或劣化、變色或染色之面 然而，如專利文獻中所揭示，形成有上塗膜之功能性 面反作為面板在更嚴苛的使用環境下使用時，對這些 ，染色劑造成的所有的變質、劣化、變色及染色：不二 定可發揮充分的耐受性，而依然有改善的餘地。 ❹ 【發明内容】 因此，本發明之目的係為提供一種不只是可抗因近年 來使用頻度增加之強刺激性清潔劑或染髮劑等染色劑造成 的變質或劣化的發生’亦可抗變色或染色的發生之功能面 板。 本發明之發明者為解決上述課題，發現藉由利用具有 特定的溶解參數(sp值)之光聚合性單體及特定的玻璃^移 溫度之光硬化性樹脂組成物，可獲得具有良好的耐藥品性 及耐染色性之功能性面板，進而完成本發明。 、 亦即，本發明之功能性面板之特徵在於包含··由溶解 參數(SP值）為20.0(J/Cmy.5以下之光聚合性單體及光聚合 性寡聚物所形成的光硬化性樹脂組成物加以硬化所構成^ 玻璃轉移溫度為50°C以上之塗佈層，·及基材層。 又，該光聚合性單體較㈣τ列式⑴巾所表示的軍體。 4 201026497 (CH2 = CR1CO〇)nR2 .......⑴ (式⑴中’ R1係表示氫原子或甲基，R2係表示碳數為 5〜20之η價的煙基’ n係表示1〜4之整數）。 ❹[Technical Field] The present invention relates to the use of a composition containing a specific photopolymerizable curable resin to improve chemical resistance and chemical dyeability. 】 As building materials, use the building materials provided on the wall surface of the enamel panel, the floor or the ceiling, and the wall that is exposed: the skin gives various functions such as sound insulation or humidity adjustment: when the material is required It needs to be damaged to resist the more stringent = ring waterproof, moisture resistance and other characteristics. In the undercoat film of the surface of the ultraviolet material ,, it is further formed by the i 妒 下 平 平 - - - U 妒 妒 妒 妒 妒 妒 妒 妒 妒 妒 妒 妒 妒 妒. "In the literature on the use of the upper coating film formed by the acrylate resin coating, the decorative sheet has a good temperature resistance when used as a water ring as described above. Water, hardness, thick a, dyeing, etc. 'Unexpected expansion (four) falling, etc. ^ In recent years, in the wall of the house, especially in the bathroom, wash i or Wei room use strong acid and other irritant Dyeing agents such as detergents or hair dyes, and increased chances. 'Because of the adhesion of these agents, not only the wall will be produced, but also A will be degraded, and it will cause discoloration or dyeing. It is necessary to say that the phenomenon of deterioration or inferiority occurs. I can't revert to the original 201026497 color'. In addition, when the dyeing occurs, it will return to the original with the increase of time. The color is more and more _ is also the reason why the color change occurs. 'The functional panel at this location is It is required to be an anti-cleaning agent or a coloring agent without causing deterioration or deterioration, discoloration or dyeing. However, as disclosed in the patent literature, the functional surface of the upper coating film is formed as an inverse When the panel is used in a more severe use environment, all the deterioration, deterioration, discoloration and dyeing caused by the dyeing agent can be fully tolerated, and there is still room for improvement. Therefore, the object of the present invention is to provide an anti-discoloration or dyeing occurrence which is not only resistant to deterioration or deterioration caused by a strong irritating detergent or hair dye such as a dyeing agent which has been frequently used in recent years. In order to solve the above problems, the inventors of the present invention have found that a photocurable resin having a specific dissolution parameter (sp value) and a photocurable resin composition having a specific glass transition temperature can be obtained. The functional panel having good chemical resistance and dyeing resistance further completes the present invention. That is, the functional panel of the present invention is characterized by containing a dissolution parameter (SP value) of 20.0 (J/Cmy. a photocurable resin composition of 5 or less photopolymerizable monomers and a photocurable resin composition which is cured to form a coating layer having a glass transition temperature of 50 ° C or higher, and Further, the photopolymerizable monomer is more than the military body represented by (4) tau (1) towel. 4 201026497 (CH2 = CR1CO〇) nR2 (1) (In the formula (1), R1 represents a hydrogen atom. Or a methyl group, and R2 represents a nicotinyl group having a carbon number of 5 to 20, and the n-form represents an integer of 1 to 4.)
再者，該光聚合性單體較佳係由異莰基（甲基）丙烯酸 醋、1，6-己一醉一（曱基）丙婦酸@旨、二經甲基三環癸烧基二 (甲基）丙稀酸酉曰、異戊基（甲基）丙婦酸醋、十二烧基（甲基) 丙稀酸酯、十三烷基（曱基）丙烯酸酯、異肉豆蔻基（曱基）丙 烯酸酯、十八烷基（甲基）丙烯酸酯、3_甲基_1>5_戊二醇二（曱 基）丙烯酸酯、新戊二醇二（曱基）丙烯酸酯、環己烷二甲醇 二（甲基）丙烯酸酯、1，9-壬二醇二（曱基）丙烯酸酯、三羥甲 基丙烷二（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯所組 成之群選出的至少1種的單體。 入，该光知合性皁體與該光聚合性寡聚物的調配量較 佳係質量比為70 : 30〜30 : 70的量。 再者’該基材層較佳係由含有不飽和聚醋樹脂、填充 1及破璃纖維或碳纖維之材質所構成。 性，本I月^功此性面板具有良好的耐藥品性及耐染色 可柄附著有含酸之清潔劑或㈣劑等染色劑，不只是 發明/f或劣化’村充分抑㈣色絲色。因此，本 :或蔚;力;===:為住宅内的浴室、洗臉 層等复仙A 兄用建材。此外，並非一定要形成下塗 址成物所I):之基特定的光硬化性樹脂 3：怖增’便可輕易實現具有優異的耐藥品 5 201026497 性及耐染色性之功能性面板。 特別是使用含不飽和聚酯 碳纖維之材料來作為基材時， 良好的耐久性之功能性面板。 樹脂、填充劑及玻璃纖維或 可獲得具有該等特性以及更 【實施方式】 以下’針對本發明詳細說明。 二性面板之特徵在於包含：由溶解參數⑽ =)為20.0(J/C叶以下之光聚合性單體及光聚合性寡聚物〇 所形成的光硬化性樹脂組成物加以硬化所構成且玻璃轉移 溫度為50oC以上之塗佈層；及基材層。 [光聚合性單體] 使用於上述光硬化性樹脂組成物之光聚合性單體的特 徵為溶解參數(SP值)在20.0(J/cm3)〇.5以下。該SP值⑹一 般係以下式之液體的莫爾蒸發能量(ΔΕν)及莫爾體積(v)來 定義。 SP 值(δ) =(δΕν/ν)0·5 再者，根據 Fedors 法，SP 值（Solubility Parameter Values;溶解參數值）可只由化學構造來推算（參照由j. Brandrup及其他所編者所編集的第4版「p〇iymer Handbook」）。此外，本說明書中之SP值係指利用Fedors 法所算出之值，該值愈低表示光聚合性單體的極性愈低。 上述光聚合性單體的SP值較佳地為19.6(J/cm3)Q·5以下，更 201026497 當為具有此種SP值之絲合性單麟，職後述之光 聚合性寡聚物有良好的相雜，並可有效地降低該單體本 身具有的極性。再者’由於所使㈣絲合性單體為低極 性’因此推測將由其所獲得的光聚合性樹脂組成物加以硬 化以形成塗佈層時，可充分抑制硬化後之塗佈層本身的反Further, the photopolymerizable monomer is preferably an isodecyl (meth) acrylate vinegar, a 1,6-hexa-indole (indenyl) acetoacetate, and a di-methyl-tricyclic fluorenyl group. Bis(di)methyl acrylate, isoamyl (methyl) acetoacetate, dodecyl (meth) acrylate, tridecyl (decyl) acrylate, isomyristyl Base (mercapto) acrylate, octadecyl (meth) acrylate, 3-methyl-1> 5-pentanediol bis(indenyl) acrylate, neopentyl glycol bis(indenyl) acrylate , cyclohexanedimethanol di(meth)acrylate, 1,9-nonanediol bis(indenyl)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tetra(meth)acrylate At least one monomer selected from the group consisting of. The amount of the photosynthetic oligomer and the photopolymerizable oligomer is preferably 70:30 to 30:70 by mass ratio of the photopolymerizable oligomer. Further, the base material layer is preferably made of a material containing an unsaturated polyester resin, a filler 1, a glass fiber or a carbon fiber. Sexuality, this I month ^ function of this panel has good chemical resistance and dyeing resistant to the acid-containing detergent or (four) agent and other dyes, not only invented / f or deteriorated 'village full (four) color silk color . Therefore, this: or Wei; force; ===: for the bathroom in the house, wash the face and other Fuxian A brother building materials. Further, it is not necessary to form a lower-coated object I): a base-specific photocurable resin 3: a sharp increase can easily realize a functional panel having excellent resistance to chemicals 5 201026497 and dye resistance. In particular, when a material containing an unsaturated polyester carbon fiber is used as a substrate, a functional panel having good durability is used. The resin, the filler, and the glass fiber may be obtained by having such characteristics and more. [Embodiment] Hereinafter, the present invention will be described in detail. The amphoteric panel is characterized in that it consists of a photocurable resin composition formed by a photopolymerizable monomer having a solubility parameter (10) = 20.0 (J/C leaf or less and a photopolymerizable oligomer 加以), and is cured. A coating layer having a glass transition temperature of 50 ° C or more; and a substrate layer. [Photopolymerizable monomer] The photopolymerizable monomer used in the above photocurable resin composition is characterized in that the dissolution parameter (SP value) is 20.0 ( J/cm3) 〇.5 or less. The SP value (6) is generally defined by the Moire's evaporation energy (ΔΕν) and the Mohr volume (v) of the liquid of the following formula: SP value (δ) = (δΕν/ν)0· 5 Furthermore, according to the Fedors method, the SP value (Solubility Parameter Values) can be estimated only from the chemical structure (refer to the fourth edition "p〇iymer Handbook" compiled by j. Brandrup and other editors). Further, the SP value in the present specification means a value calculated by the Fedors method, and the lower the value, the lower the polarity of the photopolymerizable monomer. The SP value of the photopolymerizable monomer is preferably 19.6 (J/). Cm3) Q·5 or less, more 201026497 When it is a silky single lining with such SP value, the light gathering after the job The oligo oligopolymer has good miscibility and can effectively reduce the polarity of the monomer itself. Furthermore, the photopolymerization property obtained from the silane oligomer is presumably due to the low polarity of the (4) silky monomer. When the resin composition is hardened to form a coating layer, the reverse of the coating layer itself after hardening can be sufficiently suppressed.
❹ 應性。如此，形成有上㈣佈狀本發明之功能性面板不 會和清潔劑或染色劑等產生不必要的反應，而可發現具有 良好的耐藥品性及财染色性。特财在耐染色性上發揮了 顯者的效果。 上述光聚合性單體較佳地為具有丨個以上的丙烯醯氧 基(CH2 = CHCOO-)或甲基丙烯醯氧基(Ch2 = c(CH3)c〇〇_) 之（甲基）丙烯酸酯單體，亦可為單官能性單體、雙官能性單 體及多官能性單體中之任一者。 單官能性單體譬如有：異莰基（甲基）丙烯酸酯、莰基（甲 基）丙烯酸酯、三環癸基（甲基）丙烯酸酯、二環戊基（甲基） 丙烯酸酯、二環戊烯基（甲基）丙烯酸酯、環己基（甲基）丙烯 酸醋，之脂環式(曱基)丙烯酸醋；节基(甲基)丙稀酸醋、4_ 丁基環己基（甲基）丙稀酸酯、（甲基）丙烯醯基嗎呋琳、2_羥 乙基（甲基）丙烯酸酯、2-羥丙基（甲基）丙烯酸酯、2_羥丁基 (甲基）丙烯酸酯、f基（甲基）丙烯酸酯、乙基（甲基）丙烯酸 酯、丙基（甲基）丙烯酸酯、異丙基（甲基）丙烯酸酯、丁基（甲 基）丙烯酸酯、戊基（甲基）丙烯酸酯、異丁基（甲基）丙烯酸 7 201026497 酯、第三丁基（曱基)丙烯酸酯、戊基（甲基）丙烯酸酯、異戊 基（曱基）丙烯酸酯、己基（甲基）丙烯酸酯、庚基（曱基）丙烯 酸酯、辛基（曱基）丙烯酸酯、異辛基（曱基）丙烯酸酯、2_乙 基己基（曱基）丙烯酸酯、壬基（曱基）丙烯酸酯、癸基（曱基） 丙烯酸酯、異癸基（曱基）丙烯酸酯、十一烷基（曱基）丙烯酸 酯、十二烷基（曱基）丙烯酸酯、月桂基（曱基）丙烯酸酯、十 八烷基（甲基）丙烯酸酯、十四烷基（甲基）丙烯酸酯、十六烷 基（曱基）丙烯酸酯、異十八烷基（甲基）丙烯酸酯、四氫呋喃 (甲基）丙烯酸酯、丁氧基乙基（甲基）丙烯酸酯、乙氧基二乙❹ 二醇（曱基）丙烯酸酯、聚氧伸乙基壬基苯基乙醚丙烯酸酯、 苯氧基乙基（曱基）丙烯酸酯、聚乙二醇單（曱基）丙烯酸酯、 =丙二醇單（曱基）丙烯酸酯、甲氧基乙二醇（曱基）丙烯酸 酉曰、乙氧基乙基（曱基）丙烯酸酯、甲氧基聚乙二醇（曱基）丙 稀酉文s曰、甲氧基聚丙二醇（甲基）丙烯酸酯、二甲基胺基乙基 (甲基)丙烯酸醋、二乙基胺基乙基（甲基)丙婦酸酯、7_胺基 '3,7-二甲基辛基（曱基）丙烯酸醋；乙时架（曱基)丙烯酸酯 類等。 ❹ —雙吕能性單體譬如有：乙二醇二（甲基）丙烯酸醋、四乙 二醇二(曱基)丙烯酸醋、三乙二醇二（曱基)丙烯酸醋、1,4-丁:醇一（甲基)丙稀酸醋、^卜己二醇二（甲基)丙稀酸醋、新 戊二醇二(曱基)丙烯酸®旨、參(2·經乙基)異三聚氰酸二(曱基） 丙稀酸醋、三環癸燒二甲醇二(甲基)丙輪旨、二經甲基三 環癸烧二（曱基)丙烯酸酉旨、雙酴A之環氧燒加成二醇之二 (甲基)丙烯酸酯、氫化雙齡A之環氧垸加成二醇之二（甲基） 201026497 • 稀酸知、於雙紛A之二環氧丙基醚上加成（甲基）丙烯酸 -曰之環氧（甲基)丙烯酸酯等。 酽夕g能性單體譬如有：三羥曱基丙烷三（曱基）丙烯酸 ^乙氧基化三羥曱基丙烷三（甲基）丙烯酸酯、丙氧基化三 二甲基丙烷三（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸 酉曰季戊四醇四（曱基）丙烯酸酯、二季戊四醇六（曱基）丙烯 酸^西t ——、 一一經曱基丙烧四（甲基）丙烯酸醋、二季戊四醇單羥 ❹ 基五（甲基）丙烯酸酯等。 可使用單獨1種該等光聚合性單體，亦可將2種以上 加以組合使用。 η此外’使用2種以上光聚合性單體時的δρ值係指將各 =單體具有的SP值分別乘上各個單體的調配比例（以單體 王邛的畺為1時各單體的比例）後，並把這些值加總的意 思。譬如，相對於光聚合性單體全部的量為丨，當將sp值 為19.0之光聚合性單體以3/4的量、sp值為21〇之光聚合 ❿ 性單體以1/4的量調配時，依照下列式(X)來求得所使用之 光聚合性單體整體的SP值。 光聚合性單體的 SP 值= (19.0x3/4)+(21.〇x 1/4)= 19.5· ••(X) 上述光聚合性單體中’較佳係下列式（1)所表示的單體。 (^-CR'COO^R2 ....... (1) 上述式（1)中’ Rl係表示氫原子或曱基。 9 201026497 上述式（1)中’ R2係表示碳數5〜2〇之n價的烴基，且 不含雜原子，亦可為鏈狀或環狀。又，其中的七^^可以_CH = CH-來取代。n係表示1〜4之整數。 亦即，上述式（1)中’譬如為鏈狀之飽和單體時，n=1 時R2為碳數5〜20之烷基，n= 2時R2為碳數5〜20之伸烷 基。再者，為鏈狀之飽和單體時，n=3時R2為碳數5〜20 之烷三基(alkane-triyl) ’ n=4時R2為碳數5〜20之烷四基 (alkane-tetrayl)。此種 R2 可為譬如_CH2CH3、-CH2CH2CH3、 -CH(CH3)CH3、環己基、環庚烷基、環辛烷基、環壬烷基、〇 環癸烷基等烷基；-ch2ch2-、-CH2CH2CH2·、-ch(ch3)ch2- 等伸烷基；以及下列式(2)所表示的烷三基、下列式(3)所表 示的烧四基等。 [化學式1] ch2❹ Dependability. Thus, the functional panel of the present invention formed with the upper (four) cloth does not cause an unnecessary reaction with a detergent or a dye, and can be found to have good chemical resistance and chemical dyeability. Special wealth has played a significant role in dye resistance. The photopolymerizable monomer is preferably a (meth)acrylic acid having more than one propylene oxy group (CH2 = CHCOO-) or methacryloxy group (Ch2 = c(CH3)c〇〇_). The ester monomer may also be any of a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer. Monofunctional monomers such as: isodecyl (meth) acrylate, decyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentyl (meth) acrylate, two Cyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, alicyclic (fluorenyl) acrylate; benzyl (meth) acrylate, 4 - butyl cyclohexyl (methyl ) acrylate, (meth) propylene hydrazinoline, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (methyl) Acrylate, f-based (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentane Base (meth) acrylate, isobutyl (meth) acrylate 7 201026497 ester, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (decyl) acrylate, Hexyl (meth) acrylate, heptyl (decyl) acrylate, octyl (decyl) acrylate, isooctyl (decyl) propyl Acid ester, 2-ethylhexyl (decyl) acrylate, fluorenyl (fluorenyl) acrylate, fluorenyl (fluorenyl) acrylate, isodecyl (decyl) acrylate, undecyl (fluorenyl) Acrylate, dodecyl (mercapto) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, tetradecyl (meth) acrylate, cetyl (fluorenyl) acrylate, isostearyl (meth) acrylate, tetrahydrofuran (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene diol Acrylate, polyoxyethylene ethyl phenyl ether acrylate, phenoxyethyl (decyl) acrylate, polyethylene glycol mono(decyl) acrylate, = propylene glycol mono(decyl) acrylate , methoxyethylene glycol (mercapto) ruthenium acrylate, ethoxyethyl (decyl) acrylate, methoxy polyethylene glycol (fluorenyl) propylene sulfonium sulfonate, methoxypolypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( Yl) propionic acid ester women, amine 7_ '3,7-dimethyloctyl (Yue-yl) acrylic acid vinegar; B frame time (Yue-yl) acrylate and the like. ❹ —Shuang Luneng monomer, such as: ethylene glycol di(meth)acrylic acid vinegar, tetraethylene glycol di(indenyl)acrylic acid vinegar, triethylene glycol di(indenyl)acrylic acid vinegar, 1,4- D: Alcohol mono(methyl) acrylate vinegar, hexane hexane di(methyl) acrylate vinegar, neopentyl glycol bis(indenyl) acrylate acetal, ginseng (2 · ethyl) Di-(indenyl) acrylic acid vinegar, tricyclic tert-doped dimethanol di(methyl)propane, di-methyl-tricycloanthracene di(indenyl)acrylic acid, and diterpene A Di(meth)acrylate of epoxidized addition diol, bis(methyl) of hydrogenated ruthenium addition diol of hydrogenated double age A 201026497 • Diacid known, di-epoxypropyl group An epoxy (meth) acrylate such as (meth)acrylic acid-ruthenium is added to the ether.酽 g g energy monomer such as: trihydroxy decyl propane tris(fluorenyl) acrylate ethoxylated trihydroxy decyl propane tri (meth) acrylate, propoxylated tri dimethyl propane three ( Methyl) acrylate, pentaerythritol tris (meth) acrylate pentaerythritol tetrakis(meth) acrylate, dipentaerythritol hexa(indenyl) acrylate ^ xi ——, 一 曱 丙 丙 四 ( (M) Acrylic vinegar, dipentaerythritol monohydroxydecylpenta(meth)acrylate, and the like. A single photopolymerizable monomer may be used alone or two or more of them may be used in combination. η In addition, the δρ value when two or more photopolymerizable monomers are used means that the SP value of each monomer is multiplied by the mixing ratio of each monomer (the monomer is 1 when the 邛 of the monomer is 1). After the ratio), add the meaning of these values to the total. For example, the total amount of the photopolymerizable monomer is 丨, and when the photopolymerizable monomer having an sp value of 19.0 is in an amount of 3/4, the photopolymerizable monomer having an sp value of 21 以 is 1/4. When the amount is adjusted, the SP value of the entire photopolymerizable monomer to be used is determined according to the following formula (X). SP value of the photopolymerizable monomer = (19.0x3/4) + (21.〇x 1/4) = 19.5· ••(X) Among the above photopolymerizable monomers, 'the preferred one is the following formula (1) The monomer represented. (^-CR'COO^R2 . . . (1) In the above formula (1), 'Rl represents a hydrogen atom or a fluorenyl group. 9 201026497 In the above formula (1), 'R2 represents a carbon number of 5~ 2 n n-valent hydrocarbon group, and does not contain a hetero atom, may also be a chain or a ring. Further, seven of them may be replaced by _CH = CH-. n is an integer of 1 to 4. In the above formula (1), when a saturated monomer is a chain, R2 is an alkyl group having 5 to 20 carbon atoms when n = 1, and R2 is an alkyl group having 5 to 20 carbon atoms when n = 2. When it is a chain-saturated monomer, when n=3, R2 is an alkane-triyl having a carbon number of 5 to 20 (nkane-triyl), and R2 is an alkanetetrayl group having a carbon number of 5 to 20 (alkane- Tetrayl. Such R2 may be an alkyl group such as _CH2CH3, -CH2CH2CH3, -CH(CH3)CH3, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, anthracenylalkyl; Ch2ch2-, -CH2CH2CH2, and -ch(ch3)ch2- are an alkylene group; and an alkanetriyl group represented by the following formula (2), a pyridyl group represented by the following formula (3), etc. [Chemical Formula 1] ch2
I ⑵ ❹ —CK2一"C —QSj*一·I (2) ❹ —CK2一"C —QSj*一·
I ca2 [化學式2]I ca2 [Chemical Formula 2]
I m2I m2
I —dj—：C—CH2— « ♦ ♦ (3) C02 10 201026497 R的碳數小於5時，當為鏈狀之烴基時單體的Sp值有 • 上昇的傾向，而當為環狀之烴基時則不容易取得。又，R2 的碳數超過20時，當為鏈狀之烴基時所獲得的光硬化性樹 脂組成物的破璃轉移溫度有降低的傾向，而當為環狀之烴 基時則所獲得的光硬化性樹脂組成物的交聯密度(cr〇sslink density)有降低的傾向。假設當交聯密度降得過低時由於 染髮劑等染色劑容易滲進塗佈層的内部，而使得面板有被 ❿ $色之虞。 上述式（1)所示的單體具體來說有：異莰基（曱基）丙烯 酸酯、1，6-己二醇二（曱基）丙烯酸酯、二經曱基三環癸烧基 二（曱基）丙烯酸酯、異戊基（曱基）丙烯酸酯、十二烷基（甲基) 丙烯酸酯、十三烷基（曱基）丙烯酸酯、異十四烷基（曱基）丙 稀酸酯、十八烷基（曱基）丙烯酸酯、3·甲基十^戍二醇二（甲 基）丙稀酸酯、新戊二醇二（曱基）丙烯酸酯、環己院二曱醇 二（甲基）丙烯酸酯、1,9-壬二醇二（曱基）丙烯酸酯、三羥曱 ❿ 基丙烷三（曱基）丙烯酸酯、季戊四醇四（曱基）丙烯酸酯。其 中，從提高玻璃轉移溫度的觀點來看，較佳地為具有環狀 烴基之單體，更佳地為異莰基（曱基）丙烯酸酯及二羥曱基三 環癸燒基二（曱基）丙烯酸酯。當為此種單體時，為了具有更 適合的SP值而顯示了良好的低極性傾向，並可更加提高所 獲得之功能性面板的耐藥品性及耐染色性。又，亦可有效 地發揮後述光聚合性寡聚物作為反應性稀釋劑之功能。 又，上述光聚合性單體的官能基數，通常為卜6，較佳 地為1〜4。此外，此處之官能基數係指由複數個分子來求得 201026497 基的數量’並將求得的官能基數量平均後作為1 六:六中具有的官能基數所換算的值。官能基數為1時， 有上昇的傾向，但藉由提高玻璃轉移溫度，而可 此!良好的耐藥品性及耐染色性之塗佈層所形成的功 :忠担ί。此時，較佳係利用具有環狀構造之光聚合性單 ::，坡螭轉移溫度。另-方面，官能基數為2〜6，較佳 : 夺由於有可適當地保持光硬化性組成物的交聯 傾向，故推測更容易有效地抑制特別是染色劑滲進 、内4而造成面板被染色的現象。因此，於此種情況 下亦可保持耐藥品性及耐染色性，並獲得具有良好的硬 Μ之塗佈層所形成的功能性面板。 [光聚合性募聚物] 使用於上述光硬化性樹脂組成物之光聚合性寡聚物具 體來說有譬如：胺酯系（曱基）丙烯酸酯寡聚物、環氧系（甲 基）丙烯酸酯寡聚物、乙醚系（曱基）丙烯酸酯募聚物、酯系 (曱基）丙烯酸酯募聚物、聚碳酸酯系（曱基）丙烯酸酯寡聚ζ 物、氟系（甲基)丙烯酸酯寡聚物、矽酮系（甲基）丙烯酸酯募 聚物等。該等光聚合性寡聚物可藉由使聚乙二醇、聚氧丙 二醇、聚四氫呋喃、雙酚Α型環氧樹脂、酚系酚醛清漆型 環氧樹脂、多元醇及ε-己内酯之加成物等與（曱基）丙烯酸進 行反應’或將聚異氰酸酯化合物及含有羥基之（曱基）丙烯酸 醋化合物進行胺醋化來合成。 上述光聚合性寡聚物可為單官能寡聚物、雙官能寡聚 12 201026497 物或多官能寡聚物中任一者，從實現所獲得的光硬化性樹 * 脂組成物之適當的交聯密度的觀點來看，較佳係多官能寡 聚物。 "亥#光聚合性养聚物當中，從作為功能性面板以賦予 良好的耐藥品性及耐染色性以外的特性之觀點來看，較佳 亦係胺酯系（曱基）丙烯酸酯募聚物。胺酯系（甲基）丙稀酸輯 春聚物，譬如可由聚醇與聚異氰酸醋來合成胺酯預聚物， ❹ 並藉由使該胺酯預聚物加成含有羥基之（甲基）丙嫦酸醋來 製造’亦可為含有碳酸酯骨架之胺酯系（曱基）丙烯酸酯寡聚 物。 在上述胺酯預聚物之合成中所使用的聚醇係含有複數 個經基(OH基)之化合物。具體來說有：聚鍵聚醇、聚酯聚 醇、聚四亞甲基二醇、聚丁二烯聚醇、環氧烧改質聚丁二 烯聚醇及聚異戊二烯聚醇等。可單獨使用1種該等聚醇， 亦可將2種以上加以組合使用。此外，上述聚醚聚醇可藉 φ 由加成聚合來獲得’譬如在乙二醇、丙二醇、丙三醇、三 趣甲基丙烧、季戊四醇、山梨醇等多元醇上，加成環氧乙 烷或環氧丙烷等環氧烷。又’亦可藉由開環聚合來獲得聚 醚聚醇，此種聚醚聚醇，譬如有藉由四氫呋喃(THF)之開環 聚合而獲得的聚四亞甲基二醇。 亦可藉由加成聚合來獲得上述聚酯聚醇，譬如：乙二 醇、二乙二醇、1,4-丁二醇、1,6-己二醇、丙二醇、三經甲 基乙烧、三經曱基丙燒專多元醇’以及己二酸、戊二酸、 丁二酸、癸二酸、庚二酸、辛二酸等多元碳酸來獲得。又， 13 201026497 亦可藉由開環聚合來獲得聚酯聚醇，此種聚酯聚醇有藉由 ε-己内酯之開環聚合而獲得的内酯系聚酯聚醇。 . 上述聚異氰酸酯係含有複數個異氰酸酯基(NCO基)之 化合物，具體來說有：曱苯二異氰酸酯(TDI)、二苯曱烷二 異氰酸酯(MDI)、粗製二苯曱烷二異氰酸酯（未加工MDI)、 異佛酮二異氰酸酯(IPDI)、氳化二苯甲烷二異氰酸酯、氫化 曱苯二異氰酸酯、六亞曱基二異氰酸酯(HDI)，或該等之異 三聚氰酸改質物、碳二醯亞胺改質物、二醇改質物等。可 使用早獨1種該等聚異氣酸g旨，亦可將2種以上加以組合❹ 來使用。 在進行上述胺醋預聚物的合成十，較佳地利用胺醋化 反應用之觸媒。該胺g旨化反應用觸媒有：二丁基锡二月桂 酸鹽、二丁基錫二醋酸鹽、二丁基錫硫羧酸鹽、二丁基錫 順丁浠一酸鹽、二辛基錫硫叛酸鹽、辛埽酸錫、單丁基錫 氧化物等有機錫化合物；氯化第一錫等無機錫化合物；辛 烯酸鉛等有機鉛化合物；三伸乙基二胺等環狀胺類；對甲 苯磺酸、曱磺酸、氟磺酸等有機磺酸；硫酸、磷酸、過氣❹ 酸等無機酸；曱醇納、氫氧化鐘、甲醇銘、氫氧化鈉等鹼 類；鈦酸四丁酯、鈦酸四乙酯、鈦酸四異丙酯等鈦化合物； 银化合物；喊銨鹽等。該等觸媒較佳地為有機錫化合物。 可使用單獨i種該等觸媒’亦可將2種以上加以組合來使 用:相對於100重量份之上述聚醇，上述觸媒的使用量較 佳係0.001〜2.0重量份之範圍的量。 又’加成於上述胺醋預聚物的具有經基之（甲基）丙婦酸 201026497 酯係具有1個以上的羥基’且具有1個以上的（甲基）丙稀隨 氧基(CH2=CHCOO-或CH2 = C(CH3)COO-)之化合物。該具 有羥基之（曱基）丙烯酸酯可加成在上述胺酯預聚物之異氛 酸酯基上。該具有羥基之丙烯酸酯有：2-羥基乙基丙婦酸 酯、2-羥基丙基丙烯酸酯、季戊四醇三丙烯酸酯等。可使 用單獨1種該等具有經基之丙烯酸酯，亦可將2種以上加 以組合來使用。 藉由將此種光聚合性寡聚物與上述光聚合性單體—起 調配’如後所述地’可將所獲得的光硬化性樹脂組成物加 以硬化後之塗佈層的玻璃轉移溫度最佳化，並獲得在耐藥 品性及耐染色性上發揮良好的效果之光硬化性樹脂組成 物0 [光硬化性樹脂組成物] 使用於本發明之功能性面板的光硬化性樹脂組成物係 含有上述光聚合性寡聚物與上述光聚合性單體。該等光聚 合性养聚物與光聚合性單體之調配量的質量比通常為7〇 : 30〜30 : 70，較佳地為40 : 60〜60 : 40的量。單體的調配量 太少時，所獲得之光硬化性樹脂組成物的黏度會上昇而有 塗佈性惡化之虞，且有可能無法充分發揮耐藥品性及耐染 色性。又，單體的調配量太多時，塗膜的柔軟性會降低而 有脆性變高之虞。因此，光聚合性寡聚物與光聚合性單體 的調配量在上述範圍内時，可充分發揮光聚合性單體具有 的低極性，並使將光硬化性樹脂組成物加以硬化後之塗佈 201026497 層的玻璃轉移溫度保持在適當的值。藉此，可提高因該等 SP值及玻璃轉移溫度的數值所造成的功能性面板之耐藥品 性及耐染色性。再者，光聚合性單體亦可作為對光聚合性 寡聚物有效的稀釋劑而加以作用，使光硬化性樹脂組成物 谷易呈現適當的黏度，並提供良好的塗佈性。 此外，上述光硬化性樹脂組成物，除了為具有上述特 定的SP值之光聚合性單體以外，在不損害到本發明之效果 的範圍内，可再含有上述光聚合性單體以外的單體。亦即， 調配其他的單體時’由其他單體分別的Sp值依照上述式(χ)❹ 所算出的SP值只要在上述SP值的範圍内即可。 可使用已知之光聚合開始劑於上述光硬化性樹脂組成 物。藉由在該光聚合開始劑上照射紫外線，可達成使上述 之光聚合性單體與光聚合性寡聚物開始聚合之作用。該光 聚合開始劑具體來說有譬如：4-二甲基胺基安息香酸、4-二曱基胺基安息香酸酯、2,2-二曱氧基-2-苯基苯乙酮、苯乙 酮二乙基縮酮（acetophenone diethyl ketal)、烧氧基苯乙_、 二苯甲酿縮二甲醇(benzil dimethyl ketal)、二苯基酮及3,3-❹ 二曱基-4-曱氧基二苯基酮、4,4-二曱氧基二苯基酮、4,4-二 胺基二苯基酮等之二苯基酮衍生物、苯曱醯基烴基安息香 酸酯、雙(4-二烴基胺基苯基)酮、二苯曱醯及二苯曱醯縮曱 醇等之二苯曱醢衍生物、安息香及安息香異丁基醚等之安 息香衍生物、安息香異丙基醚、2-羥基-2-曱基苯丙酮、 羥基環己基苯基酮、山酮、嗟吨酮及嘆吨酮衍生物、第、 2,4,6-三曱基苯曱醯基聯苯基氧化膦、雙(2,6-二曱氧基笨甲 16 201026497 醯基)-2,4,4-二甲基戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)_ 苯基氧化膦、2-甲基甲硫基)苯基]_2_啉基丙烷_丨，2_苄 基-2-二甲基胺基_1_(琳基苯基)_丁酮等。可單獨使用1種 5亥等光聚合開始劑，亦可併用2種以上。相對於總計為1〇〇 重量份之上述光聚合性單體及光聚合性募聚物，上述光硬 化性組成物中之光聚合開始劑的調配量較佳地為〇丨〜1〇重 量份之範圍的量。 光聚合開始劑的調配量為0.1重量份以下時，使聚合反 應開始的效果較小，另一方面，超過1〇重量份時，使聚合 反應開始的效果會達到飽和且原料費用會變高。 又，考慮到上述光硬化性組成物所要求的硬化反應性 或安定性等，可依需要進一步地含有光敏感劑。該光敏感 劑係藉由照射光而吸收能量，並使該能量或電子向聚合開 始劑移動而開始聚合之作用。該光敏感劑可例舉：對二曱 基胺基安息香酸異戊基酯等。相對於總計為100重量份之 上述光I合性單體及光聚合性募聚物，該等光敏感劑的調 配篁較佳地為0.1〜10重量份之範圍的量。 再者，考慮到上述光硬化性樹脂組成物所要求的硬化 反應性或安定性等，可依需要含有聚合抑制劑。該聚合抑 制劑有·對本二齡、對本一紛單甲基醚、對曱氧基紛、2,4_ 二曱基-6-第三丁基酚、2,6-二-第三丁基_對曱酚、丁基羥基 苯甲醚、3-羥基硫酚、α-亞硝基萘酚、對苯醌、2,5-二羥 基-對醌等。相對於總計為1〇〇重量份之上述光聚合性單體 及光聚合性寡聚物，該等聚合抑制劑的調配量較佳地為 17 201026497 0.1〜10重量份之範圍的量。 又’於上述塗佈層之形成所使用的光硬化性樹脂組成 物的稀釋溶劑可含有醚、酮、酯等有機溶劑，該有機溶劑 可例舉：丙二醇單曱醚醋酸酯(PMA)、丁酮(MEK)、曱基異 丁基綱(MIBK)、丙酮或乳酸丁酯等。可使用單獨1種該等 稀釋溶劑，亦可將2種以上加以組合來使用。 上述光硬化性組成物係如上所述地依需要來使用稀釋 /谷齊]使其成為液狀而塗佈在基材上的面。塗佈的方法可 採用已知的方法，可例舉：凹版塗佈、滾筒式塗佈、反轉〇 式塗佈、刮刀式塗佈、浸沾式塗佈、裂缝式塗佈、調整刮 刀式塗佈、擠壓式塗佈、斜板式塗佈、環棒式塗佈、淋幕 式塗佈、射出塗佈、旋轉式塗佈法等。 [塗佈層] 仆以ϊίί上塗佈上述光硬化性組成物，接下來藉由光硬 土材層上形成塗佈層。所形成之塗佈層的玻璃轉移 ，度為50。(：以上，較佳係贼以上，更佳地為阶以上。 等度的上限值未特別限制，但從原料取得容易性 $點來看’通常較佳地為·t以下。塗佈層的 1度在上述範圍内時，會和上述光 果相互作用，而可更提聚高的： $性。特肢在耐染色性上發揮了顯著的效果。 、述所塗佈之光硬化性組成物加以光硬化 般疋利用照射紫外線的方法。欲形成塗佈層之基材層上 201026497 的面可選擇表面或底面中的某一面，亦可同時選擇兩者， 依需要適當選擇即可。此外，利用紫外線來將光硬化性組 成物硬化時的光照射量通常照射強度為2〇〜2〇〇〇mW/cm2， 照射量為 100〜5000mJT/cni2。 上述塗佈層的厚度係依所要求的設計性或耐藥品性的 程度適當選擇而獲得的厚度，雖未特別限定，但通常預測 範圍為Ιμηι〜200μιη之厚度。 ❹ 此外，照射紫外線時，由於紫外線硬化反應係自由基 反應，因此容易受氧的阻礙。故在基材上塗佈上述光硬化 性組成物後，為避免與氧接觸，可在氮氣氛下將該組成物 硬化。 [基材層] 本發明之功能性面板所使用的基材層的材質有：板 石、水泥、金屬、矽酸鈣、碳酸鈣、玻璃等無機質材料； 木質材料以外有聚丙烯、聚苯乙烯、聚碳酸酯、不飽和聚 酯樹脂等有機質材料；及該等之複合材料。其中，較佳係 在有機質材料中添加有玻璃纖維或碳纖維等纖維之材質， 即所謂的FRP(Fiber Reinforced Plastics ;纖維強化塑膠）。 FRP可例舉··不飽和聚醋樹脂、填充劑及含有玻璃纖維或 石反纖維之片狀的片狀模造材料(Sheet M〇lding c〇mp〇und ; SMC)及和SMC同樣皆為複合材料且含有短纖維之塊狀的 BMC(Bulk Molding Compound ;塊狀模造材料）等。FRp 一 般係添加有熱硬化性樹脂、有機過氡化物（硬化劑）、填充 201026497 ;:2縮劑、内部離型劑、強化材料、交聯劑及增黏劑 來為斬已設定為特定的溫度之模型内並加壓，以成 右執可Γ建染材料設置場所的形狀而使用。其中，當為含 玻璃纖、填充劑以及為強化材料之 板整_強度時，可更提高所獲得之功能性面 餘和:飽:m奸，二酸等多元酸料 醇、新紅醇、三甲基吨精丙基醚、f 風化雙紛、物二環氧狀細㈣元醇所產生。 劑有碳酸鈣、氫氧化鋁等。從降低費用的觀點來 =為碳_。從提高FRP本身的耐藥品性的觀點 …、較佳地為氫氧化鋁。然而如上所述地，只要形成上 述塗佈層’即使是採用使用碳酸辦於填充劑的FRP來作為 ，材’也可充分提高功能性面板整體的耐藥品性，因此可 容易實現具有由價廉的FRP卿成的騎層之功能性面 板。 作為強化材料之玻璃纖維及碳纖維的纖維長度為 20〜50mm左右，纖維半徑為5〜25μιη左右者較適合使^ 了 較佳係於FRP中含有1G〜7G質量％的量。作為上述基材層 所使用的FRP係將該等成分混合，並藉由FRp製造裝置^ 來製造具有特定的厚度及大小之FRP。 此外二基材層的厚度可隨著功能性面板的用途而改 變，俜通常為2.5mm以上。厚度的上限未特別限制而可適 201026497 當選擇 [功能性面板] 本發明之功能性面板係含 該塗佈層卿成於該基材層h 性2與基材層’且 常為2.5mm以上較佳。功於 ^ 板整體的厚度通 φ ❹ 限制，可在基材層上的^ ^板整體^^上限未特別 層，亦可依需要而在該等从/兩者“成上述塗佈 成有由各種材質所構成的中間層3=1 卜之該:層間形 佳係將該塗佈層形成為功能性面板的最2耐一色性’較 如有用以提高基材層與塗佈層 =層。中間層譬 (und⑽at layer)，或且有用=間的接者性之底層塗佈層 樣或色彩之料層等Γ —功能性面板料性的模 處形成有：:2:獲仔的本發明之功能性面板係於基材層 ίίΐ的塗佈層，因此具有優良的_品性及 發：變質或：化？使用含酸Ϊ鹼之強刺激性清潔劑也不易 易蘇吐鐵多七仇。又，即使是使用如染髮劑之染色劑也不 X * 5木色。因此’本發明之功能性面板適合作為 特別是設^住宅_浴室或廚紅功能性面板。 又’右基材層係採用含有不飽和聚酯樹脂及玻璃纖維 或％I纖維之FRP，不只是耐藥品性及耐染色性，還可進一 步地實現具有良好的耐久性之功能性面板。 以下係根據實施例具體說明本發明，但本發明並非限 21 201026497 定於該等實施例。 實施例： [光硬化性樹脂組成物的調製] 根據表1所顯示的内容，在攪拌裝置加入光聚合性寡 聚物60重量份及光聚合性單體4〇重量份並混合，接下來 加入光聚合開始劑（IRGACURE 184，Ciba Specialty Chemicals Inc.製）1重量份，攪拌2分鐘並實施脫泡處理後， 可獲得光硬化性樹脂組成物(C1〜C11)。 ❹ 22 201026497 (¾ Ο)I —dj—:C—CH2— « ♦ ♦ (3) C02 10 201026497 When the carbon number of R is less than 5, the sp value of the monomer tends to rise when it is a chain hydrocarbon group, and is a ring shape. Hydrocarbon groups are not readily available. In addition, when the carbon number of R2 exceeds 20, the glass transition temperature of the photocurable resin composition obtained when it is a chain hydrocarbon group tends to decrease, and when it is a cyclic hydrocarbon group, the photohardening is obtained. The cross-linking density (cr〇sslink density) of the resin composition tends to decrease. It is assumed that when the crosslink density is lowered too low, the dyeing agent such as a hair dye easily penetrates into the inside of the coating layer, so that the panel has a 色 color. The monomer represented by the above formula (1) specifically includes isodecyl (decyl) acrylate, 1,6-hexanediol bis(indenyl) acrylate, and diterpene-based tricyclic fluorenyl group II. (fluorenyl) acrylate, isoamyl (decyl) acrylate, dodecyl (meth) acrylate, tridecyl (decyl) acrylate, isotetradecyl (decyl) propylene Acid ester, octadecyl (mercapto) acrylate, 3·methyl decyl diol di(meth) acrylate, neopentyl glycol bis(indenyl) acrylate, cyclohexyl ruthenium Alcohol di(meth)acrylate, 1,9-nonanediol bis(indenyl) acrylate, trishydroxypropyl propane tris(decyl) acrylate, pentaerythritol tetrakis(mercapto) acrylate. Among them, from the viewpoint of increasing the glass transition temperature, it is preferably a monomer having a cyclic hydrocarbon group, more preferably an isodecyl (mercapto) acrylate and a dihydroxy fluorenyl tricyclic fluorenyl group (曱). Base) acrylate. When it is such a monomer, it exhibits a good tendency to be low in polarity in order to have a more suitable SP value, and the chemical resistance and dyeing resistance of the obtained functional panel can be further improved. Further, the function of the photopolymerizable oligomer described later as a reactive diluent can be effectively exhibited. Further, the number of functional groups of the photopolymerizable monomer is usually from 6, preferably from 1 to 4. Further, the number of functional groups herein refers to a value obtained by multiplying the number of 201026497 groups by a plurality of molecules and averaging the number of obtained functional groups as a function of the number of functional groups in 1:6:6. When the number of functional groups is 1, there is a tendency to rise, but by increasing the glass transition temperature, the workability of the coating layer having good chemical resistance and dye resistance is loyal. In this case, it is preferred to use a photopolymerizable single:::, sloping transition temperature having a ring structure. On the other hand, the number of functional groups is from 2 to 6, preferably: since it is possible to appropriately maintain the crosslinking tendency of the photocurable composition, it is presumed that it is easier to effectively suppress the infiltration of the dye, especially the panel 4 The phenomenon of being dyed. Therefore, in this case, chemical resistance and dyeing resistance can be maintained, and a functional panel formed of a coating layer having a good hard enthalpy can be obtained. [Photopolymerizable Polymer] The photopolymerizable oligomer used in the photocurable resin composition is specifically, for example, an amine ester-based (meth) acrylate oligomer or an epoxy (meth) Acrylate oligomer, diethyl ether (mercapto) acrylate polymer, ester (mercapto) acrylate polymer, polycarbonate (mercapto) acrylate oligomer, fluorine (methyl An acrylate oligomer, an fluorenone-based (meth) acrylate polymer, and the like. The photopolymerizable oligomer can be obtained by using polyethylene glycol, polyoxypropylene glycol, polytetrahydrofuran, bisphenol quinone type epoxy resin, phenol novolak type epoxy resin, polyol, and ε-caprolactone. The adduct or the like is reacted with (mercapto)acrylic acid or synthesized by subjecting a polyisocyanate compound and a hydroxyl group-containing (mercapto)acrylic acid vinegar compound to acetalization. The photopolymerizable oligomer may be any one of a monofunctional oligomer, a difunctional oligomer 12 201026497 or a polyfunctional oligomer, from achieving an appropriate crosslinking of the obtained photocurable tree* lipid composition. From the standpoint of the density, it is preferred to be a polyfunctional oligomer. Among the photopolymerizable polymers, it is preferred to use an amine ester-based (meth) acrylate from the viewpoint of imparting good chemical resistance and dyeing resistance as a functional panel. Polymer. Amine ester-based (meth)acrylic acid spring polymer, for example, an amino ester prepolymer can be synthesized from a polyalcohol and a polyisocyanate, and the amine ester prepolymer is added to a hydroxyl group by Methyl)propionic acid vinegar can also be made into an amine ester (mercapto) acrylate oligomer containing a carbonate backbone. The polyalcohol used in the synthesis of the above amine ester prepolymer contains a plurality of compounds having a trans group (OH group). Specifically, there are: poly-linked polyalcohol, polyester polyalcohol, polytetramethylene glycol, polybutadiene polyol, epoxy-fired modified polybutadiene polyol, and polyisoprene polyol. . One type of these polyalcohols may be used alone or two or more types may be used in combination. In addition, the above polyether polyol can be obtained by addition polymerization of φ, such as ethylene glycol, propylene glycol, glycerol, trimethoprim, pentaerythritol, sorbitol and the like, and addition of epoxy B. An alkylene oxide or an alkylene oxide such as propylene oxide. Further, a polyether polyol can be obtained by ring-opening polymerization, such as a polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran (THF). The above polyester polyol can also be obtained by addition polymerization, such as: ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, trimethyl ketone It is obtained by using a polybasic carbonic acid such as adipic acid, glutaric acid, succinic acid, azelaic acid, pimelic acid or suberic acid. Further, 13 201026497 It is also possible to obtain a polyester polyol by ring-opening polymerization, which has a lactone-based polyester polyol obtained by ring-opening polymerization of ε-caprolactone. The above polyisocyanate is a compound containing a plurality of isocyanate groups (NCO groups), specifically: toluene diisocyanate (TDI), diphenylnonane diisocyanate (MDI), crude diphenylnonane diisocyanate (raw MDI), isophorone diisocyanate (IPDI), deuterated diphenylmethane diisocyanate, hydrogenated phthalic acid diisocyanate, hexamethylene diisocyanate (HDI), or isomeric cyanuric acid modification, carbon two醯 imine modified substances, diol modified substances, and the like. It is also possible to use one or more of these polyisomeric acids, or to use two or more of them in combination. In the above synthesis of the amine vinegar prepolymer, it is preferred to use a catalyst for the amine acetalization reaction. The catalyst for the reaction of the amine g is: dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin cis-butyrate, dioctyltin thiosulfate, xin An organic tin compound such as tin citrate or monobutyltin oxide; an inorganic tin compound such as chlorinated first tin; an organic lead compound such as lead octenate; a cyclic amine such as triethylethylene diamine; p-toluenesulfonic acid and hydrazine; Organic sulfonic acids such as sulfonic acid and fluorosulfonic acid; inorganic acids such as sulfuric acid, phosphoric acid, and peroxy phthalic acid; alkalis such as sodium hydride, hydrogen peroxide, methanol, and sodium hydroxide; tetrabutyl titanate and titanic acid a titanium compound such as ethyl ester or tetraisopropyl titanate; a silver compound; an ammonium salt or the like. These catalysts are preferably organotin compounds. The above-mentioned catalysts may be used alone or in combination of two or more kinds thereof. The amount of the catalyst used is preferably in the range of 0.001 to 2.0 parts by weight based on 100 parts by weight of the above-mentioned polyol. Further, the (meth)propanoid 201026497 ester having a trans group added to the above-mentioned amine vinegar prepolymer has one or more hydroxyl groups and has one or more (meth) propylene with an oxy group (CH2). Compound of =CHCOO- or CH2 = C(CH3)COO-). The hydroxy group-containing (fluorenyl) acrylate can be added to the alicyclic ester group of the above amine ester prepolymer. The hydroxy group-containing acrylate includes 2-hydroxyethyl propyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and the like. A single acrylate having a radical may be used alone or in combination of two or more. By blending such a photopolymerizable oligomer with the above photopolymerizable monomer, the glass transition temperature of the coating layer obtained by curing the obtained photocurable resin composition can be cured as described later. Photocurable resin composition which exhibits excellent effects on chemical resistance and dyeing resistance. [Photocurable resin composition] Photocurable resin composition used in the functional panel of the present invention The photopolymerizable oligomer and the photopolymerizable monomer are contained. The mass ratio of the amount of the photopolymerizable macropolymer to the photopolymerizable monomer is usually 7 〇 : 30 to 30 : 70, preferably 40 : 60 to 60 : 40. When the amount of the monomer is too small, the viscosity of the photocurable resin composition obtained increases, and the applicability deteriorates, and the chemical resistance and dyeing resistance may not be sufficiently exhibited. Further, when the amount of the monomer is too large, the flexibility of the coating film is lowered and the brittleness is high. Therefore, when the amount of the photopolymerizable oligomer and the photopolymerizable monomer is within the above range, the low polarity of the photopolymerizable monomer can be sufficiently exhibited, and the photocurable resin composition can be cured. The glass transition temperature of the layer 201026497 layer is maintained at an appropriate value. Thereby, the chemical resistance and dyeing resistance of the functional panel due to the values of the SP value and the glass transition temperature can be improved. Further, the photopolymerizable monomer can also act as a diluent effective for the photopolymerizable oligomer, so that the photocurable resin composition can easily exhibit an appropriate viscosity and provide good coatability. In addition, the photocurable resin composition may further contain a single sheet other than the photopolymerizable monomer, in addition to the photopolymerizable monomer having the specific SP value described above, insofar as the effects of the present invention are not impaired. body. In other words, when the other monomers are blended, the SP value calculated from the Sp value of the other monomer according to the above formula (χ) 只要 may be within the range of the SP value. A known photopolymerization initiator can be used for the above photocurable resin composition. By irradiating the photopolymerization initiator with ultraviolet rays, the polymerization of the above photopolymerizable monomer and the photopolymerizable oligomer can be achieved. The photopolymerization initiator is specifically, for example, 4-dimethylamino benzoic acid, 4-didecylaminobenzoate, 2,2-dimethoxy-2-phenylacetophenone, benzene Ecetophenone diethyl ketal, alkoxy benzene ketone, benzil dimethyl ketal, diphenyl ketone and 3,3-indenyl fluorenyl-4-indole a diphenyl ketone derivative such as oxydiphenyl ketone, 4,4-dimethoxy diphenyl ketone or 4,4-diaminodiphenyl ketone; phenyl hydrazino benzoic acid ester, double a benzoquinone derivative such as (4-dihydrocarbylaminophenyl) ketone, diphenyl hydrazine or diphenyl hydrazine decyl alcohol, a benzoin derivative such as benzoin and benzoin isobutyl ether, and benzoin isopropyl Ether, 2-hydroxy-2-mercaptopropiophenone, hydroxycyclohexyl phenyl ketone, ketone, xanthone and sinone derivatives, 2,4,6-trimercaptobenzoquinone biphenyl Phosphine oxide, bis(2,6-didecyloxycarbamate 16 201026497 fluorenyl)-2,4,4-dimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzhydrazide Base) phenylphosphine oxide, 2-methylmethylthio)phenyl]_2-morphylpropane 丨, 2_benzyl-2-dimethyl _1_ amine (Lin Ji phenyl) _ butanone. One kind of photopolymerization initiator such as 5 hai can be used alone, or two or more kinds can be used in combination. The amount of the photopolymerization initiator in the photocurable composition is preferably 〇丨1 to 1 part by weight based on the total amount of the photopolymerizable monomer and the photopolymerizable polymerizable component. The amount of the range. When the amount of the photopolymerization initiator is 0.1 part by weight or less, the effect of starting the polymerization reaction is small. On the other hand, when the amount is more than 1 part by weight, the effect of starting the polymerization reaction is saturated and the raw material cost is increased. Further, in consideration of the curing reactivity, stability, and the like required for the photocurable composition, a photo-sensitive agent may be further contained as needed. The photosensor absorbs energy by irradiating light and causes the energy or electron to move toward the polymerization initiator to start polymerization. The photosensitive agent may, for example, be p-dimethylamino benzoic acid isoamyl ester or the like. The amount of the photo-sensitizing agent to be added is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the photo-combining monomer and the photopolymerizable convergent polymer. In addition, a polymerization inhibitor may be contained as needed in consideration of curing reactivity, stability, and the like required for the photocurable resin composition. The polymerization inhibitor has a two-in-one, a single methyl ether, a p-methoxy group, a 2,4-didecyl-6-tert-butylphenol, and a 2,6-di-t-butyl group. P-phenol, butyl hydroxyanisole, 3-hydroxythiophenol, α-nitrosobnaphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like. The amount of the polymerization inhibitor is preferably an amount ranging from 0.1 to 10 parts by weight in the amount of 17 201026497 with respect to the photopolymerizable monomer and the photopolymerizable oligomer in a total amount of 1 part by weight. Further, the diluting solvent of the photocurable resin composition used for forming the coating layer may contain an organic solvent such as an ether, a ketone or an ester, and the organic solvent may, for example, be propylene glycol monoterpene ether acetate (PMA) or butyl. Ketone (MEK), mercaptoisobutylene (MIBK), acetone or butyl lactate. One type of these diluent solvents may be used alone or two or more types may be used in combination. The photocurable composition is applied to the surface of the substrate in a liquid form as needed, as described above. The coating method may be a known method, and may be exemplified by gravure coating, drum coating, reverse nip coating, doctor blade coating, dip coating, crack coating, and adjustment blade type. Coating, extrusion coating, slanting plate coating, ring bar coating, curtain coating, injection coating, rotary coating, and the like. [Coating layer] The above photocurable composition was applied by ruthenium, and then a coating layer was formed on the photohardened soil layer. The glass transition of the formed coating layer was 50. (The above is preferably a thief or more, more preferably a step or more. The upper limit of the degree of equivalence is not particularly limited, but from the point of view of the ease of obtaining raw materials, it is usually preferably at least t·coat layer. When 1 degree is within the above range, it will interact with the above-mentioned light fruit, and it can be more highly concentrated: $. The special limb exerts a remarkable effect on dyeing resistance. The composition is photohardened by a method of irradiating ultraviolet rays. To form a surface of the substrate layer of the coating layer on 201026497, one of the surface or the bottom surface may be selected, or both may be selected at the same time, and may be appropriately selected as needed. Further, the amount of light irradiation when the photocurable composition is cured by ultraviolet rays is usually 2 〇 to 2 〇〇〇mW/cm 2 and the irradiation amount is 100 to 5000 mJT/cni 2 . The thickness of the coating layer is The thickness obtained by appropriately selecting the desired degree of design or chemical resistance is not particularly limited, but is usually in the range of Ιμηι to 200 μm. ❹ In addition, when ultraviolet rays are irradiated, the ultraviolet curing reaction is a radical reaction. This is easily hindered by oxygen. Therefore, after the photocurable composition is applied onto a substrate, the composition can be cured in a nitrogen atmosphere in order to avoid contact with oxygen. [Substrate layer] The functional panel of the present invention The material of the substrate layer used is: inorganic materials such as slate, cement, metal, calcium silicate, calcium carbonate, and glass; and other materials such as polypropylene, polystyrene, polycarbonate, and unsaturated polyester resin. An organic material; and a composite material of the above, wherein a material such as glass fiber or carbon fiber is added to the organic material, that is, a so-called FRP (Fiber Reinforced Plastics). FRP can be exemplified. Unsaturated polyester resin, filler and sheet-like molding material containing glass fiber or stone counter fiber (Sheet M〇lding c〇mp〇und; SMC) and SMC are also composite materials and contain short fibers. Bulk BMC (Bulk Molding Compound), etc. FRp is generally added with a thermosetting resin, an organic over-tanning compound (hardener), and filled with 201026497; 2 shrinkage agent, internal release agent, The reinforcing material, the crosslinking agent and the tackifier are used in the model in which the crucible has been set to a specific temperature, and are used in the shape of the place where the right-handed construction material can be built. When the filler is used as a strengthening material, the functional surface and the obtained functional surface can be further improved: a full-size alcohol, a di-acid such as a diacid, a neoerythritol, a trimethyl ton propyl ether , f weathering double, material two epoxy-like fine (tetra) alcohol produced. The agent is calcium carbonate, aluminum hydroxide, etc. From the point of view of cost reduction = carbon _. From the point of view of improving the chemical resistance of FRP itself... Preferably, it is aluminum hydroxide. However, as described above, as long as the coating layer 'the FRP using a carbonate-based filler is formed, the material' can sufficiently improve the chemical resistance of the entire functional panel. Therefore, it is easy to realize a functional panel having a riding layer made of an inexpensive FRP. The glass fiber and the carbon fiber as the reinforcing material have a fiber length of about 20 to 50 mm, and a fiber radius of about 5 to 25 μm is preferably used in an amount of 1 G to 7 G% by mass in the FRP. The FRP used as the base material layer is mixed with these components, and an FRP having a specific thickness and size is produced by the FRp manufacturing apparatus. Further, the thickness of the two substrate layers may vary depending on the use of the functional panel, and the enthalpy is usually 2.5 mm or more. The upper limit of the thickness is not particularly limited and may be suitable for 201026497. When [Functional Panel] is selected, the functional panel of the present invention contains the coating layer in the base layer h and the substrate layer 'and often 2.5 mm or more Preferably. The thickness of the whole plate is limited by the φ ❹ limit, and the upper limit of the plate on the substrate layer is not a special layer, and may be coated as described above. The intermediate layer 3 = 1 composed of various materials: the interlayer shape is preferably such that the coating layer is formed into the most pliable one-color property of the functional panel to improve the base material layer and the coating layer = layer. The intermediate layer und (und (10) at layer), or the useful layer of the underlying coating layer or color layer, etc. - the functional panel material is formed with: 2: the invention of the invention The functional panel is attached to the coating layer of the substrate layer, so it has excellent _ character and hair: deterioration or: use of strong irritating detergent containing acid and alkali is not easy to suffocate Moreover, even if a coloring agent such as a hair dye is used, it is not X*5 wood color. Therefore, the functional panel of the present invention is suitable as a special housing/bathroom or kitchen red functional panel. It is made of FRP containing unsaturated polyester resin and glass fiber or %I fiber, not only chemical resistance and dyeing resistance. Further, a functional panel having good durability can be further realized. The present invention will be specifically described below based on examples, but the present invention is not limited to 21 201026497. Examples: [Photocurable resin composition Preparation] According to the contents shown in Table 1, 60 parts by weight of a photopolymerizable oligomer and 4 parts by weight of a photopolymerizable monomer were added to a stirring device and mixed, followed by addition of a photopolymerization initiator (IRGACURE 184, Ciba Specialty) 1 part by weight of Chemicals Inc., stirred for 2 minutes, and subjected to a defoaming treatment, a photocurable resin composition (C1 to C11) was obtained. ❹ 22 201026497 (3⁄4 Ο)
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Hu f#辑駟 寸革嫜駟 -ss 『#銻^ 寸¥湓^ 5¥蜊)蓉鉍械？-|、今龄采/0:韜蚌/(1)製蚌长< :01※ , $^$έ : 6※ : i- 25^40^s :卜※ ^4^Η^η-ί : δ , :寸※ - s$^s^s : εχ· , 51^-^s :CN^· : 一※ 201026497 [實施例1] 在FRP(DECKMAT(註冊商標)2415，DIC化工株式會社 製)所構成之基材的上方面，使上述調製的光硬化性樹脂組 成物C1塗佈為厚度20μιη。接下來，照射uv(l〇〇〇mW/cm1， 働OmJ/cm1)以使光硬化性樹脂組成物硬化而獲得功能性 面板。 [實施例2〜6] 除了分別使用上述調製的光硬化性樹脂組成物C2〜C6 ® 以外’其他皆依照實施例1來獲得功能性面板。 [比較例1〜5] 除了分別使用上述调製的光硬化性樹脂組成物C7〜c 11 以外’其他皆依照實施例1來獲得功能性面板。 (1) 玻璃轉移溫度的測定 玻璃轉移溫度（Tg)的測量係利用動態黏彈性裝置❹ (DMS6100，Seiko Instruments Inc.製）’在測量頻率：1 ·〇Ηζ， 昇溫速度：3.0°C/min的條件下進行。 24 1 耐藥品性的評估 將實施例1獲得的功能性面板浸潰在下列所示各個不 同條件的藥品，觀察功能性面板的變化，並將其變化的程 度以色差計（SpectroEye，SAKATA INX ENG.CO.，LTD 製） 201026497 依下列式（A)來求得浸潰部位與未浸潰部位的[北色差 (ΔΕ)。 AE=(Aa2 + Ab2 + AL2)1/2 .......⑷ 該數值愈小表示對藥品具有良好的耐受性，較 3.0以下，更佳地為1W。#為1 G町時可 乎 沒有變化。 碣丁 此外’利用由未塗佈光硬化性樹脂組成物之上述卿 ❹ 賴成的基材來作為對照例丨’並同樣進行耐藥品性評估。 HC1····浸潰在3質量％濃度的Ηα水溶液裏丨小時。Hu f#集驷 Inch leather 嫜驷 -ss 『#锑^ 寸¥湓^ 5¥蜊) Rong 铋? -|, 今龄采/0:韬蚌/(1)制蚌长< :01※ , $^$έ : 6※ : i- 25^40^s :卜※ ^4^Η^η-ί : δ , : inch ※ - s$^s^s : εχ· , 51^-^s :CN^· : A ※ 201026497 [Example 1] In FRP (DECKMAT (registered trademark) 2415, manufactured by DIC Chemical Co., Ltd. In the upper aspect of the substrate formed, the photocurable resin composition C1 prepared as described above is applied to a thickness of 20 μm. Next, uv (10 μm/cm1, 働OmJ/cm1) was irradiated to cure the photocurable resin composition to obtain a functional panel. [Examples 2 to 6] Functional panels were obtained in accordance with Example 1 except that the photocurable resin compositions C2 to C6 ® prepared above were used. [Comparative Examples 1 to 5] Functional panels were obtained in accordance with Example 1 except that the photocurable resin compositions C7 to C11 prepared above were used. (1) Measurement of glass transition temperature The glass transition temperature (Tg) was measured by a dynamic viscoelastic device (DMS6100, manufactured by Seiko Instruments Inc.) at the measurement frequency: 1 · 〇Ηζ, heating rate: 3.0 ° C / min Under the conditions. 24 1 Evaluation of chemical resistance The functional panels obtained in Example 1 were immersed in the various conditions of the drugs shown below, and the changes in the functional panels were observed and the degree of change was measured by a color difference meter (SpectroEye, SAKATA INX ENG .CO., LTD.) 201026497 [Northern color difference (ΔΕ) of the impregnated portion and the unimpregnated portion is obtained according to the following formula (A). AE = (Aa2 + Ab2 + AL2) 1/2 (4) The smaller the value, the better the resistance to the drug, and it is preferably 3.0 or less, more preferably 1 W. #为1 G町也可以没改变。 In addition, the substrate of the above-mentioned enamel-based composition which is not coated with the photocurable resin composition was used as a comparative example 并', and the chemical resistance evaluation was performed in the same manner. The HC1···· was immersed in an aqueous solution of 3α at a concentration of 3 mass% for a few hours.
NaOH· •次〉貝在5質量〇/0濃度的Na〇H水溶液裏i小時。 BM · · · ·浸潰在市售的洗潔劑（p〇wer Spray \如也NaOH · • times > shellfish in a 5 〇 / 0 concentration of Na 〇 H aqueous solution for i hours. BM · · · · Dip in a commercially available detergent (p〇wer Spray \如也
Magiclean(註冊商標），花王株式會社製）裏％ 小時。 將該等結果示於表2。 (表2) HC1 NaOH 市售的洗潔如 對照例1 6.34 0.13 7.78 實施例1 1.09 0.60 0.83 (3)财染色性的評估 在玻璃基板上、使上述調製的光硬化性樹脂組成物 (ci〜cii)塗佈為厚度丨〇mm。在氮氣氛下照射 UV( 1000mW/cm2 ’ 4000mJ/cm2)以使光硬化性樹脂組成物硬 化而獲得各個樣品。 將獲得的樣品浸潰在市售的染髮劑(GATSBY回復到黑 25 201026497 髮(=冊商標）·· i劑與2劑的混合物，MAND〇M株式會社 製）褢24 Λί、時並水洗，和上述⑴耐藥品性的評估同樣地以 上述色差雜來求槪潰部倾未浸潰雜的Lab色 差(ΔΕ)。 根據上述結果得知本發明之功能性面板可維 耐藥品性並發揮耐染色性佳的效果。特驳綠合⑲ 係採用異莰基（曱基）丙烯酸酯或二羥 J；生早體 基）丙烯酸酯等低極性者時， 土 =六几基二（甲 降低耐染色性。 “極性者相比，可大幅 【圖式簡單說明】 益。 【主要元件符號說明】 無0Magiclean (registered trademark), manufactured by Kao Corporation). These results are shown in Table 2. (Table 2) HC1 NaOH Commercially available cleaning as Comparative Example 1 6.34 0.13 7.78 Example 1 1.09 0.60 0.83 (3) Evaluation of the dyeability of the above-mentioned photocurable resin composition (ci~) prepared on the glass substrate Cii) coated to a thickness of 丨〇mm. Each sample was obtained by irradiating UV (1000 mW/cm2 '4000 mJ/cm2) under a nitrogen atmosphere to harden the photocurable resin composition. The obtained sample was immersed in a commercially available hair dye (GATSBY was returned to Black 25 201026497 (=registered trademark)·· a mixture of 2 agents and 2 doses, manufactured by MAND〇M Co., Ltd.) 褢24 Λί, and washed with water. In the same manner as the evaluation of the chemical resistance of the above (1), the Lab color difference (ΔΕ) in which the collapsed portion was not impregnated was obtained by the above-described color difference. From the above results, it was found that the functional panel of the present invention can maintain chemical resistance and exhibit excellent dyeing resistance. In the case of low polarity such as isodecyl (mercapto) acrylate or dihydroxy J; nascent early base acrylate, soil = hexadequid II (a reduction of dye resistance). In comparison, it can be greatly [simplified description of the schema]. [Main component symbol description] No 0
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| JP5543808B2 (en) * | 2010-01-25 | 2014-07-09 | 株式会社ブリヂストン | Photopolymerizable composition and functional panel using the same |
| CN102504496A (en) * | 2010-06-30 | 2012-06-20 | 上海晓宝增强塑料有限公司 | Preparation method of fiber-reinforced plastic |
| JP2012224669A (en) * | 2011-04-15 | 2012-11-15 | Mitsubishi Rayon Co Ltd | Active energy ray-curable coating material composition, and coated article |
| JP5860622B2 (en) * | 2011-07-19 | 2016-02-16 | 株式会社ブリヂストン | PHOTOCURABLE RESIN COMPOSITION, WATERWIRE MEMBER AND FUNCTIONAL PANEL USING THE SAME |
| JP6134473B2 (en) * | 2011-07-19 | 2017-05-24 | 株式会社ブリヂストン | PHOTOCURABLE RESIN COMPOSITION, WATERWIRE MEMBER AND FUNCTIONAL PANEL USING THE SAME |
| EP2990428A4 (en) | 2013-04-26 | 2017-01-11 | Daicel-Allnex Ltd. | Urethane (meth)acrylate and active energy ray-curable resin composition |
| JP7579663B2 (en) * | 2020-10-01 | 2024-11-08 | 中国塗料株式会社 | Active energy ray curable resin composition and substrate with cured coating |
| JP2022085047A (en) * | 2020-11-27 | 2022-06-08 | 東洋インキＳｃホールディングス株式会社 | Active energy ray curable hard coat agent, hard coat layer, optical member and electronic device |
| KR102571283B1 (en) * | 2022-01-13 | 2023-08-29 | 이영준 | Tile for swimming pool and manufacturing method therefor |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3963239B2 (en) * | 1998-04-07 | 2007-08-22 | 日本化薬株式会社 | Resin composition, lens resin composition and cured product thereof |
| JP2001240774A (en) * | 2000-02-29 | 2001-09-04 | Hitachi Chem Co Ltd | Method of producing layer having both hydrophilic antifoulancy and hard coat and plastic molded product to be obtained by this method |
| KR100563420B1 (en) * | 2000-07-19 | 2006-03-22 | 가부시키가이샤 닛폰 쇼쿠바이 | Resin composition for coating and coating composition for curing |
| JP3676260B2 (en) * | 2000-12-28 | 2005-07-27 | ナトコ株式会社 | Active energy ray curable urethane (meth) acrylate, active energy ray curable composition and use thereof |
| TW200624510A (en) * | 2004-11-08 | 2006-07-16 | Mitsubishi Chem Corp | Radiative curable composition and cured product thereof, and laminate of the cured product |
| CN101052681A (en) * | 2004-11-08 | 2007-10-10 | 三菱化学株式会社 | Radiation curable composition, cured product thereof, and laminate thereof |
| JP2007131698A (en) * | 2005-10-11 | 2007-05-31 | Mitsubishi Chemicals Corp | Radiation curable composition, cured product thereof, and laminate thereof |
| US20070197362A1 (en) * | 2006-02-02 | 2007-08-23 | Bridgestone Corporation | Conductive elastic roller and image forming apparatus comprising the same |
-
2008
- 2008-07-28 JP JP2008193412A patent/JP5548347B2/en active Active
-
2009
- 2009-07-22 KR KR1020117002244A patent/KR101196625B1/en not_active Expired - Fee Related
- 2009-07-22 WO PCT/JP2009/063127 patent/WO2010013627A1/en not_active Ceased
- 2009-07-22 CN CN2009801299643A patent/CN102112306B/en not_active Expired - Fee Related
- 2009-07-27 TW TW098125136A patent/TWI417191B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CN102112306A (en) | 2011-06-29 |
| CN102112306B (en) | 2013-12-18 |
| TWI417191B (en) | 2013-12-01 |
| KR101196625B1 (en) | 2012-11-02 |
| JP5548347B2 (en) | 2014-07-16 |
| WO2010013627A1 (en) | 2010-02-04 |
| JP2010030100A (en) | 2010-02-12 |
| KR20110038076A (en) | 2011-04-13 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |