JPH0422694B2 - - Google Patents
Info
- Publication number
- JPH0422694B2 JPH0422694B2 JP56019660A JP1966081A JPH0422694B2 JP H0422694 B2 JPH0422694 B2 JP H0422694B2 JP 56019660 A JP56019660 A JP 56019660A JP 1966081 A JP1966081 A JP 1966081A JP H0422694 B2 JPH0422694 B2 JP H0422694B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- electron beam
- impregnated
- decorative
- decorative paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000010894 electron beam technology Methods 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 9
- 229920006295 polythiol Polymers 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000000123 paper Substances 0.000 description 91
- 238000000034 method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- -1 polyol acrylates Chemical class 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- UUGXDEDGRPYWHG-UHFFFAOYSA-N (dimethylamino)methyl 2-methylprop-2-enoate Chemical compound CN(C)COC(=O)C(C)=C UUGXDEDGRPYWHG-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- KGPXEVIKDFHEEZ-UHFFFAOYSA-N 2-(dibenzylamino)ethyl prop-2-enoate Chemical compound C=1C=CC=CC=1CN(CCOC(=O)C=C)CC1=CC=CC=C1 KGPXEVIKDFHEEZ-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- NIAGUSHJWAMKBZ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound CC(=C)C(O)=O.NC1=NC(N)=NC(N)=N1 NIAGUSHJWAMKBZ-UHFFFAOYSA-N 0.000 description 1
- POYODSZSSBWJPD-UHFFFAOYSA-N 2-methylprop-2-enoyloxy 2-methylprop-2-eneperoxoate Chemical compound CC(=C)C(=O)OOOC(=O)C(C)=C POYODSZSSBWJPD-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- GAKWESOCALHOKH-UHFFFAOYSA-N 4-methoxybutyl prop-2-enoate Chemical compound COCCCCOC(=O)C=C GAKWESOCALHOKH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NOEMSRWQFGPZQS-UHFFFAOYSA-N CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO Chemical compound CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO NOEMSRWQFGPZQS-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- MPRJFHVZWIKCOO-UHFFFAOYSA-N butyl prop-2-eneperoxoate Chemical compound CCCCOOC(=O)C=C MPRJFHVZWIKCOO-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- VOBKFBGLANJANG-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CCCCCCCCCCCCOC(=O)C(C)=C VOBKFBGLANJANG-UHFFFAOYSA-N 0.000 description 1
- WMAFNLQQGPUKCM-UHFFFAOYSA-N ethoxymethyl 2-methylprop-2-enoate Chemical compound CCOCOC(=O)C(C)=C WMAFNLQQGPUKCM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DMEKUKDWAIXWSL-UHFFFAOYSA-N n,n-dimethyl-7-nitro-9h-fluoren-2-amine Chemical compound [O-][N+](=O)C1=CC=C2C3=CC=C(N(C)C)C=C3CC2=C1 DMEKUKDWAIXWSL-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical class OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は化粧板に利用される化粧紙の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for manufacturing decorative paper used for decorative boards.
「従来の技術」
化粧板の製造に利用される化粧紙には、表面硬
度、耐溶剤性、耐熱性等に優れた性質を有するメ
ラミン化粧板、ジアリルフタレート化粧板、ポリ
エステル化粧板等に利用される化粧紙や、化粧板
を製造する際に化粧紙を接着剤で化粧板用基板に
貼り合わせるだけで済む塩化ビニル化粧紙等があ
る。``Prior art'' Decorative papers used in the production of decorative boards include melamine decorative boards, diallyl phthalate decorative boards, and polyester decorative boards, which have excellent properties such as surface hardness, solvent resistance, and heat resistance. There are decorative papers such as decorative paper and vinyl chloride decorative paper, which can be manufactured simply by pasting the decorative paper to the decorative board substrate using an adhesive.
「発明が解決しようとする課題」
前者の化粧紙による化粧板は、諸物性に対して
優れた作用を有するようになるが、化粧紙の製造
の際に合成樹脂含浸液を乾燥させる工程が必要で
あり、また、化粧板の製造の際には、例えばメラ
ミン化粧板においては、化粧紙を別製のコアー紙
やオーバーレイ紙等と積層し、これを熱プレスす
る工程が必要であるため、これらの各工程におい
て煩雑な手間と大量の熱エネルギーとを要する。"Problem to be Solved by the Invention" The former type of decorative board made of decorative paper has excellent effects on various physical properties, but a step of drying the synthetic resin impregnated liquid is required when manufacturing the decorative paper. In addition, when manufacturing decorative laminates, for example, melamine decorative laminates require a process of laminating the decorative paper with separate core paper, overlay paper, etc., and heat pressing them. Each process requires complicated labor and a large amount of thermal energy.
また、後者の塩化ビニル化粧紙は、該化粧紙を
利用する化粧板の製造自体は簡単であるが、得ら
れる化粧板の表面硬度、耐溶剤性、耐熱性等の物
性が著しく劣るという欠点を有する。 In addition, the latter type of vinyl chloride decorative paper has the drawback that, although it is easy to manufacture a decorative board using the decorative paper, the physical properties of the resulting decorative board such as surface hardness, solvent resistance, and heat resistance are significantly inferior. have
これらの問題を解決する方法として、片面に絵
柄模様の印刷が施されている薄手の紙に合成樹脂
溶液からなるコーテイング剤をオーバーコートし
たもの、あるいは、同じく片面に絵柄模様の印刷
が施されている浸透性の良好な紙に、触媒が添加
されている合成樹脂溶液を含浸させ、これを加
熱、硬化させた加熱硬化型の化粧紙が提案された
が、オーバーコートによる化粧紙は、依然として
表面硬度、耐溶剤性、耐熱性等の物性が不十分で
あり、また、加熱硬化型の化粧紙は、その製造に
際して多量のエネルギーを必要とする。 As a way to solve these problems, thin paper with a pattern printed on one side is overcoated with a coating agent made of a synthetic resin solution, or a thin paper with a pattern printed on one side is overcoated with a coating agent made of a synthetic resin solution. A heat-curable decorative paper has been proposed, in which paper with good permeability is impregnated with a synthetic resin solution containing a catalyst, and then heated and cured. Physical properties such as hardness, solvent resistance, and heat resistance are insufficient, and heat-curable decorative paper requires a large amount of energy during its production.
このため、多量のエネルギーを必要とすること
なく、しかも、表面硬度、耐溶剤性、耐熱性等の
物性に対して良好な性質を有する化粧紙を得る方
法として、電子線硬化性樹脂の含浸工程と電子線
の照射とによる化粧紙の製造が検討され始めた
が、１回だけの電子線の照射により、すなわち、
効率の良い製造方法により、表面硬度、耐溶剤
性、耐熱性等の物性を十分に満足する化粧紙が得
られるような条件については、未だ解明されてい
ない。 Therefore, as a method for obtaining decorative paper that does not require a large amount of energy and has good physical properties such as surface hardness, solvent resistance, and heat resistance, the impregnation process with electron beam curable resin has been proposed. The production of decorative paper by irradiation with electron beams has begun to be considered, but with only one irradiation of electron beams,
The conditions under which decorative paper with sufficient physical properties such as surface hardness, solvent resistance, and heat resistance can be obtained by an efficient manufacturing method have not yet been elucidated.
これに対して、本発明方法は、通常使用されて
いる自己遮蔽型の電子線照射装置による１回だけ
の電子線の照射により、表面硬度、耐溶剤性、耐
熱性等に優れた性質を有する化粧紙が得られる方
法を提供する。 In contrast, the method of the present invention achieves excellent properties such as surface hardness, solvent resistance, and heat resistance by only one electron beam irradiation using a commonly used self-shielding electron beam irradiation device. To provide a method for obtaining decorative paper.
なお、因みに、紫外線硬化型の樹脂を利用する
場合には、含浸剤（コーテイング剤）中に添加さ
れる増感剤の量を加減しても、含浸用紙に含浸さ
れている紫外線硬化型樹脂を、１回の紫外線の照
射処理で完全に硬化させることは困難である。 Incidentally, when using an ultraviolet curable resin, even if the amount of sensitizer added to the impregnating agent (coating agent) is adjusted, the ultraviolet curable resin impregnated into the impregnated paper will not be affected. However, it is difficult to completely cure the material with one UV irradiation treatment.
「課題を解決するための手段」
本発明の化粧紙の製造方法は、片面に絵柄印刷
が付されている坪量20〜300g／m2の浸透性の良
好な紙を含浸用紙として利用し、該含浸用紙に対
して、分子中にエチレン性二重結合を有するプレ
ポリマーもしくはオリゴマー５重量％以上と分子
中にエチレン性二重結合を有する多官能性モノマ
ー及び／又はポリチオール95重量％以下とによる
電子線硬化性混合物を含有する100ポイズ（25℃）
以下の含浸剤を、５〜150g／m2の割合で含浸さ
せる工程と、加速電圧100〜300KVの電子線を１
回だけ照射することによつて0.5〜30Mradの線量
の電子線を照射し、含浸用紙に含浸されている電
子線硬化性混合物を硬化させ工程とにより、目的
とする化粧紙を得ることからなる。"Means for Solving the Problems" The method for producing decorative paper of the present invention uses, as impregnated paper, paper with good permeability and a basis weight of 20 to 300 g/m 2 and which has a pattern printed on one side. Based on the impregnated paper, 5% by weight or more of a prepolymer or oligomer having an ethylenic double bond in the molecule and 95% by weight or less of a polyfunctional monomer and/or polythiol having an ethylenic double bond in the molecule. 100 poise (25℃) containing electron beam curable mixture
The process of impregnating with the following impregnating agent at a rate of 5 to 150 g/m 2 and applying an electron beam with an accelerating voltage of 100 to 300 KV.
The desired decorative paper is obtained by irradiating the electron beam at a dose of 0.5 to 30 Mrad by irradiating the paper once to cure the electron beam curable mixture impregnated in the impregnated paper.
本発明の化粧紙の製造方法の各工程を図面に基
づいて説明する。 Each step of the method for producing decorative paper of the present invention will be explained based on the drawings.
本発明の化粧紙の製造方法において含浸用紙と
して利用される片面に絵柄印刷が付されている坪
量20〜300g／m2の浸透性の良好な紙２は、例え
ば、チタン紙、リンター紙、クラフト紙、上質紙
等からなる。含浸用紙の坪量が20g／m2未満の場
合には紙力不足のために、含浸剤を塗工方法にて
含浸させる場合に、均一に含浸させることが困難
となり、また、含浸用紙の坪量が300g／m2を超
えるような場合には、含浸剤の含浸作用が低下す
るため、含浸用紙の裏面に至るまで略均一に含浸
剤を含浸させ得るだけの含浸剤の浸透作用と、１
回の電子線の照射で電子線硬化性混合物を完全に
硬化させ得る電子線照射適性とが得られなくな
る。 The paper 2 with good permeability and having a basis weight of 20 to 300 g/m 2 and having a pattern printed on one side and used as the impregnated paper in the method for producing decorative paper of the present invention is, for example, titanium paper, linter paper, Made of kraft paper, high quality paper, etc. If the basis weight of the impregnated paper is less than 20g/ m2 , it will be difficult to uniformly impregnate the impregnating agent when impregnated with the coating method due to insufficient paper strength. If the amount exceeds 300 g/m 2 , the impregnating effect of the impregnating agent will decrease, so the impregnating agent's penetrating effect will be sufficient to impregnate the impregnating agent almost uniformly to the back side of the impregnated paper.
It is no longer possible to obtain electron beam irradiation suitability to completely cure the electron beam curable mixture by multiple electron beam irradiations.
なお、浸透性の良好な紙２に付されている絵柄
模様Ｍは、従来の化粧紙における絵柄模様と同様
に、既存の印刷インキ及び印刷手段によつて容易
に形成される。 Note that the picture pattern M applied to the paper 2 with good permeability can be easily formed using existing printing ink and printing means, similar to the picture pattern on conventional decorative paper.
浸透性の良好な紙２による含浸用紙に含浸され
る含浸剤は、分子中にエチレン性二重結合を有す
るプレポリマーもしくはオリゴマー５重量％以上
と分子中にエチレン性二重結合を有する多官能性
モノマー及び／又はポリチオール95重量％以下と
による電子線硬化性混合物を含有する100ポイズ
（25℃）以下のものである。 The impregnating agent that is impregnated into the impregnated paper using paper 2 with good permeability is a prepolymer or oligomer having an ethylenic double bond in the molecule of 5% or more and a polyfunctionality having an ethylenic double bond in the molecule. 100 poise (25°C) or less containing an electron beam curable mixture of monomers and/or polythiols of 95% by weight or less.
電子線硬化性混合物に利用される分子中にエチ
レン性二重結合を有するプレポリマーもしくはオ
リゴマーは、例えば、不飽和ポリエステル類、ポ
リエステルアクリレート、エポキシアクリレー
ト、ウレタンアクリレート、ポリエーテルアクリ
レート、ポリオールアクリレート、メラミンアク
リレート等による各種のアクリレート類、ポリエ
ステルメタクリレート、エポキシメタクリレー
ト、ウレタンメタクリレート、ポリエーテルメタ
クリレート、ポリオールメタクリレート、メラミ
ンメタクリレート等による各種のメタクリレート
類の１種または２種以上の混合物等である。 Prepolymers or oligomers having ethylenic double bonds in the molecule used in electron beam curable mixtures include, for example, unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, and melamine acrylates. These include one type or a mixture of two or more of various methacrylates such as polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate.
また、分子中にエチレン性二重結合を有する多
官能性モノマーとしては、
スチレン、α・メチルスチレン等によるスチレ
ン系モノマー、
アクリル酸メチル、アクリル酸−２−エチルヘ
キシル、アクリル酸メトキシエチル、アクリル酸
ブトキシエチル、アクリル酸ブチル、アクリル酸
メトキシブチル、アクリル酸フエニル等によるア
クリル酸エステル類、メタクリル酸メチル、メタ
クリル酸エチル、メタクリル酸プロピル、メタク
リル酸メトキシエチル、メタクリル酸エトキシメ
チル、メタクリル酸フエニル、メタクリル酸ラウ
リル等によるメタクリル酸エステル類、
アクリルアミド、メタクリルアミド等による不
飽和カルボン酸アミド、
アクリル酸−２−（Ｎ，Ｎ−ジエチルアミノ）
エチル、メタクリル酸（Ｎ，Ｎ−ジメチルアミ
ノ）エチル、アクリル酸−２−（Ｎ，Ｎ−ジベン
ジルアミノ）エチル、メタクリル酸（Ｎ，Ｎ−ジ
メチルアミノ）メチル、アクリル酸−２−（Ｎ，
Ｎ−ジエチルアミノ）プロピル等による不飽和酸
の置換アミノアルコールエステル類、
エチレングリコールジアクリレート、プロピレ
ングリコールジアクリレート、ネオペチルグリコ
ールジアクリレート、１，６−ヘキサンジオール
ジアクリレート、ジエチレングリコールジアクリ
レート、トレエチレングリコールジアクリレー
ト、ジプロピレングリコールジアクリレート、エ
チレングリコールジメタクリレート、ポロピレン
グリコールジメタクリレート、ジエチレングリコ
ールジメタクリレート等による多官能性化合物が
利用される。 In addition, polyfunctional monomers having an ethylenic double bond in the molecule include styrene, styrenic monomers such as α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, and butoxy acrylate. Acrylic esters such as ethyl, butyl acrylate, methoxybutyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate methacrylic acid esters, acrylamide, unsaturated carboxylic acid amide, acrylic acid-2-(N,N-diethylamino), etc. by methacrylamide, etc.
Ethyl, (N,N-dimethylamino)ethyl methacrylate, 2-(N,N-dibenzylamino)ethyl acrylate, (N,N-dimethylamino)methyl methacrylate, 2-(N,
Substituted amino alcohol esters of unsaturated acids such as N-diethylamino)propyl, ethylene glycol diacrylate, propylene glycol diacrylate, neopetyl glycol diacrylate, 1,6-hexane diol diacrylate, diethylene glycol diacrylate, treethylene glycol diacrylate Polyfunctional compounds such as acrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, polypylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. are used.
さらに、ポリチオールとしては、トリメチロー
ルプロパントリチオグリコレート、トリメチロー
ルプロパントリチオプロピオネート、ペンタエリ
スリトールテトラチオグリコーレート等が利用さ
れる。 Further, as the polythiol, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, pentaerythritol tetrathioglycolate, etc. are used.
なお、分子中にエチレン性二重結合を有するプ
レポリマーもしくはオリゴマー５重量％以上と分
子中にエチレン性二重結合を有する多官能性モノ
マー及び／又はポリチオール95重量％以下とによ
る電子線硬化性混合物を含有する含浸剤中には、
例えば、ハイドロキノン、ハイドロキノンモノメ
チルエテール、ベンゾキノン等の重合禁止剤が、
電子線の照射前に電子線硬化性混合物が硬化する
のを防止し、含浸剤による含浸工程を容易に行な
うために、必要に応じて添加される。 In addition, an electron beam curable mixture consisting of 5% by weight or more of a prepolymer or oligomer having an ethylenic double bond in the molecule and 95% by weight or less of a polyfunctional monomer and/or polythiol having an ethylenic double bond in the molecule. In the impregnating agent containing
For example, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, etc.
It is added as necessary to prevent the electron beam curable mixture from curing before irradiation with the electron beam and to facilitate the impregnation step with the impregnating agent.
含浸剤中の電子線硬化性混合物には、該電子線
硬化性混合物を含有する含浸剤の含浸適性の点か
ら、分子中にエチレン性二重結合を有するプレポ
リマーもしくはオリゴマー５重量％以上と分子中
にエチレン性二重結合を有する多官能性モノマー
及び／又はポリチオール95重量％以下との混合物
が利用される。 The electron beam curable mixture in the impregnating agent contains 5% by weight or more of a prepolymer or oligomer having an ethylenic double bond in the molecule and 5% by weight or more of a prepolymer or oligomer having an ethylenic double bond in the molecule, from the viewpoint of impregnating suitability of the impregnating agent containing the electron beam curable mixture. A mixture with a polyfunctional monomer having an ethylenic double bond therein and/or a polythiol in an amount of up to 95% by weight is used.
また、含浸剤の粘度が100ポイズ（25℃）を超
える場合には、紙２に対する含浸剤の浸透作用が
悪くなり、硬化型樹脂によつて紙２の層間強度を
高めることができなくなる。なお、含浸剤の粘度
は、含浸剤中の分子中にエチレン性二重結合を有
するプレポリマーもしくはオリゴマーと分子中に
エチレン性二重結合を有する多官能性モノマー及
び／又はポリチオールとの割合によつて、あるい
は、含浸剤を紙２の含浸させる際に、含浸剤を含
浸剤中の電子線硬化性混合物が蒸発することのな
い温度に加温する等によつて、適宜低下させ得
る。 Furthermore, if the viscosity of the impregnating agent exceeds 100 poise (25° C.), the impregnating agent's penetrating effect on the paper 2 becomes poor, and the interlaminar strength of the paper 2 cannot be increased by the curable resin. The viscosity of the impregnating agent depends on the ratio of the prepolymer or oligomer having an ethylenic double bond in the molecule and the polyfunctional monomer and/or polythiol having an ethylenic double bond in the molecule in the impregnant. Alternatively, when impregnating the paper 2 with the impregnating agent, the impregnating agent may be lowered appropriately by heating the impregnating agent to a temperature at which the electron beam curable mixture in the impregnating agent does not evaporate.
紙２に対する含浸剤の含浸は、デイツピングに
よつて、あるいは、ロールコート、カーテンフロ
ーコート、ミヤバーコート、グラビアロールコー
ト、エアナイフコート等の塗工によつて行なわれ
る。 The paper 2 is impregnated with the impregnating agent by dipping, or by coating such as roll coating, curtain flow coating, membrane coating, gravure roll coating, and air knife coating.
紙２に含浸された含浸剤中の電子線硬化性混合
物を硬化させるための電子線の照射工程は、例え
ば、窒素雰囲気中での低エネルギー電子加速器、
例えば、エネルギーサイエンスインコーポレーシ
ヨン社製のエレクトロカーテン CB 200／50／
30や、オツトデユール社製のNP−ESH150等を
利用し、加速電圧100〜300KV、照射電流０〜
100mAにより、0.5〜30Mradの線量の電子線を
１回だけ照射することによつて行なわれる。 The electron beam irradiation step for curing the electron beam curable mixture in the impregnating agent impregnated into the paper 2 is performed using, for example, a low energy electron accelerator in a nitrogen atmosphere,
For example, Electro Curtain CB 200/50/manufactured by Energy Science Inc.
30 or NP-ESH150 manufactured by Otsuto Duel, acceleration voltage 100-300KV, irradiation current 0-
It is carried out by a single irradiation with an electron beam at a dose of 0.5 to 30 Mrad at 100 mA.
本発明の化粧紙の製造方法によつて得られる化
粧紙１は、片面に絵柄印刷Ｍが付されている坪量
20〜300g／m2の浸透性の良好な紙２に含浸され
た電子線硬化性混合物が電子線の照射で硬化され
ており、その最外表面が電子線の照射で硬化され
た硬化樹脂３層で形成され、化粧紙１の全体が三
次元的に架橋した硬化樹脂３で形成される。この
ため、表面硬度、耐溶剤性、耐熱性等において極
めて優れた性質の化粧紙になる。 The decorative paper 1 obtained by the method for producing decorative paper of the present invention has a basis weight of
An electron beam curable mixture impregnated into paper 2 with good permeability of 20 to 300 g/m 2 is cured by electron beam irradiation, and the outermost surface thereof is cured by electron beam irradiation. The entire decorative paper 1 is formed of a three-dimensionally crosslinked cured resin 3. Therefore, the decorative paper has extremely excellent properties such as surface hardness, solvent resistance, and heat resistance.
また、本発明の化粧紙の製造方法によつて得ら
れた化粧紙は、該化粧紙を利用する化粧板に製造
に際しては、化粧板用基材に対して接着剤で貼着
するだけで良く、化粧板の製造工程が簡単かつ容
易である。 Furthermore, when manufacturing the decorative paper obtained by the method for producing decorative paper of the present invention into a decorative board using the decorative paper, it is sufficient to simply adhere it to the base material for the decorative board with an adhesive. , the manufacturing process of decorative board is simple and easy.
本発明の化粧紙の製造方法は、１回だけの電子
線の照射によつて含浸剤中の電子線硬化性混合物
を硬化させるものであることから、電子線の照射
を連続的に行なうことができる。このため、本発
明の化粧紙の製造方法においては、電子線の照射
によつて含浸剤中の電子線硬化性混合物を硬化さ
せた後に、得られた化粧紙を巻き取る工程を連続
して行なうことができる。したがつて、その工程
中に、煩雑な操作が必要で無く、化粧紙を効率良
く製造し得る。 Since the method for producing decorative paper of the present invention cures the electron beam-curable mixture in the impregnating agent by irradiating the electron beam only once, continuous electron beam irradiation is not required. can. Therefore, in the method for producing decorative paper of the present invention, after curing the electron beam-curable mixture in the impregnating agent by irradiation with electron beams, the step of winding up the obtained decorative paper is performed continuously. be able to. Therefore, no complicated operations are required during the process, and decorative paper can be manufactured efficiently.
また、本発明の化粧紙の製造方法は、その工程
中に、溶剤を乾燥させる工程や、含浸用紙に含浸
されているコーテイング剤中の硬化性組成物を硬
化させるための熱エネルギーを消費する工程を必
要としないため、安価な化粧紙を供給し得る。 In addition, the method for producing decorative paper of the present invention includes a step of drying the solvent and a step of consuming thermal energy for curing the curable composition in the coating agent impregnated into the impregnated paper. Since this method does not require any paper, it is possible to supply inexpensive decorative paper.
「実施例」
以下、本発明の化粧紙の製造方法の具体的な構
成と、得られた化粧紙の性質とを、実施例をもつ
て説明する。"Example" Hereinafter, the specific structure of the method for producing decorative paper of the present invention and the properties of the obtained decorative paper will be explained using Examples.
実施例 １
坪量55g／m2のチタン紙の片面にグラビア印刷
による木目柄の絵柄印刷を付した含浸用紙を得
た。Example 1 Impregnated paper with a wood grain pattern printed by gravure printing on one side of titanium paper with a basis weight of 55 g/m 2 was obtained.
次いで、この絵柄印刷面に、下記の組成〔Ａ〕
による含浸剤を50g／m2の割合にミヤバーコート
法によつて塗布し、含浸用紙の全体に対して略均
一に含浸させた。 Next, the following composition [A] is applied to this pattern printing surface.
The impregnating agent was applied at a rate of 50 g/m 2 by the Myabar coating method, and the entire impregnated paper was impregnated substantially uniformly.
組成 〔Ａ〕
(1) アクリレートオリゴマー［諸星インキ(株)］
……60重量部
(2) １，６−ヘキサンジオールジアクリレート
［日本化薬(株)］ ……40重量部
粘度：１ポイズ（25℃）
次いで、前記含浸剤の塗布面から、酸素濃度
300ppm以下の窒素雰囲気中にて、175KVに加速
されている電子線の5Mradの照射を１回だけ行
なうことにより、目的の化粧紙を得た。Composition [A] (1) Acrylate oligomer [Moroboshi Ink Co., Ltd.]
...60 parts by weight (2) 1,6-hexanediol diacrylate [Nippon Kayaku Co., Ltd.] ...40 parts by weight Viscosity: 1 poise (25°C) Next, the oxygen concentration was determined from the surface where the impregnating agent was applied.
The desired decorative paper was obtained by performing only one irradiation of 5 Mrad with an electron beam accelerated to 175 KV in a nitrogen atmosphere of 300 ppm or less.
得られた化粧紙の表面硬度は鉛筆硬度の4H以
上であり、耐薬品性、耐溶剤性、耐汚染性に優れ
ていた。 The surface hardness of the obtained decorative paper was 4H or higher on a pencil hardness, and it had excellent chemical resistance, solvent resistance, and stain resistance.
また、この化粧紙をパーテイクルボードにウレ
タン系接着剤で貼着したところ、積層板に必要と
されるに十分な接着強度が得られた。 Furthermore, when this decorative paper was attached to particle board using a urethane adhesive, sufficient adhesive strength required for a laminate was obtained.
実施例 ２
実施例１で利用したものと同一の木目柄の絵柄
印刷を有するチタン紙からなる含浸用紙の絵柄印
刷面に、下記の組成［Ｂ］による含浸剤を30g／
m2の割合にフアウンテンコート法によつて塗布
し、含浸用紙の全体に対して略均一に含浸させ
た。Example 2 30 g of an impregnating agent having the following composition [B] was applied to the pattern printed surface of impregnated titanium paper having the same wood grain pattern printed as that used in Example 1.
m 2 of the impregnated paper by the fountain coating method, and the entire impregnated paper was impregnated almost uniformly.
組成 〔Ｂ〕
(1) 分子中にエチレン性二重結合を有するプレポ
リマー ……20重量部
(2) ポリチオール ……80重量部
粘度：3.4ポイズ（25℃）
次いで、前記含浸剤の塗布面から、酸素濃度
300ppm以下の窒素雰囲気中にて、175KVに加速
されている電子線による3Mradの照射を１回だ
け行なうことにより、目的の化粧紙を得た。Composition B , oxygen concentration
The desired decorative paper was obtained by performing irradiation of 3 Mrad with an electron beam accelerated to 175 KV only once in a nitrogen atmosphere of 300 ppm or less.
得られた化粧紙の表面硬度は鉛筆硬度の2H以
上であり、耐薬品性、耐溶剤性、耐汚染性に優れ
ていた。 The surface hardness of the obtained decorative paper was 2H or more of pencil hardness, and it had excellent chemical resistance, solvent resistance, and stain resistance.
また、この化粧紙をパーテイクルボードにウレ
タン系接着剤で貼着したところ、積層板に必要と
されるに十分な接着強度が得られた。 Furthermore, when this decorative paper was attached to particle board using a urethane adhesive, sufficient adhesive strength required for a laminate was obtained.
「効果」
本発明の化粧紙の製造方法においては、坪量20
〜300g／m2の浸透性の良好な紙を含浸用紙とし
て利用し、分子中にエチレン性二重結合を有する
プレポリマーもしくはオリゴマー５重量％以上と
分子中にエチレン性二重結合を有する多官能性モ
ノマー及び／又はポリチオール95重量％以下とに
よる電子線硬化性混合物を含有する100ポイズ
（25℃）以下の含浸剤を、５〜150g／m2の割合で
含浸させ、かつ、加速電圧100〜300KVの電子線
を0.5〜30Mradの線量で照射する等の構成を組み
合わせて利用することにより、含浸用紙に対して
は、電子線硬化性混合物を含有する含浸剤を含浸
用紙の裏面に至るまで略均一に含浸させることが
でき、また、含浸用紙中に含浸、保持させてある
電子線硬化性混合物を、通常利用されている自己
遮蔽型電子線加速装置による１回だけの電子線の
照射により、含浸用紙の裏面側に位置する電子線
硬化性混合物までも完全に硬化させ得る電子線照
射適性とを満足する。"Effect" In the method for producing decorative paper of the present invention, the basis weight is 20
~300g/ m2 paper with good permeability is used as impregnated paper, and 5% by weight or more of prepolymer or oligomer having ethylenic double bonds in the molecule and polyfunctionality having ethylenic double bonds in the molecule are used. An impregnating agent of 100 poise (25°C) or less containing an electron beam curable mixture of 95% by weight or less of polypropylene monomer and/or polythiol is impregnated at a rate of 5 to 150 g/ m2 , and an accelerating voltage of 100 to 150 g/m2. By using a combination of configurations such as irradiation with a 300 KV electron beam at a dose of 0.5 to 30 Mrad, impregnated paper can be coated with an impregnating agent containing an electron beam curable mixture almost all the way to the back side of the impregnated paper. It can be uniformly impregnated, and the electron beam curable mixture impregnated and held in the impregnated paper is irradiated with an electron beam only once using a commonly used self-shielding electron beam accelerator. It satisfies the suitability for electron beam irradiation to completely cure even the electron beam curable mixture located on the back side of the impregnated paper.
したがつて、本発明の化粧紙の製造方法におい
ては、１回の電子線の照射により、表面硬度、耐
溶剤性、耐熱性等の物性を十分に満足する化粧紙
が、効率の良い製造条件にて得られる。 Therefore, in the method for producing decorative paper of the present invention, it is possible to produce decorative paper that fully satisfies physical properties such as surface hardness, solvent resistance, and heat resistance by one irradiation with an electron beam under efficient manufacturing conditions. Obtained at
図は、本発明の化粧紙の製造方法によつて得ら
れた化粧紙の１例を模型的に示す断面図である。
１……化粧紙、２……坪量20〜300g／m2の浸
透性の良好な紙による含浸用紙、３……電子線に
よつて硬化された樹脂、Ｍ……絵柄模様。
The figure is a cross-sectional view schematically showing an example of decorative paper obtained by the method for manufacturing decorative paper of the present invention. 1... Decorative paper, 2... Impregnated paper made of paper with good permeability having a basis weight of 20 to 300 g/ m2 , 3... Resin cured by electron beam, M... Pattern.
Claims (1)
300g／m2の浸透性の良好な紙に対して、分子中
にエチレン性二重結合を有するプレポリマーもし
くはオリゴマー５重量％以上と分子中にエチレン
性二重結合を有する多官能性モノマー及び／又は
ポリチオール95重量％以下とによる電子線硬化性
混合物を含有する100ポイズ（25℃）以下の含浸
剤を、５〜150g／m2の割合で含浸させた後、加
速電圧100〜300KVの電子線を１回だけ照射する
ことによつて0.5〜30Mradの電子線量を照射し、
含浸されている電子線硬化性混合物を硬化させる
ことを特徴とする化粧紙の製造方法。1 Basis weight 20~ with pattern printed on one side
300 g/m 2 of paper with good permeability, 5% by weight or more of a prepolymer or oligomer having an ethylenic double bond in the molecule and a polyfunctional monomer and/or a polyfunctional monomer having an ethylenic double bond in the molecule. Or, after impregnating with an impregnating agent of 100 poise (25°C) or less containing an electron beam curable mixture of 95% by weight or less of polythiol at a rate of 5 to 150 g/ m2 , an electron beam at an accelerating voltage of 100 to 300 KV is applied. Irradiate an electron dose of 0.5 to 30 Mrad by irradiating it only once,
A method for producing decorative paper, comprising curing an impregnated electron beam curable mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1966081A JPS57133066A (en) | 1981-02-13 | 1981-02-13 | Decorative paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1966081A JPS57133066A (en) | 1981-02-13 | 1981-02-13 | Decorative paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57133066A JPS57133066A (en) | 1982-08-17 |
| JPH0422694B2 true JPH0422694B2 (en) | 1992-04-20 |
Family
ID=12005395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1966081A Granted JPS57133066A (en) | 1981-02-13 | 1981-02-13 | Decorative paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57133066A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59112095A (en) * | 1982-12-15 | 1984-06-28 | 東洋インキ製造株式会社 | Decorative paper and production thereof |
| DE3418282A1 (en) * | 1984-05-17 | 1985-11-21 | Hoechst Ag, 6230 Frankfurt | DECORATIVE PLATE WITH IMPROVED SURFACE PROPERTIES |
| JPS62142527U (en) * | 1986-03-04 | 1987-09-08 | ||
| JPH0661839B2 (en) * | 1988-12-14 | 1994-08-17 | 凸版印刷株式会社 | Method for manufacturing embossing die for decorative board |
| CN108049246A (en) * | 2018-01-22 | 2018-05-18 | 中山松德印刷机械有限公司 | A kind of production equipment for producing woodgrained paper dipping paper |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS555912A (en) * | 1978-06-28 | 1980-01-17 | Asahi Chem Ind Co Ltd | Half-cured sheet forming material |
-
1981
- 1981-02-13 JP JP1966081A patent/JPS57133066A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS555912A (en) * | 1978-06-28 | 1980-01-17 | Asahi Chem Ind Co Ltd | Half-cured sheet forming material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57133066A (en) | 1982-08-17 |
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