JPH01105737A - Decorative sheet and decorative plywood of thermoplastic resin - Google Patents
Decorative sheet and decorative plywood of thermoplastic resinInfo
- Publication number
- JPH01105737A JPH01105737A JP63178228A JP17822888A JPH01105737A JP H01105737 A JPH01105737 A JP H01105737A JP 63178228 A JP63178228 A JP 63178228A JP 17822888 A JP17822888 A JP 17822888A JP H01105737 A JPH01105737 A JP H01105737A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- decorative
- amino
- decorative board
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011120 plywood Substances 0.000 title claims abstract description 82
- 229920005992 thermoplastic resin Polymers 0.000 title description 7
- 229920003180 amino resin Polymers 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 239000011342 resin composition Substances 0.000 claims abstract description 42
- -1 amino compound Chemical class 0.000 claims abstract description 28
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 54
- 239000000123 paper Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 16
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 8
- 229920000180 alkyd Polymers 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000002932 luster Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 41
- 238000001723 curing Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229910052719 titanium Inorganic materials 0.000 description 19
- 239000010936 titanium Substances 0.000 description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000013007 heat curing Methods 0.000 description 7
- 239000002655 kraft paper Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000007602 hot air drying Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010058109 Hangnail Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241001149163 Ulmus americana Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、表面硬度が大きく、光沢、可撓性、耐光性、
耐汚染性、耐水性、耐薬品性および耐クラツク性に優れ
た化粧板および表面硬度、光沢、耐光性、耐汚染性、耐
水性、耐薬品性および耐クラツク性に優れた化粧合板に
関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention has high surface hardness, gloss, flexibility, light resistance,
Concerning decorative laminates with excellent stain resistance, water resistance, chemical resistance, and crack resistance, and decorative plywood with excellent surface hardness, gloss, light resistance, stain resistance, water resistance, chemical resistance, and crack resistance. be.
（従来技術および発明が解決しようとする課題）従来公
知のオーバーレイ化粧板および化粧合板にはポリ塩化ビ
ニル樹脂フィルムやポリエステルフィルムに着色あるい
は模様を印刷しベニヤ合板やハードボードなどに貼着し
た熱可塑性樹脂化粧板および化粧合板が知られている。(Prior Art and Problems to be Solved by the Invention) Conventionally known overlay decorative boards and decorative plywood are thermoplastic resin films that are colored or printed with patterns on polyvinyl chloride resin films or polyester films and then adhered to plywood or hardboard. Resin decorative boards and decorative plywood are known.
またメラミン樹脂、ベンゾグアナミン樹脂、フェノール
樹脂、不飽和ポリエステル樹脂などの単独または共縮合
樹脂を着色あるいは模様を印刷した紙または布に含浸せ
しめると同時に硬化せしめる方法による熱硬化性樹脂化
粧板および該含浸紙または含浸布を基板と一体化して硬
化せしめる方法による熱硬化性樹脂化粧合板などがある
。Also, thermosetting resin decorative laminates and impregnated paper made by impregnating colored or patterned paper or cloth with a single or co-condensed resin such as melamine resin, benzoguanamine resin, phenol resin, or unsaturated polyester resin and simultaneously curing the resin. Alternatively, there is a thermosetting resin decorative plywood made by integrating an impregnated cloth with a substrate and curing it.
熱可塑性樹脂化粧板および化粧合板は優れた可撓性を有
し加工が自由であるが表面硬度、耐熱性、耐薬品性が不
良であシ、熱硬化性樹脂化粧板および化粧合板は表面硬
度が高く、耐熱性、耐薬品性にも侵れているが、可撓性
に乏しく運搬や加工の際にクラックを生成したシ、破壊
を起こし易く、また温湿度などの環境条件の変化に、よ
シフラックを生成しやすいことや耐光性が悪いなどの欠
点がある。Thermoplastic resin decorative boards and decorative plywood have excellent flexibility and can be processed freely, but they have poor surface hardness, heat resistance, and chemical resistance.Thermosetting resin decorative boards and decorative plywood have poor surface hardness. Although it has high heat resistance and chemical resistance, it has poor flexibility and is prone to cracks and breakage during transportation and processing, and is susceptible to changes in environmental conditions such as temperature and humidity. It has drawbacks such as easy generation of oxidative flux and poor light resistance.
例えばメラミン樹脂を用いた化粧板や化粧合板では、成
形加工時の硬化条件において硬化を進めると、光沢、耐
水性、耐薬品性などが向上するが、逆に硬化が進むにつ
れて耐クラツク性が低下するという欠点があった。この
ように、全ての諸物性を満たす化粧板や化粧合板は知ら
れていなかった。For example, in decorative boards and plywood made of melamine resin, as the curing process progresses under the curing conditions during molding, gloss, water resistance, chemical resistance, etc. improve, but conversely, as curing progresses, crack resistance decreases. There was a drawback to that. As described above, decorative laminates and decorative plywood that satisfy all physical properties have not been known.
一方、本発明で用いられるシクロヘキサンカルボグアナ
ミンまたはノルボルナンカルボグアナミンと半和ホ＃尋
メラミンとの共縮合物および該共縮合物を成形材料とし
て使用されることはＵＳＰ３．３７９，６６１号に開示
されておシ、該成形材料から得られた成形品は、耐光性
および耐汚染性に優れていることも知られていた。しか
しながら、該共縮合物を化粧板や化粧合板に使用するこ
とは記載されておらず、成形方法の異なる成形材料の成
形方法を化粧板や化粧合板に適用することはできず、ま
た化粧板や化粧合板の製造に適した上記共縮合物の製法
を公知事実から見出すのは困難であった。また、この共
縮合物の可撓性および耐クラツク性に関する記載もなく
、との共縮合物が化粧板や化粧合板に要求される諸性能
を与える可能性を上記公知事実から見出すのは困難であ
った。On the other hand, the co-condensate of cyclohexanecarboguanamine or norbornanecarboguanamine and half-polymerized melamine used in the present invention and the use of the co-condensate as a molding material are disclosed in US Pat. No. 3,379,661. It was also known that molded articles obtained from the molding material have excellent light resistance and stain resistance. However, there is no description of the use of the co-condensate for decorative laminates or decorative plywood, and it is not possible to apply molding methods for molding materials that require different molding methods to decorative laminates or decorative plywood. It was difficult to find out from known facts a method for producing the above-mentioned co-condensate suitable for producing decorative plywood. Furthermore, there is no description regarding the flexibility and crack resistance of this co-condensate, and it is difficult to find out from the above-mentioned known facts that a co-condensate with there were.
従って、本発明の目的は、新規な化粧板および化粧合板
を提供することにある。Therefore, an object of the present invention is to provide a novel decorative board and decorative plywood.
本発明の他の目的は、表面硬度が大きく、可撓性、光沢
、耐光性、耐汚染性、耐水性、耐薬品性および耐クラツ
ク性に優れている化粧板および表面硬度、光沢、耐光性
、耐汚染性、耐水性、耐薬品性および耐クラツク性が優
れておシ、樹脂含浸シート層が基板と一体化されてなる
化粧合板を提供することＫある。Another object of the present invention is to provide a decorative board with high surface hardness and excellent flexibility, gloss, light resistance, stain resistance, water resistance, chemical resistance, and crack resistance, and a decorative board with high surface hardness, gloss, and light resistance. Another object of the present invention is to provide a decorative plywood having excellent stain resistance, water resistance, chemical resistance and crack resistance, and in which a resin-impregnated sheet layer is integrated with a substrate.
（課題を解決するための手段および作用）これらの諸目
的は、式１
（ただし、式中、ＸはＣＨ！であシ、またｎはＯｌたは
１である。）で表わされる少なくとも１種のカルボグア
ナミンｔａ）を必須成分として含むアミノ化合物置とホ
ルムアルデヒドとの反応生成物であるアミノ樹脂（Ｉ）
を含有してなる樹脂組成物をシート状物に含浸させかつ
硬化させてなる樹脂含浸シート層を表面に有してなる熱
硬化性樹脂化粧板によシ達成される。(Means and effects for solving the problem) These objectives are achieved by at least one type represented by formula 1 (wherein, X is CH!, and n is Ol or 1). Amino resin (I) which is a reaction product of an amino compound containing carboguanamine ta) as an essential component and formaldehyde
This is achieved by a thermosetting resin decorative board having a resin-impregnated sheet layer on its surface, which is obtained by impregnating and curing a sheet material with a resin composition containing the following.
これらの諸目的はまた式Ｉで表わされる少なくとも１種
のカルボグアナミン（ａ）を必須成分として含むアミノ
化合物置とホルムアルデヒドとの反応生成物であるアミ
ノ樹脂（Ｉ）を含有してなる樹脂組成物をシート状物に
含浸させかつ硬化させてなる樹脂含浸シート層が基板と
一体化されてなる化させかつ該含浸シート状物の硬化層
を表面に有してなるものである。また、化粧合板とは、
前記樹脂含浸シート状物の硬化層と基板とが一体化され
てなるものである。These objects also provide a resin composition comprising an amino resin (I) which is a reaction product of an amino compound containing as an essential component at least one carboguanamine (a) represented by formula I and formaldehyde. A resin-impregnated sheet layer obtained by impregnating and curing a sheet-like material is integrated with a substrate, and has a cured layer of the impregnated sheet-like material on its surface. Also, what is decorative plywood?
The cured layer of the resin-impregnated sheet material and the substrate are integrated.
本発明において使用される樹脂組成物は、式Ｉで表わさ
れる少なくとも１ｆ！Ｊのカルボグアナミン（ａｌを必
須成分として含むアミノ化合物図とホルムアルデヒドと
の反応生成物であるアミノ樹脂（りを含有してなるもの
である。式■で表わされるカルボグアナミン（ａｔとし
ては、式…で表わされるシクロヘキサンカルボグアナミ
ンおよび弐■で表わされるノルボルナンカルボグアナミ
ンがアシ、アミノ化合物図は、該カルボグアナミンの１
種または２種を任意の割合で必須に含んでなるものであ
る。The resin composition used in the present invention has at least 1f! J's carboguanamine (an amino compound diagram containing al as an essential component) is a reaction product of formaldehyde and is a reaction product of carboguanamine (carboguanamine represented by formula 2) (at is the formula... Cyclohexanecarboguanamine represented by 2 and norbornanecarboguanamine represented by
It essentially contains one species or two species in any proportion.
本発明において、アミノ化合物図として、カルボグアナ
ミン（ａｌを用いる意義は、従来の化粧板や化粧合板の
特徴である表面硬度、光沢、耐汚染性、耐水性、耐薬品
性などの性能や美観を損なうことなく、得られる化粧板
や化粧合板に優れた可撓性、耐クラツク性および耐光性
を賦与するとともに、後述のように化粧板または化粧合
板の製造工程での加工性を向上させる点にある。In the present invention, the significance of using carboguanamine (al) as an amino compound diagram is to improve performance and aesthetics such as surface hardness, gloss, stain resistance, water resistance, and chemical resistance, which are characteristics of conventional decorative boards and decorative plywood. In addition to imparting excellent flexibility, crack resistance and light resistance to the resulting decorative laminate or decorative plywood without damaging them, it also improves workability in the manufacturing process of decorative laminates or decorative plywood as described below. be.
本発明のアミノ樹脂（Ｉ）は、製造法によシ脂溶性また
は水溶性の性質を持ち、後述するシート状物の含浸工程
において有機溶剤の溶液または水溶液として使用するこ
とができる。The amino resin (I) of the present invention has fat-soluble or water-soluble properties depending on the manufacturing method, and can be used as an organic solvent solution or an aqueous solution in the step of impregnating a sheet-like material, which will be described later.
脂溶性のアミノ樹脂（Ｉ）を得る場合には、アミノ化合
物図とホルムアルデヒドとを水溶液中で加熱反応させ、
水および未反応ホルムアルデヒドを追い出したのち室温
まで冷却して固体のアミノ樹脂（Ｉ）を得るのが一般的
である。この際使用するホルムアルデヒド量は、アミノ
化合物図１モルに対して１．２〜１０モル、特に１．５
〜４．０モルの範囲が好ましい。すなわち、１０モルを
越えて使用してもその効果は低く、一方、１．２モル未
満では充分に反応が進行しないからである。使用するホ
ルムアルデヒドとしてはパラホルムアルデヒドまたは市
販のホルマリン水溶液を用いるのが簡便である。使用す
るアミノ化合物置中にはアミノ樹脂（Ｉ）の脂溶性を損
なわない範囲であればメラミン、ベンゾグアナミン、ア
セトグアナミンなどのトリアジン類や尿素、ジシアンジ
アミド、フェノール類が含まれてもよい。しかし、カル
ボグアナミン（ａｌを用いた場合の特徴である可撓性、
耐クラツクる。したがって、アミノ化合物図中のカルボ
グアナミン（ａ）の含有量は、好ましくは６０〜１００
重量係、より好ましくは９５〜１００重（Ｉ％である。When obtaining a fat-soluble amino resin (I), the amino compound diagram and formaldehyde are heated and reacted in an aqueous solution,
Generally, after water and unreacted formaldehyde are expelled, the mixture is cooled to room temperature to obtain a solid amino resin (I). The amount of formaldehyde used at this time is 1.2 to 10 mol, especially 1.5 mol, per 1 mol of the amino compound.
A range of 4.0 mol is preferred. That is, even if more than 10 moles are used, the effect will be low, whereas if less than 1.2 moles, the reaction will not proceed sufficiently. As the formaldehyde used, it is convenient to use paraformaldehyde or a commercially available formalin aqueous solution. The amino compounds used may contain triazines such as melamine, benzoguanamine, acetoguanamine, urea, dicyandiamide, and phenols as long as they do not impair the fat solubility of the amino resin (I). However, the flexibility, which is a characteristic of using carboguanamine (al),
Resistant to cracks. Therefore, the content of carboguanamine (a) in the amino compound diagram is preferably 60 to 100.
Weight ratio, more preferably 95 to 100 weight (I%).
この脂溶性のアミ／樹脂（［）のメタノール混和度Ｍｌ
は、１〜２００、特に１〜１５０の範囲が好適である。Methanol miscibility Ml of this fat-soluble amino/resin ([)
is preferably in the range of 1 to 200, particularly 1 to 150.
すなわち、メタノール混和度Ｍ１が１未満では該アミノ
樹脂（Ｉ）の縮合度が高すぎて有機溶剤への溶解度が低
下し、逆に２００を越える場合は縮合度が低すぎて成形
が困難になる場合がある。That is, if the methanol miscibility M1 is less than 1, the degree of condensation of the amino resin (I) will be too high and the solubility in organic solvents will decrease, and if it exceeds 200, the degree of condensation will be too low and molding will become difficult. There are cases.
なお、ここでいうメタノール混和度Ｍ１とは脂溶性のア
ミノ樹脂（Ｉ） ２ ｇをメタノール５ｄに溶解させ、
２５℃で水を滴下して白濁を生じるまでに要した滴下水
１ｋ Ｗｔ （Ｆ）から次式により算出されるものであ
る。In addition, methanol miscibility M1 here refers to 2 g of fat-soluble amino resin (I) dissolved in 5 d of methanol,
It is calculated from the following formula from 1 kWt (F) of dropped water required to produce white turbidity when water is dropped at 25°C.
メタノール混和度Ｍｌ ＝ （Ｗ、／２ ） Ｘ １０
０また脂溶性のアミノ樹脂（Ｉ）に、必要に応じて脂溶
性のベンゾグアナミン樹脂、不飽和ポリエステル樹脂、
アルキッド樹脂、フェノール樹脂などの熱硬化性樹脂を
加えて樹脂組成物とし、該樹脂組成物をシート状物に含
浸させて化粧板や化粧合板を製造することもできる。こ
れらの熱硬化性樹脂は、カルボグアナミン（ａ）の特徴
を損なわない範囲で使用するのが好ましく、通常アミノ
樹脂（Ｉ）１００重量部に対して１０〜１５０重量部、
好ましくは１０〜１００重量部の範囲で用いる。なかで
も不飽和ポリエステル樹脂および／またはアルキッド樹
脂を用いると、該樹脂組成物をシート状物に含浸後乾燥
させた際に、発泡および樹脂のはがれが全くみられず、
作業性が向上する。Methanol miscibility Ml = (W, /2) x 10
0 In addition, to the fat-soluble amino resin (I), if necessary, a fat-soluble benzoguanamine resin, an unsaturated polyester resin,
A decorative board or plywood can also be produced by adding a thermosetting resin such as an alkyd resin or a phenol resin to form a resin composition, and impregnating a sheet-like material with the resin composition. These thermosetting resins are preferably used within a range that does not impair the characteristics of carboguanamine (a), and are usually 10 to 150 parts by weight, based on 100 parts by weight of amino resin (I).
It is preferably used in an amount of 10 to 100 parts by weight. Among them, when an unsaturated polyester resin and/or an alkyd resin is used, no foaming or peeling of the resin is observed when the resin composition is impregnated into a sheet material and then dried.
Improves work efficiency.
上記樹脂組成物は、有機溶剤からなる溶媒に溶解させ、
該溶液をシート状物に含浸させ、乾燥後硬化させると化
粧板や化粧合板が得られる。The resin composition is dissolved in a solvent consisting of an organic solvent,
A sheet material is impregnated with the solution, dried, and then cured to obtain a decorative board or plywood.
この除用いることのできる有機溶剤としては、例えばア
セトン、メチルエチルケトン、シクロヘキサノンなどの
ケトン類、酢酸エチル、酢酸ブチルなどのエステル類お
よびメタノール、エタノール、ブタノールなどの脂肪族
飽和アルコールとヘキサン、シクロヘキサン、石油エー
テルなどの脂肪族炭化水素および／−ｊたはベンゼン、
トルエン、キシレンなどの芳香族炭化水素との混合溶媒
などを挙げることができるが、含浸用のシート状物とし
て着色や印刷加工を施された紙および／または布を用い
るときは、一般にケトン類およびエステル類を溶媒とす
ると脱色が起こる場合もあるので、脂肪族飽和アルコー
ルと脂肪族炭化水素および／または芳香族炭化水素との
混合溶媒を用いるのが適当である。Examples of organic solvents that can be used for this removal include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, aliphatic saturated alcohols such as methanol, ethanol, and butanol, and hexane, cyclohexane, and petroleum ether. aliphatic hydrocarbons such as and/or benzene,
Examples include mixed solvents with aromatic hydrocarbons such as toluene and xylene, but when using colored or printed paper and/or cloth as a sheet material for impregnation, ketones and Since decolorization may occur when esters are used as a solvent, it is appropriate to use a mixed solvent of an aliphatic saturated alcohol and an aliphatic hydrocarbon and/or an aromatic hydrocarbon.
水溶性のアミノ樹脂（Ｉ）は、メラミンおよび／または
尿素を含むアミノ化合物置をホルムアルデヒドと反応さ
せると得られるが化粧板や化粧合板の性能からみてカル
ボグアナミン（ａ）とメラミンとからなるアミノ化合物
置を用いるのが好ましい。Water-soluble amino resin (I) is obtained by reacting an amino compound containing melamine and/or urea with formaldehyde, but from the viewpoint of the performance of decorative boards and decorative plywood, it is an amino compound consisting of carboguanamine (a) and melamine. It is preferable to use the
具体的な製造方法を挙げるならば、カルボグアナミン（
ａｌとメラミンとをホルムアルデヒドの水溶液中で加熱
反応させたのち、室温まで冷却して得られる反応溶液を
アミノ樹脂（Ｉ）の水溶液として使用する。この場合、
均一で安定な溶液となるためには、反応終了時の反応溶
液中の固形分が４０〜７０重量係とするのが好ましい。To give a specific manufacturing method, carboguanamine (
Al and melamine are reacted by heating in an aqueous formaldehyde solution, and then cooled to room temperature, and the resulting reaction solution is used as an aqueous solution of amino resin (I). in this case,
In order to obtain a uniform and stable solution, it is preferable that the solid content in the reaction solution at the end of the reaction is 40 to 70% by weight.
化粧板や化粧合板を製造する場合には、得られる反応液
に、必要によシさらに水および／ま九は水溶性の有機溶
剤を加え、所望の濃度の樹脂溶液としたのち、該溶液を
シート状物に含浸させる方法が一般的である。When manufacturing decorative boards or decorative plywood, water and/or a water-soluble organic solvent are added to the resulting reaction solution as necessary to obtain a resin solution with a desired concentration, and then the solution is A common method is to impregnate a sheet-like material.
この際使用できる水溶性の有機溶剤としては、メタノー
ル、エタノール、インプロパツール、アセトンなどが適
当である。Suitable water-soluble organic solvents that can be used in this case include methanol, ethanol, impropatol, acetone, and the like.
ミ
また、アミノ化合前回に含まれるメラ≠ン量は、アミノ
樹脂（ｆ）が充分な水溶性を持ちかつカルボグアナミン
（ａ）の特徴である可撓性、耐クラツク性などの諸性能
を損なわない範囲の使用量が好ましく、通常２０〜８０
重−ｆｆｉｑｂ、よシ好ましくは２０〜４０重量係であ
る。但し、水溶性のアミノ樹脂（Ｉ）を得る場合もアミ
ノ化合物図中のカルボグアナミン（ａｔＯ量は多い程好
ましく、従ってカルボグアナミン（ａ）の量は２０〜８
０重量係、よシ好ましくは６０〜８０重量係とするのが
好適である。また、カルボグアナミン（ａｌおよびメラ
ミン以外のアよい。使用するホルムアルデヒド量は、ア
ミノ化合物（Ａ）１モルに対して１．２〜１０モル、特
に１．５〜４．０モルの範囲で用いるのが好ましい。す
なわち、１．２モル以下では反応が充分進行せず、一方
、１０モルを越えてもその効果はそれほどでもなく、経
済的に好ましくない。水溶性のアミノ樹脂（りを用いて
化粧板および化粧合板を製造する際は、アミノ樹脂（Ｉ
）が均一で安定な溶液となることが好ましく、そのため
にはアミノ樹脂（りが適度の縮合度をもつのが好ましい
。この縮合度の目安としては、反応生成物であるアミノ
樹脂（りの水溶液のメタノール混和度Ｍ２を測定するの
が簡便である。Furthermore, the amount of melanin contained before amino compounding is such that the amino resin (f) has sufficient water solubility and impairs various properties such as flexibility and crack resistance, which are characteristics of carboguanamine (a). The amount used is preferably within the range of 20 to 80%.
It is preferably 20-40% by weight. However, when obtaining a water-soluble amino resin (I), the amount of carboguanamine (atO) in the amino compound diagram is preferably as large as possible; therefore, the amount of carboguanamine (a) is 20 to 8
It is suitable that the weight ratio is 0, preferably 60 to 80. In addition, carboguanamine (other than al and melamine) may be used. The amount of formaldehyde used is 1.2 to 10 mol, particularly 1.5 to 4.0 mol, per 1 mol of amino compound (A). In other words, if the amount is less than 1.2 mol, the reaction will not proceed sufficiently, while if it exceeds 10 mol, the effect will not be so great and it is economically undesirable. When manufacturing boards and decorative plywood, amino resin (I
) is preferably a homogeneous and stable solution, and for this purpose it is preferable that the amino resin (ri) has an appropriate degree of condensation.As a guideline for this degree of condensation, It is convenient to measure the methanol miscibility M2.
なお、アミノ樹脂（りの水溶液のメタノール混和度Ｍ２
は、アミノ化合物置とホルムアルデヒドを水溶液中で反
応させたのちの反応溶液５ｇをメタノール５−に溶解さ
せ、２５℃で水を滴下し、白濁を生じるまでに要した滴
下水量ｗｔ （ｙ）から次式よシ求められたものである
。In addition, the methanol miscibility M2 of the aqueous solution of amino resin
After reacting the amino compound and formaldehyde in an aqueous solution, 5 g of the reaction solution is dissolved in methanol 5-, and water is added dropwise at 25°C. This is what was asked for in the formula.
メタノール混和度Ｍｔ ＝（Ｗｔ１５）Ｘ １００水溶
性のアミノ樹脂（Ｉ）のメタノール混和度Ｍ２は、３０
〜２００、よシ好ましくは９０〜２００である。すなわ
ち、３０未満あるいは２００を越えるとアミノ樹脂（夏
）の溶液の安定性が悪く、性能の優れた化粧板や化粧合
板を得ることが困難である。また、該アミノ樹脂（Ｉ）
の溶液に、従来公知のメラミン樹脂の改質剤、例えばポ
リビニルアルコールやポリビニルアセテートなどを加え
て化粧板や化粧合板に供することもできる。Methanol miscibility Mt = (Wt15)X 100 Methanol miscibility M2 of water-soluble amino resin (I) is 30
-200, preferably 90-200. That is, when it is less than 30 or more than 200, the stability of the amino resin (summer) solution is poor, making it difficult to obtain decorative laminates and decorative plywood with excellent performance. Moreover, the amino resin (I)
It is also possible to add a conventionally known modifier for melamine resin, such as polyvinyl alcohol or polyvinyl acetate, to the solution and use it for decorative board or decorative plywood.
本発明におけるアミノ樹脂（りを含んでなる樹脂組成物
を用いて化粧板や化粧合板を作成する場合には、樹脂組
成物をシート状物に含浸したのちに、乾燥、硬化させれ
ばよい。When creating a decorative board or decorative plywood using the resin composition containing an amino resin in the present invention, it is sufficient to impregnate a sheet-like material with the resin composition and then dry and harden it.
シート状物に対するアミノ樹脂（Ｉ）の含浸量は樹脂固
形分換算でシート状物に対して７０〜１５０重量係、好
ましくは９０〜１３０重量係である。The amount of amino resin (I) impregnated into the sheet material is 70 to 150 weight percent, preferably 90 to 130 weight percent, based on the resin solid content.
該シート状物に樹脂組成物を含浸するには一般には該樹
脂組成物を適当なる有機溶剤および／または水の溶液と
なし、該溶液を該シート状物に塗布するかまたは該シー
ト状物を該溶液に浸漬した後、常温ないし加熱下に乾燥
して、揮発分を可及的に除去することにより容易に達成
することができる。To impregnate the sheet material with a resin composition, the resin composition is generally dissolved in a suitable organic solvent and/or water, and the solution is applied to the sheet material. This can be easily achieved by immersing in the solution and then drying at room temperature or under heating to remove as much volatile matter as possible.
用いられるシート状物としては、液状の組成物が容易に
含浸し得るシート状物のものであれば特に制限されない
が、工業的に入手が容易でかつ任好適である。The sheet-like material to be used is not particularly limited as long as it can be easily impregnated with the liquid composition, but any sheet-like material is suitable and is industrially easily available.
また、硬化させる場合には、必要に応じて硬化触媒を加
え、硬化を促進させることも可能であυ、硬化触媒とし
ては特に制限されるものではないが、従来公知の熱硬化
性樹脂の硬化触媒、例えばパラトルエンスルホン酸、塩
化アンモニウムなトラ挙げることができ、アミノ樹脂（
りの成分に応じて適当な触媒を選択して用いることがで
きる。In addition, when curing, it is possible to add a curing catalyst to accelerate curing if necessary.The curing catalyst is not particularly limited, but conventionally known thermosetting resins can be cured. Catalysts may be mentioned, such as para-toluenesulfonic acid, ammonium chloride, amino resins (
An appropriate catalyst can be selected and used depending on the components.
本発明の熱硬化性樹脂化粧板は、前記手順で得られるア
ミノ樹脂（Ｉ）を含んでなる樹脂組成物をシート状物に
含浸した後、乾燥、硬化して得られる樹脂含浸シート層
を表面に有してなるものであシ、種々の方法によって得
ることができる。その具体例としては、例えば
（Ｉ−ａ） 樹脂組成物を含浸したシート状物を加圧
下に加熱硬化する方法、
（２−ａ） 樹脂組成物を含浸したシート状物の２枚
以上を積層し、加圧下に加熱硬化する方法、（３−ａ）
樹脂組成物を含浸したシート状物の１枚以上とアミ
ノ樹脂（Ｉ）以外の熱硬化性樹脂（Ｉｆ）の組成物を含
浸したシート状物および／または熱可塑性樹脂の組成物
を含浸したシート状物の１枚以上とを積層し、加圧下に
加熱硬化する方法、
（４−ａ） 樹脂組成物を含浸したシート状物の１枚
以上を加圧下に加熱硬化して得られる樹脂含浸シート層
を、熱硬化性樹脂（ＩＩ）の組成物を含浸・硬化したシ
ート状物の１枚以上および／または熱可塑性樹脂を含浸
したシート状物の１枚以上と適当な接着剤を用いて接着
する方法等を挙げることができる。これら方法における
加圧は鏡面板を用いて行うと表面が高光沢で美麗な化粧
板に仕上がるので好ましい。また、上記した具体的な方
法のうち、特に（３−ａ）および（４−ａ）の方法によ
って得られた化粧板は若干高価なものになるが、硬度、
耐光性、光沢、耐汚染性、耐クラツク性、耐水性、耐薬
品性などの化粧板にとって重要な表面物性と可撓性およ
び耐クラツク性とが共に極めて優れた化粧板が得られる
ものである。The thermosetting resin decorative board of the present invention includes a resin-impregnated sheet layer obtained by impregnating a sheet material with a resin composition containing the amino resin (I) obtained in the above procedure, drying and curing the resin composition on the surface. It can be obtained by various methods. Specific examples thereof include (I-a) a method of heating and curing a sheet-like material impregnated with a resin composition under pressure; (2-a) a method of laminating two or more sheet-like materials impregnated with a resin composition; and heat curing under pressure, (3-a)
One or more sheets impregnated with a resin composition, a sheet impregnated with a composition of a thermosetting resin (If) other than the amino resin (I), and/or a sheet impregnated with a composition of a thermoplastic resin (4-a) A resin-impregnated sheet obtained by laminating one or more sheets of a resin composition and heating and curing the same under pressure. The layer is bonded to one or more sheets impregnated and cured with a thermosetting resin (II) composition and/or one or more sheets impregnated with a thermoplastic resin using a suitable adhesive. Examples of methods include: It is preferable to apply pressure in these methods by using a mirror-finished plate, since this results in a beautiful decorative board with a high gloss surface. Furthermore, among the above-mentioned specific methods, the decorative laminates obtained by methods (3-a) and (4-a) in particular are somewhat expensive, but
It is possible to obtain a decorative board that has extremely excellent surface properties such as light resistance, gloss, stain resistance, crack resistance, water resistance, chemical resistance, etc., which are important for decorative boards, as well as flexibility and crack resistance. .
本発明の化粧合板は、前記樹脂含浸シート層が基板と一
体化されてなるものである。基板には天然、合成あるい
は無機、有機を問わず種々のものが使用できるが、通常
ベニヤ合板、硬質繊維板、パーチクルボードなどが好適
に用いられる。該基板に樹脂含浸シート層を一体化する
には従来から公知の方法によればよく、具体的には例え
ば（Ｉ−ｂ） 樹脂組成物を含浸したシート状物の１
枚以上を基板に貼着し、加圧下に加熱硬化する方法、
（２−ｂ） 樹脂組成物を含浸したシート状物の１枚
以上とアミノ樹脂（Ｉ）以外の熱硬化性樹脂（ＩＩ）の
組成物を含浸したシート状物および／または熱可塑性樹
脂の組成物を含浸したシート状物の１枚以上とを基板に
積層・貼着し、加圧下に加熱硬化する方法
等を挙げることができる。The decorative plywood of the present invention is one in which the resin-impregnated sheet layer is integrated with a substrate. Although various substrates can be used, whether natural, synthetic, inorganic, or organic, veneer plywood, hard fiberboard, particle board, etc. are usually suitably used. A conventionally known method may be used to integrate the resin-impregnated sheet layer with the substrate, and specifically, for example, (I-b) 1 of the sheet-like material impregnated with the resin composition.
(2-b) one or more sheets impregnated with a resin composition and a thermosetting resin (II) other than the amino resin (I); Examples include a method of laminating and pasting one or more sheets impregnated with the composition and/or one or more sheets impregnated with a thermoplastic resin composition on a substrate, and heating and curing under pressure. can.
本発明の化粧板や化粧合板を得る際の硬化温度は８０〜
３００℃の範囲で選択すればよいが、好ましいのは１１
０〜２５０℃の範囲である。硬化時間は上記硬化温度範
囲に対し、通常１〜６０分が適当である。また、加圧は
３に９／ｃｒ１以上が必要である。３＃ｔ／ｄ（未満の
圧力では実質的に完全平滑な表面が得られ難い。The curing temperature when obtaining the decorative board or decorative plywood of the present invention is 80~
It may be selected within the range of 300°C, but 11 is preferable.
It is in the range of 0 to 250°C. The appropriate curing time is usually 1 to 60 minutes within the above curing temperature range. Further, the pressure needs to be 3 to 9/cr1 or more. If the pressure is less than 3#t/d, it is difficult to obtain a substantially completely smooth surface.
また、（３−ａ）、（４−ａ）および（２−ｂ）の方法
にトルエン樹脂、アミノアルデヒド樹脂、不飽和ポリエ
ステル樹脂またはそれらの混合物が適当であり、熱可塑
性樹脂としては塩化ビニル、酢酸ビニル、スチレンの重
合体または共重合体が適当である。In addition, toluene resin, aminoaldehyde resin, unsaturated polyester resin, or a mixture thereof is suitable for the methods (3-a), (4-a), and (2-b), and as the thermoplastic resin, vinyl chloride, Polymers or copolymers of vinyl acetate and styrene are suitable.
（発明の効果）
本発明の熱硬化性樹脂化粧板は、特定構造のカルボグア
ナミン（ａ）を必須に含むアミノ化合物置から得られる
アミノ樹脂（Ｉ）を用いてなることにより、表面硬度、
光沢、母半目−耐汚染性、耐水性、耐光性、耐薬品性が
優れておシ、しかも耐クラツク性および可撓性にも優れ
ていることによシ、適当な接着剤を用いて様々な形状の
家具、テーブルや壁などに極めて容易に貼着でき、その
表面を長期間に亘って保護することができる。また、本
発明の化粧合板は硬度、光沢、考中神−耐光性、耐汚染
性、耐水性、耐薬品性、耐クラツク性に優れているため
に、製造時や使用時において化粧板同士のまたは他の物
品との接触などによる傷付きや割れなどが発生すること
もなく、切削加工なども容易で、屋内外での長期の使用
に十分耐えるものである。従って本発明の化粧合板は、
例えば壁材、机、テーブル、実験台等の表面材、コンク
リートパネル、天井材、間仕切材等の用途に好適に用い
ることができる。(Effects of the Invention) The thermosetting resin decorative board of the present invention uses an amino resin (I) obtained from an amino compound that essentially contains carboguanamine (a) with a specific structure, thereby improving surface hardness and
It has excellent gloss, half-color - stain resistance, water resistance, light resistance, and chemical resistance, as well as excellent crack resistance and flexibility. It can be attached extremely easily to furniture, tables, walls, etc. of various shapes, and the surface can be protected for a long period of time. In addition, the decorative plywood of the present invention has excellent hardness, gloss, light resistance, stain resistance, water resistance, chemical resistance, and crack resistance, so the decorative plywood has excellent hardness, gloss, light resistance, stain resistance, water resistance, chemical resistance, and crack resistance. Moreover, it does not suffer from scratches or cracks due to contact with other articles, is easy to cut, and is sufficiently durable for long-term use indoors and outdoors. Therefore, the decorative plywood of the present invention is
For example, it can be suitably used for wall materials, surface materials for desks, tables, laboratory benches, etc., concrete panels, ceiling materials, partition materials, and the like.
本発明に用いられるアミノ樹脂（Ｉ）は、製造処いずれ
の方法でも行なうことができる。また、該アミノ樹脂（
Ｉ）を有機溶媒の溶液や水溶液としても均一で安定であ
シ、シート状物に均一に含浸させ、性能の優れた化粧板
や化粧合板が得られる。The amino resin (I) used in the present invention can be produced by any method. In addition, the amino resin (
I) is uniform and stable even as an organic solvent solution or an aqueous solution, and can be uniformly impregnated into a sheet material to obtain decorative laminates and decorative plywood with excellent performance.
また、脂溶性のアミノ樹脂（りを用いて化粧板や化粧合
板を製造した場合、硬化条件の範囲が広く成形加工がし
やすく、またホット−ホット成形してもそシも少なく成
形効率に優れた特徴をもつものである。In addition, when decorative laminates and decorative plywood are manufactured using fat-soluble amino resins, molding can be easily performed over a wide range of curing conditions, and even with hot-hot molding, there is less cracking and the molding efficiency is excellent. It has characteristics.
（実施例）
以下、実施例によって本発明を更に詳細に説明するが、
本発明は以下の実施例のみによって制限されるものでは
ない。尚、例中の部および係は特にことわシのない限シ
全て重量による。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited only by the following examples. In addition, all parts and units in the examples are by weight unless otherwise specified.
製造例１
撹拌機、還流冷却器および温度計を備えた反応容器にシ
クロヘキサンカルボグアナミン１００部、ホルムアルデ
ヒド３７％水溶液１２７部および炭酸ナトリウム１０％
水溶液０．３３部を仕込み撹拌しながら９０℃で２時間
反応させた。その後１００℃で４時間加熱して縮合反応
を進行させると共に水および未反応ホルムアルデヒドを
留去し、更に１２０℃まで加熱して残存する水および未
反応ホルムアルデヒドを除去して固形のアミノ樹脂（Ｉ
−１）を得た。このアミノ樹脂（Ｉ−１）のメタノール
混和度Ｍ１は７であった。Production Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 100 parts of cyclohexanecarboguanamine, 127 parts of a 37% formaldehyde aqueous solution, and 10% sodium carbonate were added.
0.33 part of an aqueous solution was charged and reacted at 90° C. for 2 hours with stirring. Thereafter, it was heated at 100°C for 4 hours to advance the condensation reaction and water and unreacted formaldehyde were distilled off, and further heated to 120°C to remove remaining water and unreacted formaldehyde to form a solid amino resin (I
-1) was obtained. The methanol miscibility M1 of this amino resin (I-1) was 7.
製造例２〜４
製造例１において、用いた原料の組成および反応時の条
件を第１表に示した通シとする以外は製造例１と同様の
操作をくり返してアミノ樹脂（■−２）〜（Ｉ−４）を
得た。これらアミノ樹脂（■−１）〜（Ｉ−４）のメタ
ノール混和度Ｍ１は第１表に示した通シであった。Production Examples 2 to 4 Amino resin (■-2) was produced by repeating the same operations as in Production Example 1 except that the composition of the raw materials used and the reaction conditions were as shown in Table 1. ~(I-4) was obtained. The methanol miscibility M1 of these amino resins (■-1) to (I-4) was as shown in Table 1.
製造例５
製造例１で用いたのと同様の反応容器にシクロヘキサン
カルボグアナミン７０部、メラミン３０部およびホルム
アルデヒド３７％水溶液１５６部を仕込み、更に炭酸ナ
トリウム５％水溶液により内容物のｐＨを８．０に調整
した。撹拌しながら９５℃で４０分間反応させた後、室
温まで冷却してアミノ樹脂の水溶液（Ｉ−５）を得た。Production Example 5 In a reaction vessel similar to that used in Production Example 1, 70 parts of cyclohexanecarboguanamine, 30 parts of melamine, and 156 parts of a 37% formaldehyde aqueous solution were charged, and the pH of the contents was adjusted to 8.0 with a 5% aqueous sodium carbonate solution. Adjusted to. After reacting at 95° C. for 40 minutes with stirring, the mixture was cooled to room temperature to obtain an aqueous amino resin solution (I-5).
このアミノ樹脂の水溶液（Ｉ−５）の濃度、メタノール
混和度Ｍ２および安定性は第２表に示した通りであった
。The concentration, methanol miscibility M2, and stability of this amino resin aqueous solution (I-5) were as shown in Table 2.
製造例６〜９
製造例５において、用いた原料の組成および反応時間を
第２表に示した通シとする以外は製造例５と同様の操作
をくシ返してアミノ樹脂の水溶液（Ｉ−６）〜（Ｉ−９
）を得た。これらアミノ樹脂の水溶液（Ｉ−６）〜（Ｉ
−９）の濃度、メタノール混和度Ｍ２および安定性は第
２表に示した通シであった。Production Examples 6 to 9 In Production Example 5, an aqueous solution of amino resin (I- 6) ~ (I-9
) was obtained. Aqueous solutions (I-6) to (I
The concentration, methanol miscibility M2, and stability of -9) were consistent with those shown in Table 2.
以下、アミノ樹脂（Ｉ−１）〜（Ｉ−９）を用いて第３
表のような配合で樹脂組成物溶液（Ｉ）〜（Ｘ）を調製
し、各実施例に用いた。Hereinafter, using amino resins (I-1) to (I-9), the third
Resin composition solutions (I) to (X) were prepared with the formulations shown in the table and used in each example.
実施例１
紙を浸漬後室源で風乾し、１００℃にて１０分間熱風乾
燥して樹脂分が原紙に対し１２０％含浸した化粧紙を得
た。この樹脂分が含浸した化粧紙１枚を厚さ０．３ｔｎ
ｔｘ、重さ２４２１！ ／ ｍのフェノール分間加熱硬
化して表面硬度の大きい美麗なる化粧板（Ｉ）を得た。Example 1 After soaking, the paper was air-dried indoors and dried with hot air at 100° C. for 10 minutes to obtain decorative paper in which the base paper was impregnated with 120% resin. One sheet of decorative paper impregnated with this resin has a thickness of 0.3tn.
tx, weight 2421! /m of phenol for a minute to obtain a beautiful decorative board (I) with a high surface hardness.
この化粧板（Ｉ）を曲率半径４０ｍｍ面を有する家具に
ネオプレン系接着剤を用い貼着したところ、化粧板（Ｉ
）は何ら異常なく美麗な状態を保持していた。When this decorative board (I) was attached to furniture having a surface with a radius of curvature of 40 mm using a neoprene adhesive, the decorative board (I)
) was in beautiful condition with no abnormalities.
この化粧板（Ｉ）の性能を第４表に示した。The performance of this decorative board (I) is shown in Table 4.
なお、樹脂組成物溶液（Ｉ）は室温で１ケ月以上放置し
ても沈殿が生じることなく安定であった。The resin composition solution (I) remained stable without precipitation even after being left at room temperature for more than one month.
実施例２
樹脂組成物溶液（ＩＩ）に大理石模様を印刷した厚さ０
．２龍、重さ１２０．Ｓ’／ｍの化粧紙を含浸後室源で
風乾し１００℃にて１２分間乾燥して樹脂分が原紙に対
し１２３％含浸した化粧紙を得た。この樹脂分が含浸し
た化粧紙と厚さ０．３ ｍ 、 重さ２４２１ ／
ｍ”のフェノール樹脂含浸クラフト紙および塩化ビニル
樹脂を含浸せしめた８０番白色ブロード生地をそれぞれ
１枚ずつ積層し、クロム鍍金鏡面板を用いて温度１５０
℃、圧力２５＃／ｆｆｌの条件で１０分間熱圧着して光
沢のある美麗な化粧板（２）を得た。得られた化粧板（
２）を実施例１と同様にして家具に貼着したところ、化
粧板（２）は何ら異常が発生しなかった。この化粧板（
２）の性能を第４表に示し念。Example 2 Marble pattern printed on resin composition solution (II) thickness 0
．． 2 dragons, weight 120. After impregnating decorative paper of S'/m, it was air-dried in a room at 100° C. for 12 minutes to obtain a decorative paper impregnated with 123% resin based on the base paper. Decorative paper impregnated with this resin, thickness 0.3 m, weight 2421 /
M" phenolic resin-impregnated kraft paper and vinyl chloride resin-impregnated No. 80 white broadcloth were laminated one by one and heated to a temperature of 150 using a chrome-plated mirror plate.
℃ and a pressure of 25#/ffl for 10 minutes to obtain a beautiful glossy decorative board (2). The resulting decorative board (
When 2) was attached to furniture in the same manner as in Example 1, no abnormality occurred in the decorative board (2). This decorative board (
The performance of 2) is shown in Table 4.
なお、樹脂組成物溶液（ＩＩ）は、室温で１ケ月以上放
置しても沈殿が生じることなく安定であった。Note that the resin composition solution (II) remained stable without precipitation even after being left at room temperature for one month or more.
実施例３
実施例１における樹脂組成物溶液（Ｉ）の代わシに樹脂
組成物溶液（ＩＩＩ）を用いた以外は実施例１と同様な
操作を繰シ返し光沢のある美麗な化粧板（３）を得た。Example 3 A glossy and beautiful decorative board (3 ) was obtained.
この化粧板（３）の性能を第４表に示した。The performance of this decorative board (3) is shown in Table 4.
また、得られた化粧板（３）を実施例１と同様にして家
具に貼着したところ化粧板（３）は何ら異常なく美麗な
状態を保持していた。Further, when the obtained decorative board (3) was attached to furniture in the same manner as in Example 1, the decorative board (3) remained in a beautiful state without any abnormality.
なお、樹脂組成物溶液（ｍ）は室温で１ケ月以上放置し
ても沈殿が生じることなく安定であった。The resin composition solution (m) remained stable without precipitation even after being left at room temperature for more than one month.
実施例４
樹脂組成物溶液（Ｉ）に白色無地の重さＳｏｌ！／ｒｒ
ｔのコツトンリンター紙を浸漬させた後、室温で風乾し
１００℃にて１０分間熱風乾燥して、樹脂分が原紙に対
して１１０％含浸したコツトンリンター紙を得た。該コ
ツトンリンター紙を６枚重ね、ステンレス鋼鏡面板を用
いて圧力３０に９／ｃ１１１、温度１５０℃の条件で１
０分間加熱硬化させて光沢のある美麗な化粧板（４）を
得た。この化粧板（４）の性能を第４表に示した。また
１、７１８ Ｋ−６９１１に基づいて曲げ強度を測定し
たところ４３０ｋｇｆ／ｉであつ九。Example 4 The weight of white solid color Sol! in the resin composition solution (I). /rr
After soaking the cotton linter paper of No. t, it was air-dried at room temperature and hot air-dried at 100° C. for 10 minutes to obtain cotton linter paper impregnated with 110% of the resin content based on the base paper. Six sheets of the cotton linter paper were stacked and heated using a stainless steel mirror plate under the conditions of a pressure of 30 9/c111 and a temperature of 150°C.
A beautiful glossy decorative board (4) was obtained by heating and curing for 0 minutes. The performance of this decorative board (4) is shown in Table 4. In addition, when the bending strength was measured based on 1,718 K-6911, it was 430 kgf/i.
実施例５
樹脂組成物溶液（Ｉ）に白色無地の厚さ０．１２ ｍ、
重さ１００，９／ｍのチタン紙を浸漬させた後室温で風
乾し、１００℃にて２０分間熱風乾燥させ樹脂分が原紙
に対して１１０％含浸したチタン紙を得た。該チタン紙
１枚と厚さ０．３ ｔｓｘ 、重さ２４２１１／ｒｒｌ
のフェノール樹脂含浸クラフト紙１枚を重ねステンレス
鋼鏡面板を用いて圧力１５＃／ｃ７Ｉｌ。Example 5 A plain white color was applied to the resin composition solution (I) to a thickness of 0.12 m.
A titanium paper weighing 100.9/m was immersed, air-dried at room temperature, and then dried with hot air at 100°C for 20 minutes to obtain a titanium paper impregnated with resin at 110% of the base paper. One sheet of titanium paper, thickness 0.3 tsx, weight 24211/rrl
Layer one sheet of phenolic resin-impregnated kraft paper and apply pressure to 15#/c7Il using a stainless steel mirror plate.
温度１５０℃の条件で１０分間加熱硬化させて、光沢あ
る美麗な化粧板（５）を得た。この化粧板（５）の性能
を第４表に示した。A glossy and beautiful decorative board (5) was obtained by heating and curing at a temperature of 150° C. for 10 minutes. The performance of this decorative board (5) is shown in Table 4.
実施例６〜１２
実施例５において、用いる樹脂組成物溶液、該溶液を浸
漬した後のチタン紙の熱風乾燥条件および化粧板を得る
際の加熱硬化条件を第４表に示した通りとする以外は実
施例５と同様な操作をくυ返して光沢のある美麗な化粧
板（６）〜（Ｉ２を得た。これら化粧板（６）〜α２の
性能を第４表に示した。Examples 6 to 12 In Example 5, except that the resin composition solution used, the hot air drying conditions of the titanium paper after soaking in the solution, and the heat curing conditions when obtaining the decorative board were as shown in Table 4. The same operations as in Example 5 were repeated to obtain glossy and beautiful decorative laminates (6) to (I2). The performances of these decorative laminates (6) to α2 are shown in Table 4.
なお、実施例６における熱風乾燥後のチタン紙は発泡お
よび樹脂のはがれが全くなく取り扱いがよシ容易であっ
た。In addition, the titanium paper after hot air drying in Example 6 had no foaming or peeling of the resin, and was easy to handle.
比較例１
ベンゾグアナミン樹脂（ＤＢＧ、日本触媒化学工業株式
会社会牲製）５０部、ｐ−）ルエンスルホン酸１．０部
、ラウリン酸０．７５部、メタノール４０部およびトル
エン１０部からなる比較用樹脂組成物溶ｇ、（ビ）を調
製した。該溶液を実施例４における樹脂組成物溶液（Ｉ
）の代わシに用いた以外は実施例４と同様の操作を繰シ
返し比較用化粧板（Ｉ）を得た。この比較用化粧板（Ｉ
）の性能を第４表に示した。Comparative Example 1 A comparative product consisting of 50 parts of benzoguanamine resin (DBG, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.), 1.0 part of p-)luenesulfonic acid, 0.75 part of lauric acid, 40 parts of methanol, and 10 parts of toluene. Resin composition solutions G and (VI) were prepared. The solution was mixed with the resin composition solution in Example 4 (I
) The same operation as in Example 4 was repeated to obtain a comparative decorative board (I), except that the same procedure was repeated as in Example 4. This comparative decorative board (I
) performance is shown in Table 4.
比較例２
製造例１で用いたのと同様な容器にメラミン１２６部、
ホルムアルデヒド３７％水溶液２４３部を仕込み、炭酸
ナトリウム５％水溶液を加えて反応溶液のｐＨを８．０
に調節した後、撹拌しなから６５℃まで加熱した。更に
６５℃で１５分間撹拌を続けた。反応終了後、反応溶液
を冷却し、メタノールを加えて不揮発分５０％の比較用
アミノ樹脂（Ｉ）の溶液を得た。Comparative Example 2 In a container similar to that used in Production Example 1, 126 parts of melamine,
243 parts of a 37% formaldehyde aqueous solution was charged, and a 5% sodium carbonate aqueous solution was added to adjust the pH of the reaction solution to 8.0.
After adjusting the temperature to 65° C., the mixture was heated to 65° C. without stirring. Stirring was continued for an additional 15 minutes at 65°C. After the reaction was completed, the reaction solution was cooled and methanol was added to obtain a solution of comparative amino resin (I) with a non-volatile content of 50%.
この比較用アミノ樹脂（Ｉ）の溶液２００部、塩化アン
モニウム０．１部およびラウリン酸１．５部を撹拌混合
して比較用樹脂組成物溶液（■′）を得た。こ色
の比較用樹脂組成物溶液（■′）に白楡無地の厚さ０．
１２翼罵、重さ１００．９／ぜのチタン紙を浸漬させ室
温で風乾した。このチタン紙を８０℃にて１５分間熱風
乾燥した後、該チタン紙１枚と厚さ０、３ ｍ 、重さ
２４２９／ｒｒｌのフェノール樹脂含浸クラフト紙１枚
を重ね、ステンレス鋼の鏡面板を用いて圧力１５に９／
ｃｒｉｌ、温度１３０℃の条件で１０分間加熱硬化させ
て比較用化粧板（２）を得た。200 parts of this comparative amino resin (I) solution, 0.1 part of ammonium chloride, and 1.5 parts of lauric acid were mixed with stirring to obtain a comparative resin composition solution (■'). The dark colored comparison resin composition solution (■') was coated with a plain white elm color with a thickness of 0.
Titanium paper with a weight of 100.9 mm was soaked and air-dried at room temperature. After drying this titanium paper with hot air at 80°C for 15 minutes, one sheet of titanium paper was layered with one sheet of phenolic resin-impregnated kraft paper with a thickness of 0.3 m and a weight of 2429/rrl, and a stainless steel mirror plate was placed on top of it. Using pressure 15 to 9/
A decorative board (2) for comparison was obtained by heating and curing at a temperature of 130° C. for 10 minutes.
この比較用化粧板（２）の性能を第４表に示した。The performance of this comparative decorative board (2) is shown in Table 4.
第４表には実施例１〜１２および比較例１〜２における
化粧板（Ｉ）〜α２および比較用化粧板（Ｉ）〜（２）
の作成条件および各項目の評価結果を示した。評価結果
はそれぞれ以下の基準で判定した。Table 4 shows decorative laminates (I) to α2 in Examples 1 to 12 and comparative examples 1 to 2 and comparative decorative laminates (I) to (2).
The preparation conditions and evaluation results for each item are shown. The evaluation results were judged based on the following criteria.
なお、項目末尾に（、■）が有るものは、ＪＩＳ Ｋ
６９０２（Ｉ９７７）に基づく試験を行なったことを示
す。In addition, items with (,■) at the end of the item are JIS K
6902 (I977) was conducted.
表面硬度 ＪＡＳ特殊合板に基づく引っかき硬度Ａ試験
を行ない、適合基準に合格するものを○、不合格のもの
を×とした。Surface Hardness A scratch hardness A test based on JAS special plywood was conducted, and those that passed the compliance criteria were rated ○, and those that failed were rated ×.
耐光性 フェードテスターにて２００時間照射後の黄変
度を調べ、Δｂ （Ｌａｂ）値により以下の基準で判定
した。Light resistance The degree of yellowing after 200 hours of irradiation was examined using a fade tester, and judged based on the Δb (Lab) value according to the following criteria.
００．５未満
Δ ０．５以上３未満
× ３ 以上
耐水性（Ｊ） 耐煮沸性の試験を行ない、層間はく離
の無いものを○、有るものをＸとした。Less than 00.5 Δ 0.5 or more and less than 3 × 3 or more Water resistance (J) A boiling resistance test was conducted, and those with no interlayer peeling were rated ○, and those with peeling were rated X.
耐汚染性（Ｊ） 耐汚染性の試験を行ない、以下の基
準で判定した。Stain resistance (J) A stain resistance test was conducted and judged based on the following criteria.
○ 変化の無いもの
Δ 洗剤または乾燥布で容易に除去可能なもの、または
、洗剤または乾燥布で処理してもうすく変化の残るもの
× 著しい変化のもの
耐クラツク性穴あけパンチ後の外観を調べ以下の基準で
判定した。○ Items with no change Δ Items that can be easily removed with detergent or dry cloth, or items that remain after treatment with detergent or dry cloth Judgment was made using the following criteria.
○ 変化の無いもの
Δ 穴の縁にささくれが生じるもの
× われ、ひびまたははがれが生じたもの耐薬品性 Ｊ
ＡＳ特殊合板に基づく耐アルカリ試験および耐酸試験を
行ない、変化の無いものを０１変化の有るものをＸとし
た。○ No changeΔ Items with hangnails on the edge of the hole × Items with cracks or peeling Chemical resistance J
An alkali resistance test and an acid resistance test were conducted based on AS special plywood, and those with no change were rated 0 and those with change were rated X.
実施例１３ 樹脂組成物溶液（Ｉ）に白色無地の厚さ０．１２ｍｍ。Example 13 The resin composition solution (I) was a plain white color with a thickness of 0.12 mm.
重さ１００＃／ｍのチタン紙を浸漬させた後、室温で風
乾した。該チタン紙を１００℃にて第５表のごとく各時
間で熱風乾燥させた後、該チタン紙１枚と厚さ０．３
ｍａｔ ｓ重さ２４２Ｎ／ぜのフェノール樹脂含浸クラ
フト紙１枚を重ね、ステンレス鋼鏡面板を用いて圧力１
５ｋｇ／ｆｆｌ、温度１５０℃の条件で１０分間加熱硬
化させ、乾燥時間と得られた化粧板の硬化状態の関係を
調べた。その結果は第５表に示したごとくであり、広範
な熱風乾燥時間において適性な硬化状態の光沢のある美
麗な化粧板が得られた。Titanium paper weighing 100 #/m was immersed and then air-dried at room temperature. After drying the titanium paper with hot air at 100°C for various times as shown in Table 5, one sheet of the titanium paper and a thickness of 0.3
1 sheet of phenolic resin-impregnated kraft paper weighing 242 N/day was stacked, and a pressure of 1 was applied using a stainless steel mirror plate.
The decorative board was cured by heating for 10 minutes at a weight of 5 kg/ffl and a temperature of 150°C, and the relationship between the drying time and the cured state of the obtained decorative board was investigated. The results are shown in Table 5, and a glossy and beautiful decorative board in an appropriately cured state was obtained over a wide range of hot air drying times.
また風乾したチタン紙を１００℃、２０分間の条件下で
熱風乾燥させた後、該チタン紙１枚と厚さ０．３ｍｍ、
重さ２４２．！ｉ＋／ぜのフェノール樹脂含浸クラフト
紙１枚を重ね、ステンレス鋼鏡面板を用いて圧力１５に
９／ｃｒＡの条件で第１図に示した鏡面板温度および加
熱硬化時間で硬化させ、得られた化粧板の硬化状態の関
係を調べた。結果を第１図に示した。第１図に示したご
とく、広範な鏡面な
板温度と加熱硬化時間において適性亭硬化状態の光沢あ
る美麗な化粧板が得られた。In addition, after drying the air-dried titanium paper with hot air at 100°C for 20 minutes, one sheet of titanium paper and a sheet of 0.3 mm thick,
Weight 242. ! One sheet of i+/ze's phenolic resin-impregnated kraft paper was stacked and cured using a stainless steel mirror plate at a pressure of 15 to 9/crA at the mirror plate temperature and heat curing time shown in Figure 1. The relationship between the hardening state of the decorative board was investigated. The results are shown in Figure 1. As shown in FIG. 1, a glossy and beautiful decorative board in an appropriately cured state was obtained under a wide range of mirror-like board temperatures and heat-curing times.
硬化状態は得られ念化粧板を用いてＪＩＳ Ｋ ６９０
２（Ｉ９７７）に基づく耐汚染性、耐煮沸性の試験を行
ない、以下の基準で判定した。The hardened state is obtained and JIS K 690 is obtained using a decorative board.
2 (I977), stain resistance and boiling resistance tests were conducted, and judgments were made based on the following criteria.
未硬化；耐汚染性が変化有υ、あるいは耐煮沸性で眉間
はく離が有るもの
過硬化；耐煮沸性で層間はく離があるもの適正硬化；耐
汚染性、耐煮沸性共に変化の無いもの
第 ５ 表
硬化状態は化粧板を用いてＪＩＳＫ６９０２（Ｉ９７７
）に基づく耐汚染性および耐煮沸試験を行ない、両方共
に合格したものを○、どちらか−方または両方共に不合
格のものを×とした。Uncured; stain resistance changes or boiling resistance with peeling between the eyebrows Overcured; boiling resistance with interlayer peeling Appropriately cured; no change in stain resistance or boiling resistance No. 5 The surface hardening state is determined by JISK6902 (I977) using a decorative board.
), stain resistance and boiling resistance tests were conducted, and those that passed both were rated ○, and those that failed either or both were rated x.
合格の基準
耐汚染性 変化無し
耐煮沸性 層間はく離無し
実施例１４
実施例５におけるフェノール含浸クラフト紙の代わりに
厚さ４朋のベニヤ合板を用いた以外は、実施例５と同様
の操作を繰シ返し、光沢のある美麗な化粧合板（Ｉ）を
得た。この化粧合板（Ｉ）の性能を第６表に示した。Acceptance criteria Stain resistance No change Boiling resistance No delamination Example 14 The same operation as in Example 5 was repeated except that 4 mm thick plywood was used instead of the phenol-impregnated kraft paper in Example 5. After turning over, a beautiful glossy decorative plywood (I) was obtained. The performance of this decorative plywood (I) is shown in Table 6.
実施例１５〜２３
実施例１４において用いる樹脂組成物溶液、該溶液に浸
漬した後のチタン紙の熱風乾燥条件および化粧合板を得
る際の加熱硬化条件を第６表に示した通シとする以外は
、実施例１４と同様な操作を繰り返し、光沢ある美麗な
化粧合板（２）〜ｔｌｌを得意。これら化粧合板（２）
〜翰の性能を第６表に示した。Examples 15 to 23 The resin composition solution used in Example 14, the hot air drying conditions for the titanium paper after immersed in the solution, and the heat curing conditions for obtaining decorative plywood were other than those shown in Table 6. Repeated the same operation as in Example 14, and was good at producing glossy and beautiful decorative plywood (2) to tll. These decorative plywood (2)
The performance of ~Ken is shown in Table 6.
比較例３
実施例工４における樹脂組成物溶液（Ｉ）の代わシに比
較用樹脂組成物溶液（■′）を用いた以外は、実施例１
４と同様の操作を繰シ返し、比較用化粧合板（Ｉ）を得
た。この比較用化粧合板（Ｉ）の性能を第６表に示した
。Comparative Example 3 Example 1 except that the comparative resin composition solution (■') was used instead of the resin composition solution (I) in Example Process 4.
The same operation as in 4 was repeated to obtain decorative plywood (I) for comparison. The performance of this comparative decorative plywood (I) is shown in Table 6.
比較例４
比較例２におけるフェノール樹脂含浸クラフト紙の代わ
シに厚さ４龍のベニヤ合板を用いた以外は、比較例２と
同様な操作を繰り返し比較用化粧合板（２）を得た。こ
の比較用化粧合板（２）の性能を第６表に示した。Comparative Example 4 Comparative decorative plywood (2) was obtained by repeating the same operations as in Comparative Example 2, except that veneer plywood with a thickness of 4 mm was used instead of the phenol resin-impregnated kraft paper in Comparative Example 2. The performance of this comparative decorative plywood (2) is shown in Table 6.
第６表には実施例１４〜２３および比較例３〜４におけ
る化粧合板（Ｉ）〜ＣＩＧＩおよび比較用化粧合板（Ｉ
）〜（２）の作成条件および各項目の評価結果を示した
。評価結果はそれぞれ以下の基準で判定した。Table 6 shows decorative plywood (I) to CIGI in Examples 14 to 23 and comparative examples 3 to 4 and comparative decorative plywood (I).
) to (2), the preparation conditions and evaluation results for each item are shown. The evaluation results were judged based on the following criteria.
なお、項目末尾に（、■）が有るものはＪＩＳ Ｋ ６
９０２（Ｉ９７７）に基づく試験を行なったことを示す
。In addition, items with (, ■) at the end of the item are JIS K 6.
902 (I977).
表面硬度 ＪＡＳ特殊合板に基づく引っかき硬度Ａ試験
を行ない、適合基準に合格するものを○、不合格のもの
を×とした。Surface Hardness A scratch hardness A test based on JAS special plywood was conducted, and those that passed the compliance criteria were rated ○, and those that failed were rated ×.
耐光性 フェードテスターにて２００時間照射後の黄変
度を調べ、Δｂ（Ｌａｂ）値によυ以下の基準で判定し
た。Light resistance The degree of yellowing after 200 hours of irradiation was examined using a fade tester, and judged based on the Δb (Lab) value on the basis of υ or less.
× ３ 以上
耐水性 ＪＡＳ特殊合板に基づく１類浸せきはくシ試験
を行ない、適合基準に合格するものを○、不合格のもの
を×とした。Water resistance of × 3 or more A class 1 immersion foil test based on JAS special plywood was conducted, and those that passed the conformity criteria were rated ○, and those that failed were rated ×.
耐汚兜虫Ｊ）耐汚染性の試験を行ない、以下の基準で判
定した。Dirt Resistance Helmet J) A stain resistance test was conducted and judged based on the following criteria.
○ 変化の無いもの
Δ 洗剤または乾燥布で容易に除去可能なもの、または
、洗剤または乾燥布で処理してもうすく変化の残るもの
× 著しい変化のもの
耐クラツク性 、Ｊ Ａ Ｓ特殊合板の寒熱繰返しＡ試
験を行ない、割れまたはふくれが生じるまでの試験回数
を求めた。○ Items with no change Δ Items that can be easily removed with detergent or dry cloth, or items that remain unchanged even after treatment with detergent or dry cloth The A test was repeated and the number of tests until cracking or blistering occurred was determined.
耐薬品性 、Ｊ Ａ Ｓ特殊合板に基づく耐アルカリ試
験および耐酸試験を行ない、変化の無いものを○、変化
の有るものを×とした。Chemical resistance: An alkali resistance test and an acid resistance test based on JAS special plywood were conducted, and those with no change were rated ○, and those with changes were rated ×.
実施例２４
樹脂組成物溶液（Ｉ）に白色無地の厚さ０．１２ ｒａ
ｍ、重さ１００ｇ／ｍのチタン紙を浸漬させた後室温で
風乾した。該チタン紙を１００℃にて第７表のごとく各
時間で熱風乾燥させた後、該チタン紙１枚を厚さ４ ｔ
ｘｘのベニヤ合板に重ねステンレス鋼鏡面板を用いて圧
力１５に９／ｃｄ、温度１５０℃の条件で１０分間加熱
硬化させ、乾燥時間と得られた化粧合板の硬化状態の関
係を調べた。その結果は第７表に示したごとくであシ、
広範な熱風乾燥時間において適性な硬化状ｊの光沢のあ
る美麗な化粧合板が得られた。Example 24 Resin composition solution (I) was coated with white solid color to a thickness of 0.12 ra
Titanium paper weighing 100 g/m was immersed and then air-dried at room temperature. After drying the titanium paper with hot air at 100°C for various times as shown in Table 7, one sheet of the titanium paper was dried with a thickness of 4 t.
A mirror-finished stainless steel plate was placed on top of the veneer plywood of No. XX and heat-cured for 10 minutes at a pressure of 15 to 9/cd and a temperature of 150° C., and the relationship between the drying time and the hardening state of the resulting decorative plywood was investigated. The results are as shown in Table 7.
A glossy and beautiful decorative plywood with an appropriate cured state was obtained over a wide range of hot air drying times.
また風乾したチタン紙を１００℃、２０分間の条件下で
熱風乾燥させた後、該チタン紙１枚を厚さ４朋のベニヤ
合板に重ね、ステンレス鋼鏡面板を用いて圧力１５＃／
ｆｆｌの条件で第２図に示した鏡面板温度および加熱硬
化時間で硬化させ、得られた化粧合板の硬化状態の関係
を調べた。結果を第２図に示した。第２図に示したごと
く広範な鏡面板温度と加熱硬化時間において適性な硬化
状態の光沢ある美麗な化粧合板が得られた。In addition, after drying the air-dried titanium paper with hot air at 100°C for 20 minutes, one sheet of the titanium paper was stacked on a 4mm thick plywood board, and a stainless steel mirror plate was used to apply pressure of 15#/
The decorative plywood was cured under the conditions of ffl at the mirror surface plate temperature and heat curing time shown in FIG. 2, and the relationship between the cured state of the obtained decorative plywood was investigated. The results are shown in Figure 2. As shown in FIG. 2, a glossy and beautiful decorative plywood in an appropriate cured state was obtained under a wide range of specular plate temperatures and heat curing times.
硬化状態は得られた化粧合板を用いてＪＡＳ特殊合板に
基づく１類浸せきはぐり試験を行ない、その適合基準に
合格するものを適正硬化とし、不合格のものを未硬化ま
たは過硬化とした。To determine the cured state, the obtained decorative plywood was subjected to a type 1 immersion test based on JAS special plywood, and those that passed the compliance criteria were considered properly cured, and those that failed were considered uncured or overcured.
第 ７ 表
硬化状態は化粧合板を用いてキＡＳ特殊合板に基づく１
類浸せきはくシ試験およびＪＩＳ Ｋ ６９０２（Ｉ９
７７）に基づく耐汚染性試験を行ない、両方共に合格す
るものを○、どちらか一方あるいは両方共に不合格のも
のを×とした。Table 7 The hardened state is based on KiAS special plywood using decorative plywood.
Immersion test and JIS K 6902 (I9
A stain resistance test based on 77) was conducted, and those that passed both were marked as ○, and those that failed either or both were marked as x.
合格の基準 １類浸せき 。Criteria for passing Type 1 immersion.
はくシ試験、ＪＡＳ特殊合板の適合基準と同じ耐汚染試
験；変化無しFoil test, stain resistance test same as JAS special plywood compliance standard; no change
【図面の簡単な説明】
第１図は本発明による化粧板の実施例１３における鏡面
板温度と時間との関係による適正硬化領域を示すグラフ
であシ、また第２図は本発明による化粧合板の実施例２
４における鏡面板温度と時間との関係による適正硬化領
域を示すグラフである。
特許出願人 日本触媒化学工業株式会社第１図
鏡面板温度（℃）
第２図
鏡面板温度（”Ｃ）
昭和６３年９月Δ 日[BRIEF DESCRIPTION OF THE DRAWINGS] Fig. 1 is a graph showing the appropriate curing range according to the relationship between the temperature and time of the mirror plate in Example 13 of the decorative plywood of the present invention, and Fig. 2 is a graph of the decorative plywood of the present invention. Example 2 of
4 is a graph showing the appropriate curing range according to the relationship between mirror plate temperature and time in Example 4. Patent applicant: Nippon Shokubai Kagaku Kogyo Co., Ltd. Figure 1 Mirror surface plate temperature (℃) Figure 2 Mirror surface plate temperature (''C) September Δ Day, 1988
Claims (1)
である。）で表わされる少なくとも１種のカルボグアナ
ミン（ａ）を必須成分として含むアミノ化合物（Ａ）と
ホルムアルデヒドとの反応生成物であるアミノ樹脂（
I ）を含有してなる樹脂組成物をシート状物に含浸させ
かつ硬化させてなる樹脂含浸シート層を表面に有してな
る熱硬化性樹脂化粧板。 ２、シート状物が紙、布および木質単板よりなる群から
選ばれた少なくとも１種のものである請求項１記載の熱
硬化性樹脂化粧板。 ３、アミノ樹脂（ I ）が脂溶性である請求項１記載の
熱硬化性樹脂化粧板。 ４、アミノ化合物（Ａ）中のカルボグアナミン（ａ）の
含有量が６０〜１００重量％である請求項３記載の熱硬
化性樹脂化粧板。 ５、アミノ化合物（Ａ）中のカルボグアナミン（ａ）の
含有量が９５〜１００重量％である請求項４記載の熱硬
化性樹脂化粧板。 ６、アミノ樹脂（ I ）のメタノール混和度Ｍ１が１〜
２００である請求項３記載の熱硬化性樹脂化粧板。 ７、樹脂組成物が更に不飽和ポリエステル樹脂およびア
ルキッド樹脂よりなる群から選ばれた少なくとも１種の
樹脂を含有してなる請求項３記載の熱硬化性樹脂化粧板
。 ８、アミノ樹脂（ I ）１００重量部に対して不飽和ポ
リエステル樹脂およびアルキッド樹脂よりなる群から選
ばれた少なくとも１種の樹脂を１０〜１５０重量部の割
合で含有してなる請求項７記載の熱硬化性樹脂化粧板。 ９、アミノ樹脂（ I ）が水溶性である請求項１記載の
熱硬化性樹脂化粧板。 １０、アミノ化合物（Ａ）がメラミンを２０〜８０重量
％含むものである請求項９記載の熱硬化性樹脂化粧板。 １１、アミノ化合物（Ａ）がメラミンを２０〜４０重量
％含むものである請求項１０記載の熱硬化性樹脂化粧板
。 １２、アミノ樹脂（ I ）のメタノール混和度Ｍ２が３
０〜２００である請求項１０または１１記載の熱硬化性
樹脂化粧板。 １３、アミノ樹脂（ I ）のメタノール混和度Ｍ２が９
０〜２００である請求項１２記載の熱硬化性樹脂化粧板
。 １４、アミノ化合物（Ａ）１モルに対してホルムアルデ
ヒドを１．２〜１０モルの割合で用いてなる請求項１記
載の熱硬化性樹脂化粧板。 １５、式 I ▲数式、化学式、表等があります▼（ I ） （但し、式中、ＸはＣＨ＿２であり、またｎは０または
１である。）で表わされる少なくとも１種のカルボグア
ナミン（ａ）を必須成分として含むアミノ化合物（Ａ）
とホルムアルデヒドとの反応生成物であるアミノ樹脂（
I ）を含有してなる樹脂組成物をシート状物に含浸さ
せかつ硬化させてなる樹脂含浸シート層が基板と一体化
されてなる化粧合板。 １６、シート状物が紙、布および木質単板からなる群か
ら選ばれた少なくとも１種のものである請求項１５記載
の化粧合板。 １７、アミノ樹脂（ I ）が脂溶性である請求項１５記
載の化粧合板。 １８、アミノ化合物（Ａ）中のカルボグアナミン（ａ）
の含有量が６０〜１００重量％である請求項１７記載の
化粧合板。 １９、アミノ化合物（Ａ）中のカルボグアナミン（ａ）
の含有量が９５〜１００重量％である請求項１８記載の
化粧合板。 ２０、アミノ樹脂（ I ）のメタノール混和度Ｍ１が１
〜２００である請求項１７記載の化粧合板。 ２１、樹脂組成物が更に不飽和ポリエステル樹脂および
アルキッド樹脂よりなる群から選ばれた少なくとも１種
の樹脂を含有してなる請求項１７記載の化粧合板。 ２２、アミノ樹脂（ I ）１００重量部に対して不飽和
ポリエステル樹脂およびアルキッド樹脂よりなる群から
選ばれた少なくとも１種の樹脂を１０〜１５０重量部の
割合で用いる請求項２１記載の化粧合板。 ２３、アミノ樹脂（ I ）が水溶性である請求項１５記
載の化粧合板。 ２４、アミノ化合物（Ａ）がメラミンを２０〜８０重量
％含むものである請求項２３記載の化粧合板。 ２５、アミノ化合物（Ａ）がメラミンを２０〜４０重量
％含むものである請求項２４記載の化粧合板。 ２６、アミノ樹脂（ I ）のメタノール混和度Ｍ２が３
０〜２００である請求項２４または２５記載の化粧合板
。 ２７、アミノ樹脂（ I ）のメタノール混和度Ｍ２が９
０〜２００である請求項２６記載の化粧合板。 ２８、アミノ化合物（Ａ）１モルに対してホルムアルデ
ヒドを１．２〜１０モルの割合で用いてなる請求項１５
記載の化粧合板。[Claims] 1. Formula I ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (However, in the formula, X is XH_2, and n is 0 or 1
It is. ) Amino resin (
A thermosetting resin decorative board having a resin-impregnated sheet layer on its surface, which is obtained by impregnating and curing a sheet material with a resin composition containing I). 2. The thermosetting resin decorative board according to claim 1, wherein the sheet-like material is at least one member selected from the group consisting of paper, cloth, and wood veneer. 3. The thermosetting resin decorative board according to claim 1, wherein the amino resin (I) is fat-soluble. 4. The thermosetting resin decorative board according to claim 3, wherein the content of carboguanamine (a) in the amino compound (A) is 60 to 100% by weight. 5. The thermosetting resin decorative board according to claim 4, wherein the content of carboguanamine (a) in the amino compound (A) is 95 to 100% by weight. 6. Methanol miscibility M1 of amino resin (I) is 1 to
4. The thermosetting resin decorative board according to claim 3, wherein the thermosetting resin decorative board is 200%. 7. The thermosetting resin decorative board according to claim 3, wherein the resin composition further contains at least one resin selected from the group consisting of unsaturated polyester resins and alkyd resins. 8. The resin according to claim 7, which contains at least one resin selected from the group consisting of unsaturated polyester resins and alkyd resins in a ratio of 10 to 150 parts by weight per 100 parts by weight of the amino resin (I). Thermosetting resin decorative board. 9. The thermosetting resin decorative board according to claim 1, wherein the amino resin (I) is water-soluble. 10. The thermosetting resin decorative board according to claim 9, wherein the amino compound (A) contains 20 to 80% by weight of melamine. 11. The thermosetting resin decorative board according to claim 10, wherein the amino compound (A) contains 20 to 40% by weight of melamine. 12. Methanol miscibility M2 of amino resin (I) is 3
The thermosetting resin decorative board according to claim 10 or 11, which has a molecular weight of 0 to 200. 13. Methanol miscibility M2 of amino resin (I) is 9
13. The thermosetting resin decorative board according to claim 12, which has a molecular weight of 0 to 200. 14. The thermosetting resin decorative board according to claim 1, wherein formaldehyde is used in a ratio of 1.2 to 10 moles per mole of the amino compound (A). 15, Formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, in the formula, X is CH_2, and n is 0 or 1.) At least one type of carboguanamine (a ) as an essential component (A)
Amino resin (which is the reaction product of formaldehyde and
A decorative plywood comprising a resin-impregnated sheet layer formed by impregnating and curing a sheet material with a resin composition containing I) and integrated with a substrate. 16. The decorative plywood according to claim 15, wherein the sheet-like material is at least one selected from the group consisting of paper, cloth, and wood veneer. 17. The decorative plywood according to claim 15, wherein the amino resin (I) is fat-soluble. 18. Carboguanamine (a) in amino compound (A)
The decorative plywood according to claim 17, wherein the content of is 60 to 100% by weight. 19. Carboguanamine (a) in amino compound (A)
The decorative plywood according to claim 18, wherein the content is 95 to 100% by weight. 20, methanol miscibility M1 of amino resin (I) is 1
18. The decorative plywood according to claim 17, which has a molecular weight of 200 to 200. 21. The decorative plywood according to claim 17, wherein the resin composition further contains at least one resin selected from the group consisting of unsaturated polyester resins and alkyd resins. 22. The decorative plywood according to claim 21, wherein at least one resin selected from the group consisting of unsaturated polyester resins and alkyd resins is used in a ratio of 10 to 150 parts by weight based on 100 parts by weight of the amino resin (I). 23. The decorative plywood according to claim 15, wherein the amino resin (I) is water-soluble. 24. The decorative plywood according to claim 23, wherein the amino compound (A) contains 20 to 80% by weight of melamine. 25. The decorative plywood according to claim 24, wherein the amino compound (A) contains 20 to 40% by weight of melamine. 26, methanol miscibility M2 of amino resin (I) is 3
The decorative plywood according to claim 24 or 25, which has a particle size of 0 to 200. 27, methanol miscibility M2 of amino resin (I) is 9
The decorative plywood according to claim 26, which has a molecular weight of 0 to 200. 28. Claim 15, wherein formaldehyde is used in a ratio of 1.2 to 10 mol per 1 mol of the amino compound (A).
Decorative plywood as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63178228A JPH01105737A (en) | 1987-07-21 | 1988-07-19 | Decorative sheet and decorative plywood of thermoplastic resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-179953 | 1987-07-21 | ||
| JP17995387 | 1987-07-21 | ||
| JP63178228A JPH01105737A (en) | 1987-07-21 | 1988-07-19 | Decorative sheet and decorative plywood of thermoplastic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01105737A true JPH01105737A (en) | 1989-04-24 |
Family
ID=26498476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63178228A Pending JPH01105737A (en) | 1987-07-21 | 1988-07-19 | Decorative sheet and decorative plywood of thermoplastic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01105737A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3379661A (en) * | 1965-10-21 | 1968-04-23 | Plastics Mfg Company | Molding composition containing a saturated alicyclic guanamine and cured articles ofimproved stain resistance and light resistance thereof |
| JPS5430263A (en) * | 1977-08-11 | 1979-03-06 | Toppan Printing Co Ltd | Production of decorative material |
| JPS5929155A (en) * | 1982-08-11 | 1984-02-16 | 住友ベークライト株式会社 | Melamine resin decorative board |
-
1988
- 1988-07-19 JP JP63178228A patent/JPH01105737A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3379661A (en) * | 1965-10-21 | 1968-04-23 | Plastics Mfg Company | Molding composition containing a saturated alicyclic guanamine and cured articles ofimproved stain resistance and light resistance thereof |
| JPS5430263A (en) * | 1977-08-11 | 1979-03-06 | Toppan Printing Co Ltd | Production of decorative material |
| JPS5929155A (en) * | 1982-08-11 | 1984-02-16 | 住友ベークライト株式会社 | Melamine resin decorative board |
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