JPH04351674A - Coating composition and its cured product - Google Patents
Coating composition and its cured productInfo
- Publication number
- JPH04351674A JPH04351674A JP15094691A JP15094691A JPH04351674A JP H04351674 A JPH04351674 A JP H04351674A JP 15094691 A JP15094691 A JP 15094691A JP 15094691 A JP15094691 A JP 15094691A JP H04351674 A JPH04351674 A JP H04351674A
- Authority
- JP
- Japan
- Prior art keywords
- coating composition
- resin
- coating
- cured product
- film
- 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
- 239000008199 coating composition Substances 0.000 title claims description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 abstract description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 description 18
- 239000000057 synthetic resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000001723 curing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical class 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- -1 dioxane Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- XNDAGYLOQWQWIM-UHFFFAOYSA-N 2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropanoate Chemical compound CC(C)(C)COC(=O)C(C)(C)CO XNDAGYLOQWQWIM-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は硬化物が耐磨耗性に優れ
、硬化収縮が小さく、各種プラスチックフィルムに塗布
し硬化してもカールやそりの少ない基材との密着性に優
れた塗料組成物及びその硬化物に関する。[Industrial Application Field] The present invention is a coating material whose cured product has excellent abrasion resistance, low curing shrinkage, and excellent adhesion to substrates with little curling or warping even when applied to various plastic films and cured. The present invention relates to a composition and a cured product thereof.
【0002】0002
【従来の技術】ポリメチルメタクリレート樹脂、ポリカ
ーボネート樹脂、ポリアリルジグリコールカーボネート
樹脂、ポリスチレン樹脂、スチレンーアクリロニトリル
共重合樹脂(AS樹脂)、ポリ塩化ビニル樹脂、アセテ
ート樹脂、アクリロニトリルーブタジエンースチレン共
重合樹脂(ABS樹脂)、ポリエステル樹脂等から製造
された合成樹脂成形品はガラス製品に比較して軽量で耐
衝撃性に優れているばかりでなく、安価で成形加工が容
易であるなど種々の利点を有しており、有機板ガラス、
鏡、看板、ディスプレー、スクリーン、その他多くの分
野で使用されている。これらの合成樹脂成形品はその表
面の耐磨耗性が不足しているため成形品の輸送中部品の
取付時或いは使用中に他の物体との接触、衝突、引っか
きなどの作用によって表面が損傷が受け製品歩留を低下
させたり、美観がそこなわれたりする。このような合成
樹脂成形品の欠点を改良する方法が従来より種々検討さ
れてきており、例えば多官能アクリレート単量体と有機
溶剤からなる被覆材を合成樹脂成形品の表面に塗布し、
溶剤を乾燥後紫外線照射により硬化被膜を形成させる方
法が数多く提案されている。(例えば特開昭53−10
4638、特開昭53−102936、特開昭54−9
7633、特開昭56−861等を参照)[Prior art] Polymethyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, polystyrene resin, styrene-acrylonitrile copolymer resin (AS resin), polyvinyl chloride resin, acetate resin, acrylonitrile-butadiene-styrene copolymer resin Synthetic resin molded products made from ABS resin (ABS resin), polyester resin, etc. are not only lighter and have better impact resistance than glass products, but also have various advantages such as being inexpensive and easy to mold. It has organic plate glass,
It is used in mirrors, signboards, displays, screens, and many other areas. The surface of these synthetic resin molded products lacks abrasion resistance, so the surface may be damaged by contact with other objects, collisions, scratches, etc. during transportation, installation, or use of the molded product. This may reduce the yield of the product or impair its aesthetic appearance. Various methods have been studied to improve these drawbacks of synthetic resin molded products, such as applying a coating material made of a polyfunctional acrylate monomer and an organic solvent to the surface of the synthetic resin molded product,
Many methods have been proposed in which a cured film is formed by drying a solvent and then irradiating it with ultraviolet rays. (For example, JP-A-53-10
4638, JP-A-53-102936, JP-A-54-9
7633, JP-A-56-861, etc.)
【0003】0003
【発明が解決しようとする課題】多官能アクリレート単
量体を主成分とする被覆材は耐磨耗性に優れ、密着性等
には問題が発生していないが、硬化収縮が大きく、各種
プラスチックのフィルム製品に使用するとカールやそり
が大きく問題である。[Problems to be Solved by the Invention] Coating materials containing polyfunctional acrylate monomers as a main component have excellent abrasion resistance and have not caused any problems in adhesion, etc., but they have large curing shrinkage and are used for various plastics. When used in film products, curling and warping are a major problem.
【0004】0004
【課題を解決するための手段】上記の課題を解決するた
め、本発明者らは鋭意研究の結果、特定の化合物を含有
してなる塗料組成物を開発し本発明に到達した。即ち本
発明は[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have developed a coating composition containing a specific compound as a result of intensive research and have arrived at the present invention. That is, the present invention
【0005】1. 式(1)で示される化合物(A)
、1. Compound (A) represented by formula (1)
,
【0006】[0006]
【化2】[Case 2]
【0007】(式中、RはH又はCH3 である。)有
機溶剤(B)及び任意成分として光重合開始剤(C)を
含むことを特徴とする塗料組成物
2. 第1項記載の塗料組成物の硬化物に関する。(In the formula, R is H or CH3.) A coating composition characterized in that it contains an organic solvent (B) and a photopolymerization initiator (C) as an optional component. The present invention relates to a cured product of the coating composition according to item 1.
【0008】次に本発明の塗料組成物の各構成成分につ
いて説明する。本発明に使用する式(1)で示される化
合物(A)の具体例としては、例えばNext, each component of the coating composition of the present invention will be explained. Specific examples of the compound (A) represented by formula (1) used in the present invention include, for example:
【0009】[0009]
【化3】[Chemical formula 3]
【0010】(新日鉄化学(株)製、カルドエポキシア
クリレート樹脂、ASF−400)等を挙げることがで
きる。(manufactured by Nippon Steel Chemical Co., Ltd., cardo epoxy acrylate resin, ASF-400).
【0011】本発明で使用する有機溶剤(B)の具体例
としては、例えばエタノール、イソプロパノール、ノル
マルプロパノール、イソブチルアルコール、ノルマルブ
チルアルコールなどのアルコール類、ベンゼン、トルエ
ン、キシレン、エチルベンゼンなどの芳香族炭化水素類
、アセトン、メチルエチルケトンなどのケトン類、ジオ
キサンなどのエーテル類、酢酸エチル、酢酸n−プロピ
ル、酢酸n−ブチル、プロピオン酸エチルなどの酸エス
テル類などを挙げることができる。これらの有機溶剤は
1種を単独で使用してもよく、また2種以上を混合して
使用してもよい。これらの有機溶剤は基材となる合成樹
脂の種類によっては、透明な目的で使用するものを曇ら
させたり、着色基材の染顔料を溶出して変色させたり、
又は基材そのものにクラツクを発生しやすくしたりする
場合があるので、使用する有機溶剤の種類は表面に硬化
被膜を形成させる基材の種類或いは目的に応じて適宜選
択して使用することが望ましい。有機溶剤(B)の使用
量は、式(1)で示される化合物(A)100重量部に
対して10〜1000重量部が好ましく、特に好ましく
は50〜500重量部である。Specific examples of the organic solvent (B) used in the present invention include alcohols such as ethanol, isopropanol, normal propanol, isobutyl alcohol, and normal butyl alcohol, and aromatic carbonized solvents such as benzene, toluene, xylene, and ethylbenzene. Examples include hydrogens, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, and acid esters such as ethyl acetate, n-propyl acetate, n-butyl acetate, and ethyl propionate. These organic solvents may be used alone or in combination of two or more. Depending on the type of synthetic resin used as the base material, these organic solvents may cloud the material used for transparent purposes, elute dyes and pigments from the colored base material, and cause discoloration.
Otherwise, it may cause cracks to occur in the substrate itself, so it is desirable to select the type of organic solvent to be used depending on the type of substrate on which a cured film is to be formed or the purpose. . The amount of the organic solvent (B) used is preferably 10 to 1000 parts by weight, particularly preferably 50 to 500 parts by weight, based on 100 parts by weight of the compound (A) represented by formula (1).
【0012】本発明の塗料組成物の硬化物は常法により
紫外線又は電子線を照射し硬化させて得ることができる
。具体例には例えば本発明の塗料組成物を合成樹脂成形
品の表面に塗布し、硬化被膜を形成せしめるため、紫外
線、電子線或いは放射線など活性エネルギー線を照射す
る。その中でも紫外線照射による方法が実用的な面から
みて最も好ましい硬化方法である。The cured product of the coating composition of the present invention can be obtained by irradiating it with ultraviolet rays or electron beams and curing it in a conventional manner. For example, the coating composition of the present invention is applied to the surface of a synthetic resin molded article, and active energy rays such as ultraviolet rays, electron beams, or radiation are irradiated to form a cured film. Among these, the method using ultraviolet irradiation is the most preferred curing method from a practical standpoint.
【0013】紫外線を塗布被膜の硬化エネルギー線とし
て利用する場合には、塗料組成物中に紫外線照射によっ
て重合開始反応を開始しうる光重合開始剤(C)を加え
ておくことが好ましい。このような光重合開始剤(C)
の具体例としては、例えばベンジルジメチルケタール、
1−ヒドロキシシクロヘキシルフェニルケトン、2−ヒ
ドロキシ−2−メチル−1−フェニルプロパン−1−オ
ン、ベンゾフェノン、2,2−ジエトキシアセトフェノ
ン等などを挙げることができる。これらの光重合開始剤
(C)は単独で使用してもよいし2種以上組合せて用い
てもよい。これら光重合開始剤(C)の塗料組成物中へ
の添加量は(A)成分100重量部に対して0〜20重
量部が好ましく、特に好ましくは0.01〜10重量部
である。When ultraviolet rays are used as energy rays for curing the coated film, it is preferable to add a photopolymerization initiator (C) capable of initiating a polymerization reaction upon irradiation with ultraviolet rays to the coating composition. Such a photoinitiator (C)
Specific examples include benzyl dimethyl ketal,
Examples include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, and 2,2-diethoxyacetophenone. These photopolymerization initiators (C) may be used alone or in combination of two or more. The amount of these photopolymerization initiators (C) added to the coating composition is preferably 0 to 20 parts by weight, particularly preferably 0.01 to 10 parts by weight, per 100 parts by weight of component (A).
【0014】本発明の塗料組成物は各成分を常温〜80
℃で混合溶解して得ることができる。[0014] The coating composition of the present invention contains each component at room temperature to 80°C.
It can be obtained by mixing and dissolving at ℃.
【0015】本発明の塗料組成物は、更に必要に応じて
テトラヒドロ(メタ)アクリレート、アクリロイルモル
ホリン、イソボルニル(メタ)アクリレート、ヒドロキ
シピバリン酸ネオペンチルグリコールジ(メタ)アクリ
レート、トリメチロールプロパントリ(メタ)アクリレ
ート、ペンタエリスリトールトリ(メタ)アクリレート
、ペンタエリストールテトラ(メタ)アクリレート、ジ
ペンタエリスリトールペンタ及びヘキサ(メタ)アクリ
レート等の反応性単量体、光安定剤(例えばヒンダード
アミン系)、紫外線吸収剤、酸化防止剤、レベリング剤
、帯電防止剤、界面活性剤、重合禁止剤等を使用するこ
とができる。The coating composition of the present invention may further contain tetrahydro(meth)acrylate, acryloylmorpholine, isobornyl(meth)acrylate, neopentyl hydroxypivalate glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, if necessary. Reactive monomers such as acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta and hexa(meth)acrylate, light stabilizers (e.g. hindered amine type), ultraviolet absorbers, Antioxidants, leveling agents, antistatic agents, surfactants, polymerization inhibitors, etc. can be used.
【0016】次に、上述した塗料組成物を用いた耐磨耗
性合成樹脂成形品の製造は本発明の塗料組成物を合成樹
脂成形品の表面に塗布した後、活性エネルギー線を照射
することによって製造される。本発明の塗料組成物を用
いて耐磨耗性合成樹脂成形品を製造する場合に用いられ
る合成樹脂成形品としては、熱可塑性樹脂、熱硬化性樹
脂を問わず各種合成樹脂成形品、例えばポリメチルメタ
アクリレート樹脂、ポリカーボネート樹脂、ポリアリル
ジグリコールカーボネート樹脂、ポリスチレン樹脂、ア
クリロニトリルースチレン共重合樹脂(AS樹脂)、ポ
リ塩化ビニル樹脂、アセテート樹脂、ABS樹脂、ポリ
エステル樹脂などから製造されるシート状成形品、フィ
ルム状成形品、ロッド状成形品ならびに各種射出成形品
などが具体例として挙げられる。前記した各種成形品は
そのままでも使用することができるが、必要であれば洗
浄、エッチング、コロナ放電、活性エネルギー線照射、
染色、印刷などの前処理を施したものも使用できる。ま
た合成樹脂成形品に対する本発明の塗料組成物の塗布方
法としては刷毛塗り、流し塗り、スプレー塗布、スピン
コート、浸漬塗布などの方法が採用される。それぞれの
方法には一長一短があり、合成樹脂成形品に対する要求
性能或いはその使用用途によって塗布方法も選択するこ
とが好ましい。塗料組成物の合成樹脂成形品の表面に対
する塗布量としては、塗料組成物中に含まれる揮発分の
量或いは目的によっても異なるが、合成樹脂成形品の表
面に形成される硬化被膜の膜厚が1〜30μの範囲にな
るように塗布することが好ましい。又、表面に硬化被膜
を形成された合成樹脂成形品の用途によっては、硬化被
膜を形成させた後に適当な加熱下で曲げ加工を行ったり
、切断ならびに穴あけなどの切削加工を行ったり、部品
取付時に或は使用中に大きい変形歪みが加わったりなど
の苛酷な条件にも耐えることが要求される。このような
場合には、硬化被膜自体の可撓性ならびに基材樹脂との
密着性などの特性に優れていることが必要であるが、第
2の因子として硬化被膜の膜厚がある。即ち膜厚として
は薄いもの程好ましいが、薄くなると耐磨耗性が低下す
るのでそのバランスを考慮して、このような場合は、硬
化被膜の膜厚を1〜9μの範囲にすることが好ましい。Next, manufacturing a wear-resistant synthetic resin molded article using the above-mentioned coating composition involves applying the coating composition of the present invention to the surface of the synthetic resin molding and then irradiating it with active energy rays. Manufactured by. The synthetic resin molded products used when manufacturing wear-resistant synthetic resin molded products using the coating composition of the present invention include various synthetic resin molded products, regardless of thermoplastic resin or thermosetting resin, such as polyester resin molded products. Sheet molding made from methyl methacrylate resin, polycarbonate resin, polyallyl diglycol carbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin (AS resin), polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, etc. Specific examples include molded products, film-shaped molded products, rod-shaped molded products, and various injection molded products. The various molded products described above can be used as they are, but if necessary, they may be cleaned, etched, corona discharged, irradiated with active energy rays, etc.
Materials that have undergone pretreatment such as dyeing or printing can also be used. Further, as a method for applying the coating composition of the present invention to a synthetic resin molded article, methods such as brush coating, flow coating, spray coating, spin coating, and dip coating are employed. Each method has its advantages and disadvantages, and it is preferable to select the coating method depending on the required performance of the synthetic resin molded article or its intended use. The amount of the coating composition to be applied to the surface of the synthetic resin molded article varies depending on the amount of volatile matter contained in the coating composition and the purpose, but it depends on the thickness of the cured film formed on the surface of the synthetic resin molded article. It is preferable to apply the coating so that the thickness is in the range of 1 to 30 μm. In addition, depending on the use of synthetic resin molded products with a hardened film formed on the surface, after the hardened film has been formed, bending under appropriate heating, cutting, drilling, etc. may be performed, or parts may be attached. It is required to withstand severe conditions such as being subjected to large deformation strains at times or during use. In such a case, it is necessary that the cured film itself has excellent properties such as flexibility and adhesion to the base resin, and the second factor is the thickness of the cured film. In other words, the thinner the film thickness, the more preferable it is, but as it becomes thinner, the abrasion resistance decreases, so in such a case, it is preferable to keep the thickness of the cured film in the range of 1 to 9 μm, taking into consideration the balance. .
【0017】活性エネルギー線を照射する工程では、合
成樹脂成形品表面に塗布された塗膜に活性化エネルギー
線を照射して硬化せしめられるが、好ましくは活性エネ
ルギー線で硬化を行う前に特定の条件下に置いて合成樹
脂成形品の表面に塗布した塗料組成物の被膜中に含まれ
る有機溶剤(B)を50重量%以上揮発させた後、活性
エネルギー線を照射した方がよい。塗布した被膜を硬化
せしめるためには具体的にはキセノンランプ、低圧水銀
灯、中圧水銀灯、高圧水銀灯又は超圧水銀灯などの光源
から発せられる紫外線又は通常20〜2000KVの電
子線加速器から取り出される電子線、α線、β線、γ線
などの放射線などの活性エネルギー線を照射する。In the step of irradiating active energy rays, the coating film applied to the surface of the synthetic resin molded product is cured by irradiating the coating film with activation energy rays. Preferably, a specific coating film is applied before curing with active energy rays. It is better to volatilize 50% by weight or more of the organic solvent (B) contained in the film of the coating composition applied to the surface of the synthetic resin molded article under conditions, and then irradiate it with active energy rays. In order to cure the coated film, specifically, ultraviolet rays emitted from a light source such as a xenon lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, or super pressure mercury lamp, or an electron beam taken out from an electron beam accelerator of usually 20 to 2000 KV are used. , irradiation with active energy rays such as alpha, beta, and gamma rays.
【0018】[0018]
【実施例】以下本発明を実施例により更に具体的に説明
する。
実施例1〜4、比較例1
表1に示す配合組成(数値は重量部で表示)に従って各
配合成分を混合することにより本発明の塗料組成物を調
整し、これに厚さ0.1mmのメタクリル樹脂製シート
を浸漬した後、ゆっくりと引上げシートの表面に該塗料
組成物の塗布被膜を形成せしめた。次いで有機溶剤を5
0℃で5分間で揮発させ、紫外線(2KW高圧水銀灯)
を照射し、シートの表面に約5μの厚みで硬化被膜を形
成させた。各種性能評価(鉛筆硬度、スチールウール擦
傷テスト、密着性カールの発生の有無)を行い同じ表1
に示した。[Examples] The present invention will now be explained in more detail with reference to Examples. Examples 1 to 4, Comparative Example 1 A coating composition of the present invention was prepared by mixing each compounding component according to the formulation shown in Table 1 (values are expressed in parts by weight), and a coating composition of the present invention with a thickness of 0.1 mm was prepared. After the methacrylic resin sheet was immersed, the coating composition was slowly pulled up to form a coating film on the surface of the sheet. Then add 5 organic solvents
Volatize for 5 minutes at 0°C and apply ultraviolet light (2KW high pressure mercury lamp)
was irradiated to form a cured film with a thickness of about 5 μm on the surface of the sheet. Various performance evaluations (pencil hardness, steel wool abrasion test, presence or absence of adhesion curl) were conducted and the same Table 1 was conducted.
It was shown to.
【0019】鉛筆硬度
JIS K5651−1966に準じた鉛筆硬度スチ
ールウール擦傷テスト
スチールウール#0000を使用して硬化被膜の表面を
こすってその傷つきの程度で評価した。
○……強くこすって傷がつかない
△……強くするとやや傷がつき、弱くこすっても傷がつ
かない
×……弱くこすっても傷がつくPencil hardness Steel wool scratch test in accordance with JIS K5651-1966 Steel wool #0000 was used to rub the surface of the cured film and the degree of scratches was evaluated. ○...No scratches even when rubbed hard △...Slight scratches occur when rubbed hard, no scratches even when rubbed weakly×...Scratch occurs even when rubbed weakly
【0020】密着性
硬化被膜に切れ目を入れて一辺1mmの正方形の小片を
100個刻み、その表面にセロハンテープをはり付け直
ちにはがした。そのとき残った硬化被膜の小片の数によ
って表した。その数の多いほど密着性がすぐれている。[0020] Cuts were made in the adhesive cured film to cut into 100 square pieces of 1 mm on each side, and cellophane tape was attached to the surface and immediately removed. It was expressed by the number of small pieces of the cured film remaining at that time. The larger the number, the better the adhesion.
【0021】カールの発生
○……カール或はそりの発生がほとんどない△……カー
ル或はそりの発生がややあり×……カール或はそりが大
きい0021: Occurrence of curl ○... Hardly any occurrence of curl or warp △... Slight occurrence of curl or warpage ×... Large amount of curl or warpage
【0022】
表1
実 施 例 比
較例
1 2
3 4*4 1(A) 成分 AS
F−400*1 35 33
28 35(B) 成分 n−プロピ
ルアルコール 55 55 55
55 55 キシレン
10 10
10 10 10(C) 成分
イルガキュアー184 *2 1.7 1.
7 1.7 1.
7 KAYARAD DPHA*3
5 33
テトラヒドロフルフリルアクリレート
2 2
2 鉛 筆 硬
度 8H 8H 8
H 7H 8H スチ
ールウール擦傷テスト ○ ○
○ ○ ○
密 着 性 100/
100 100/100 100/100 100/1
00 100/100 カールの発
生 ○ ○
○ ○ ×[0022]
Table 1
Implementation example Comparative example
1 2
3 4*4 1(A) Component AS
F-400*1 35 33
28 35(B) Component n-propyl alcohol 55 55 55
55 55 Xylene 10 10
10 10 10 (C) Component
Irgacure 184 *2 1.7 1.
7 1.7 1.
7 KAYARAD DPHA*3
5 33
Tetrahydrofurfuryl acrylate
2 2
2 Pencil hard
degree 8H 8H 8
H 7H 8H Steel wool abrasion test ○ ○
○ ○ ○
Adhesion 100/
100 100/100 100/100 100/1
00 100/100 Curl formation ○ ○
○ ○ ×
【0023】
注 *1 ASE−400:新日鉄化学(株)製、
前記式(2)の化合物、カルドエポキシアクリレート樹
脂
*2 イルガキュア−184:チバ・ガイギー社製、
光重合開始剤
*3 KAYARAD DPHA:日本化薬(株)
製、ジペンタエリスリトールペンタ及びヘキサアクリレ
ート混合物
*4 実施例4の硬化は電子線加速器(175KeV
)を用いて電子線を照射し硬化させた。[0023]
Note *1 ASE-400: Manufactured by Nippon Steel Chemical Co., Ltd.
Compound of formula (2), cardo epoxy acrylate resin *2 Irgacure-184: manufactured by Ciba Geigy,
Photoinitiator *3 KAYARAD DPHA: Nippon Kayaku Co., Ltd.
Co., Ltd., dipentaerythritol penta and hexaacrylate mixture *4 Example 4 was cured using an electron beam accelerator (175 KeV
) and was cured by irradiation with an electron beam.
【0024】[0024]
【発明の効果】本発明の塗料組成物の硬化物は耐磨耗性
に優れ、硬化収縮が小さく、各種プラスチックのシート
或はフィルム製品に塗布し硬化したものは、カールやそ
りの発生はみられない。[Effects of the Invention] The cured product of the coating composition of the present invention has excellent abrasion resistance and small curing shrinkage, and when applied to various plastic sheets or film products and cured, curling and warping do not occur. I can't do it.
Claims (2)
】 (式中、RはH又はCH3 である。)有機溶剤(B)
及び任意成分として光重合開始剤(C)を含むことを特
徴とする塗料組成物。Claim 1: A compound (A) represented by formula (1), [Chemical formula 1]
] (In the formula, R is H or CH3.) Organic solvent (B)
and a coating composition comprising a photopolymerization initiator (C) as an optional component.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15094691A JPH04351674A (en) | 1991-05-28 | 1991-05-28 | Coating composition and its cured product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15094691A JPH04351674A (en) | 1991-05-28 | 1991-05-28 | Coating composition and its cured product |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04351674A true JPH04351674A (en) | 1992-12-07 |
Family
ID=15507876
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15094691A Pending JPH04351674A (en) | 1991-05-28 | 1991-05-28 | Coating composition and its cured product |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04351674A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001040248A (en) * | 1999-07-27 | 2001-02-13 | Sanyo Chem Ind Ltd | Active energy ray-curable coating composition |
US7361432B2 (en) * | 2001-02-01 | 2008-04-22 | National Institute Of Advanced Industrial Science And Technology | Composition for hologram-recording material, hologram-recording medium, and process for producing the same |
-
1991
- 1991-05-28 JP JP15094691A patent/JPH04351674A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001040248A (en) * | 1999-07-27 | 2001-02-13 | Sanyo Chem Ind Ltd | Active energy ray-curable coating composition |
US7361432B2 (en) * | 2001-02-01 | 2008-04-22 | National Institute Of Advanced Industrial Science And Technology | Composition for hologram-recording material, hologram-recording medium, and process for producing the same |
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