JPH0214272A - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- JPH0214272A JPH0214272A JP16257588A JP16257588A JPH0214272A JP H0214272 A JPH0214272 A JP H0214272A JP 16257588 A JP16257588 A JP 16257588A JP 16257588 A JP16257588 A JP 16257588A JP H0214272 A JPH0214272 A JP H0214272A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- polyol
- polyurethane resin
- coating composition
- polycarbonate
- 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.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 29
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 45
- 229920005862 polyol Polymers 0.000 claims abstract description 44
- 150000003077 polyols Chemical class 0.000 claims abstract description 32
- 239000004417 polycarbonate Substances 0.000 claims abstract description 28
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 19
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- -1 ester polyol Chemical class 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000002991 molded plastic Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000003973 paint Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 238000005507 spraying Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 11
- 238000001723 curing Methods 0.000 description 9
- 150000005846 sugar alcohols Polymers 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010137 moulding (plastic) Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 241001233242 Lontra Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は自動車部品等のプラスチック成型物の表面に塗
膜を形成する塗料組成物に関し、更に詳しくは、耐候性
、耐１’＋’ｌｌ性、可撓性及び弾性に優れた被膜を高
い硬化速度で与えることができる塗料組成物に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a coating composition that forms a coating film on the surface of a plastic molded object such as an automobile part. The present invention relates to a coating composition that can provide a coating with excellent properties, flexibility, and elasticity at a high curing rate.
（従来の技術及びその問題点）
従来、自動車部品の中でもバンパー等の如く弾性をイｆ
するプラスチック成型物用の塗料には、可撓性及び弾性
を有すると同時に、長時間の屋外使用に耐え得る耐候性
と酸、アルカリやガソリン等の有機溶剤に対する耐薬、
９性が要求される。(Prior art and its problems) Conventionally, among automobile parts, elasticity has been improved, such as in bumpers, etc.
Paints for plastic moldings have flexibility and elasticity, weather resistance that can withstand long-term outdoor use, and chemical resistance against acids, alkalis, and organic solvents such as gasoline.
Nineness is required.
従来この様な目的に使用する塗料としては、アジピン酸
及び芳香族ジカルボン酸と多価アルコールとから調製し
たポリエステルポリオールを主剤とし、ポリイシシアネ
ートを硬化剤とする２液型塗料及びポリエステルポリオ
ールとアクリルポリオールとの混合物を主剤とする同様
な塗料の使用が試みられてきた。Conventionally, paints used for this purpose include two-component paints that have a polyester polyol prepared from adipic acid, aromatic dicarboxylic acid, and polyhydric alcohol as the main ingredient and polyisocyanate as a curing agent, and two-component paints that use polyester polyol and acrylic as a curing agent. Attempts have been made to use similar paints based on mixtures with polyols.
しかしながら、従来の塗料では可撓性及び弾性の点では
満足できるものの、長時間の屋外使用に耐えられる耐候
性という点で必ずしも充分ではなかった。However, although conventional paints are satisfactory in terms of flexibility and elasticity, they are not necessarily sufficient in weather resistance to withstand long-term outdoor use.
又、従来の塗料では、塗膜の硬化に長時間を要し生産性
の点で不満があった。In addition, with conventional paints, it takes a long time to cure the coating film, resulting in dissatisfaction with productivity.
従って、本発明の目的は従来技術の問題点を解決し、可
撓性、弾性及び耐久性を有すると同時に塗膜形成速度が
大であるプラスチック成型物用の塗料組成物を提供する
ことである。SUMMARY OF THE INVENTION It is therefore an object of the present invention to solve the problems of the prior art and to provide a coating composition for plastic moldings that has flexibility, elasticity and durability and at the same time has a high coating film formation rate. .
（問題点を解決する為の手段）。(Means for solving problems).
上記目的は以下の本発明によって達成される。The above objects are achieved by the present invention as described below.
すなわち、本発明は、ポリカーボネートポリオール又は
ポリカーボネートエステルポリオールと、２価アルコー
ル及び３価アルコールの混合物と、ジイソシアネートと
を重合反応させて得られる０６価２０乃至６０の末端氷
酸基を有する分子量２，０００乃至７，０００のポリウ
レタン樹脂の有機溶剤溶液と、上記有機溶剤溶液中に含
まれるポリウレタン樹脂の水酸基に対してイソシアネー
ト基が０．８乃至２．０当量となる割合でポリカーボネ
ートとを混合してなるプラスチック成型物用塗料組成物
である。That is, the present invention provides a polycarbonate polyol or a polycarbonate ester polyol, a mixture of dihydric alcohol and trihydric alcohol, and a diisocyanate, which are obtained by a polymerization reaction and have a molecular weight of 2,000 and have a terminal glacial acid group with a 06 valence of 20 to 60. or 7,000 polyurethane resin in an organic solvent and polycarbonate in a ratio such that the isocyanate group is 0.8 to 2.0 equivalent to the hydroxyl group of the polyurethane resin contained in the organic solvent solution. This is a coating composition for plastic molded articles.
（作 用）
被膜形成成分の主成分として、ポリカーボネートポリオ
ール又はポリカーボネートエステルポリオールと、２価
アルコール及び３価アルコールの混合物と、ジイソシア
ネートとを重合反応させて得られる０６価２０乃至６０
の末端氷酸基を打する分子ｈｔ２，０００乃至７，００
０のポリウレタン樹脂を使用することによって、可撓性
、弾性及び耐久性を有する被膜を与えると同時に、塗膜
形成速度が大であるプラスチック成型物用塗料組成物が
提供される。(Function) As the main component of the film-forming component, 06 valence 20 to 60 obtained by polymerizing polycarbonate polyol or polycarbonate ester polyol, a mixture of dihydric alcohol and trihydric alcohol, and diisocyanate.
Molecules that hit the terminal glacial group of h2,000 to 7,00
By using a polyurethane resin of 0.0, a coating composition for plastic moldings is provided which provides a coating having flexibility, elasticity and durability, and at the same time has a high coating film formation rate.
（好ましい実施態様）
次に好ましい実施態様を挙げて本発明を更に詳しく説明
する。(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.
本発明において使用するポリカーボネートポリオールと
は、従来公知の多価アルコールとホスゲン、クロルギ酸
エステル、ジアルキルカーボネート又はジアリルカーボ
ネート等のカーボネートとの縮合によって得られる末端
氷酸基のポリオールであり、種々の分子量のものが得ら
れ又市場から入手して使用できる。本発明において特に
好適なポリカーボネートボッオールは、多価アルコール
として１．６−ヘキサンジオール、１．４−ブタンジオ
ール、１．３−ブタンジオール、ネオペンチルグリコー
ル又は１．５−ベンタンジオールを使用したものであり
、その分子量は約５００乃至２．０００で、そのＯＨ価
が約５０乃至２００の範囲のものである。The polycarbonate polyol used in the present invention is a polyol with a terminal glacial acid group obtained by condensing a conventionally known polyhydric alcohol with a carbonate such as phosgene, chloroformate, dialkyl carbonate, or diallyl carbonate, and has various molecular weights. It can be obtained from the market and used. Particularly suitable polycarbonate bottles in the present invention are those using 1.6-hexanediol, 1.4-butanediol, 1.3-butanediol, neopentyl glycol or 1.5-bentanediol as the polyhydric alcohol. The molecular weight is approximately 500 to 2,000, and the OH value is approximately 50 to 200.
又、本発明において使用するポリカーボネートエステル
ポリオールとは、上記のポリカーボネートポリオールと
多価カルボン酸又は多価カルボン酸と多価アルコールと
の混合物カプロラクトンとを反応させて得られる末端氷
酸基のポリオールであり、多価カルボン酸及び多価アル
コールとしては従来公知のものがいずれも使用可能であ
るが、特に好適な多価カルボッ酸は１，１０−デカンジ
カルボン酸であり、多価アルコールとしてはｌ。Further, the polycarbonate ester polyol used in the present invention is a polyol with a terminal glacial acid group obtained by reacting the above-mentioned polycarbonate polyol with a polyhydric carboxylic acid or a mixture of a polyhydric carboxylic acid and a polyhydric alcohol, caprolactone. As the polyhydric carboxylic acid and polyhydric alcohol, any conventionally known ones can be used, but a particularly suitable polycarboxylic acid is 1,10-decanedicarboxylic acid, and the polyhydric alcohol is 1,10-decanedicarboxylic acid.
６−ヘキサンジオールである。このポリカーボネートエ
ステルポリオールにおけるポリカーボネートポリオール
と多価カルボン酸又は多価カルボン酸と多価アルコール
の混合物又はカプロラクトンとの使用比率は約前者１０
０重量部当り後者が５乃至２００重量部の割合が好まし
い。6-hexanediol. In this polycarbonate ester polyol, the ratio of polycarbonate polyol and polyhydric carboxylic acid or a mixture of polyhydric carboxylic acid and polyhydric alcohol or caprolactone is about 10
A ratio of 5 to 200 parts by weight of the latter per 0 parts by weight is preferred.
特に好ましいものはその分子量は約５００乃至２．００
０で、そのＯＨ価が約５０乃至２００のの範囲のもので
ある。このポリカーボネートエステルポリオールは框独
で使用してもよいし、又、１）η記ポリカーボネートポ
リオールと混合して使用してもよい。Especially preferred ones have a molecular weight of about 500 to 2.00.
0, and its OH number ranges from about 50 to 200. This polycarbonate ester polyol may be used alone, or may be used in combination with 1) the polycarbonate polyol listed in η.
本発明において使用する２価アルコールとしては、従来
公知の２価アルコールがいずれも使用できるが、特に好
適なものとしては、１，６−ヘキサンジオール、１．４
−ブタンジオール、１゜３−ブタンジオール、ネオペン
チルグリコール又は１．５−ベンタンジオール等が挙げ
られる。As the dihydric alcohol used in the present invention, any conventionally known dihydric alcohol can be used, but particularly preferred ones include 1,6-hexanediol, 1.4-hexanediol,
-butanediol, 1.3-butanediol, neopentyl glycol or 1.5-bentanediol.
又、本発明において使用する３価アルコールとしては従
来公知の３価アルコールがいずれも使用できるが、特に
好適なものはトリメチロールプロパン及びグリセリンで
ある。Further, as the trihydric alcohol used in the present invention, any conventionally known trihydric alcohol can be used, but particularly preferred are trimethylolpropane and glycerin.
以上の如き２価アルコールと３価アルコールとは当量比
で前者１当量当り後者が約０．２乃至２当量の割合で使
用するのが好ましい。The dihydric alcohol and trihydric alcohol described above are preferably used in an equivalent ratio of about 0.2 to 2 equivalents of the latter per 1 equivalent of the former.
又、２価アルコールと３価アルコールとの合計量は、前
記ポリカーボネートポリオール又はポリカーボネートエ
ステルポリオール１当量当り約０．５乃至３当量の割合
で使用するのが好ましい。The total amount of dihydric alcohol and trihydric alcohol is preferably about 0.5 to 3 equivalents per equivalent of the polycarbonate polyol or polycarbonate ester polyol.
本発明で使用するジイソシアネットとしては、従来公知
のものはいずれも使用できるが、耐候性の面からは脂肪
族ジイソシアネートが望ましく、例えば、イソホロンジ
イソシアネート、ヘキサメチレンジイソシアネート、４
．４−ジシクロヘキシルメタンジイソシアネート、リジ
ンジイソシアネート等か挙げられ、他の好適なものとし
てはキシリレンジイソシアネート等が耐候性に優れたも
のとして挙げられる。As the diisocyanate used in the present invention, any conventionally known diisocyanate can be used, but from the viewpoint of weather resistance, aliphatic diisocyanates are preferable, such as isophorone diisocyanate, hexamethylene diisocyanate,
．． Examples include 4-dicyclohexylmethane diisocyanate and lysine diisocyanate, and other suitable examples include xylylene diisocyanate, which has excellent weather resistance.
上記ジイソシアネートは前記ポリオール成分（２価アル
コール及び３価アルコールを含む）１当量当り約０．６
乃至０．ｇ当量の割合で使用し、得られるポリウレタン
樹脂のＯＨ価が２０乃至６０の末端氷酸基をイｆする分
子量ｚ、ｏｏｏ７５至７，０００の範囲とする。The diisocyanate is about 0.6 per equivalent of the polyol component (including dihydric alcohol and trihydric alcohol).
to 0. The molecular weight z is in the range of 75 to 7,000 so that the resulting polyurethane resin has an OH value of 20 to 60 and a terminal glacial acid group.
本発明において使用する有機溶剤は、上記ポリウレタン
樹脂を溶解する有機溶剤であればいずれのものでもよい
が、好ましいものとしては、アセトン、メチルエチルケ
トン、メチルイソブチルケトン、酢酸エチル、酢酸ブチ
ル、テトラヒドロフラン、トルエン、キシレンン及びそ
れらの混合物が挙げられる。The organic solvent used in the present invention may be any organic solvent as long as it dissolves the polyurethane resin, but preferred ones include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, Mention may be made of xylenes and mixtures thereof.
本発明で使用するポリウレタン樹脂は上記原料から常法
に従って製造できるものであり、例えば、前記ポリカー
ボネートポリオール又はポリカーボネートエステルポリ
オール、２価アルコール及び３価アルコールとの混合物
及びジイソシアネートを、重合生成物のＯＨ価が２０乃
至６０、分子量が２，０００乃至７，０００となる割合
で、有機溶剤中で、例えば、約９０乃至１３０℃で約２
乃至８時間反応させることによって得られ、得られたポ
リウレタン樹脂は一旦有機溶剤から分離して使用するこ
とも可能であるが、−数的には樹脂濃度を調節してその
まま溶液として使用することが好ましい。The polyurethane resin used in the present invention can be produced from the above-mentioned raw materials according to a conventional method. is 20 to 60 and the molecular weight is 2,000 to 7,000 in an organic solvent at about 90 to 130°C, for example, about 2.
The polyurethane resin obtained by reacting for 8 hours can be used after being separated from the organic solvent, but numerically it is possible to adjust the resin concentration and use it as a solution as it is. preferable.
上記ポリウレタン樹脂のＯＨ価が２０未満である場合に
は、得られる塗膜の架橋密度が低く十分な耐久性が得ら
れず、一方、ＯＨ価が６０を越えると架橋密度が高くな
りすぎ、得られる塗膜の可撓性が低下するので好ましく
ない。If the OH value of the polyurethane resin is less than 20, the resulting coating film will have a low crosslinking density and will not have sufficient durability. On the other hand, if the OH value exceeds 60, the crosslinking density will be too high and the resulting coating film will not have sufficient durability. This is not preferable because the flexibility of the coated film decreases.
又、分子量が２，０００未満で、は塗膜形成速度が低く
作業性が低下し、一方分子量が７，０００を越えると塗
装時に塗膜形成成分の含有率が低くなり同様に作業性が
低下するので好ましくない。In addition, if the molecular weight is less than 2,000, the coating film formation rate is low and workability is reduced, while if the molecular weight exceeds 7,000, the content of film-forming components during painting is low and workability is similarly reduced. Therefore, it is not desirable.
本発明で使用するポリイシシアネートとは、従来塗料や
接着剤の分野で架橋剤又は硬化剤として広く使用されて
いるポリイシシアネートであり、公知のものはいずれも
使用でき、例えば、前記脂肪族ジイソシアネートの水付
加物、トリメチロールプロパン付加体、自己縮合体等が
好ましく使用される。これらのポリイシシアネートは前
記ポリウレタン樹脂の水酸基の１当計当り約０．８乃至
２当量の割合で使用するのが好ましい。The polyisocyanate used in the present invention is a polyisocyanate that has been widely used as a crosslinking agent or curing agent in the field of paints and adhesives, and any known ones can be used. Water adducts, trimethylolpropane adducts, self-condensates, and the like of diisocyanates are preferably used. These polyisocyanates are preferably used in an amount of about 0.8 to 2 equivalents per equivalent of hydroxyl groups in the polyurethane resin.
本発明の塗料組成物は前記ポリウレタン樹脂の有機溶剤
溶液に」二記のポリイシシアネートを混合して得られる
が、着色塗）漠が必要である場合には前記ポリウレタン
樹脂の有機溶剤溶液に酸化チタン、カーボンブラック、
フタロシアニンブルーその他の公知の顔料を所望の割合
で添加することができ、その他充填剤、帯電防止剤、安
定剤、酸化防止剤、紫外線吸収剤等の如く必要に応じて
種々の添加剤も配合することができる。The coating composition of the present invention can be obtained by mixing the above polyisocyanate in an organic solvent solution of the polyurethane resin, but if coloring is required, the organic solvent solution of the polyurethane resin can be oxidized. titanium, carbon black,
Phthalocyanine blue and other known pigments can be added in desired proportions, and various other additives such as fillers, antistatic agents, stabilizers, antioxidants, ultraviolet absorbers, etc. can also be added as necessary. be able to.
（実施例）
次に実施例及び比較例を挙げて本発明を更に具体的に説
明する。尚、文中部又は％とあるのは特に断りの無い限
り重量基準である。(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples. It should be noted that unless otherwise specified, the terms in the text or % are based on weight.
実施例１
ジエチルカーボネート３５０部及び１．６−ヘキサンジ
オール７０８部を１２０℃乃至２００℃で１５時間反応
させ、その後１５０℃に冷却し、３０乃至５０ｍｍＨｇ
に減圧して残留するエタノールを十分留去し、７８６部
のポリカーボネートポリオールを得た。このポリオール
のＯＨ価は４２７である。このポリオールの中に１，６
−ヘキサンジオール２３６部と１．１０−デカンジカル
ボン酸９２０部を入れ、約２００乃至２２０℃で８時間
反応させ、３０乃至５０ｍｍＨｇで減圧反応を行い、最
終的に１，７５０部のポリカーボネートエステルポリオ
ールを得た。このポリオールの分子量は約１，６５０で
あり、ＯＨ価は約６８であった。Example 1 350 parts of diethyl carbonate and 708 parts of 1,6-hexanediol were reacted at 120°C to 200°C for 15 hours, then cooled to 150°C, and heated to 30 to 50 mmHg.
The remaining ethanol was sufficiently distilled off under reduced pressure to obtain 786 parts of polycarbonate polyol. The OH value of this polyol is 427. In this polyol, 1,6
- Add 236 parts of hexanediol and 920 parts of 1.10-decanedicarboxylic acid, react at about 200 to 220°C for 8 hours, perform a reduced pressure reaction at 30 to 50 mmHg, and finally add 1,750 parts of polycarbonate ester polyol. Obtained. This polyol had a molecular weight of about 1,650 and an OH value of about 68.
このポリオール１，２４０部、１．４−ブタンジオール
４５部及びトリメチロールプロパン３３．５部にメチル
イソブチルケトン５３２部及びトルエン５３２部を加え
均一に混合したものにイソホロンジイソシアネート２７
８部を添加し１１０乃至１１５℃で５時間反応させポリ
ウレタン樹脂の有機溶剤溶液を得た。To 1,240 parts of this polyol, 45 parts of 1,4-butanediol, and 33.5 parts of trimethylolpropane, 532 parts of methyl isobutyl ketone and 532 parts of toluene were added and mixed uniformly, and 27 parts of isophorone diisocyanate was added.
8 parts were added and reacted at 110 to 115° C. for 5 hours to obtain an organic solvent solution of polyurethane resin.
このポリウレタン樹脂溶液の不揮発分は６０％で粘度は
４，２００ｃｐｓであった。又、このポリウレタン樹脂
のＯＨ価は約２６で、分子量は約６．５００であった。The nonvolatile content of this polyurethane resin solution was 60% and the viscosity was 4,200 cps. Further, the OH number of this polyurethane resin was about 26, and the molecular weight was about 6.500.
次いで前記のポリウレタン樹脂溶液１００部にルチル型
酸化チタン４５部、酸化防止剤０． １部及び紫外線吸
収剤０．１部を添加して混練し着色されたポリウレタン
樹脂溶液を得た。この着色樹脂溶液１５０部に対してボ
ッイソシアネート（ダイブラコートＰＵ−Ｅ−ハードナ
ー、大ロ精化工業製）１１．８部を添加し、２液型の本
発明の塗料組成物を得た。尚、この塗料組成物の中に含
まれるポリウレタン樹脂のＯＨ基に対するポリイシシア
ネート中のイソシアネート基の当量比は１．３である。Next, 45 parts of rutile titanium oxide and 0.0 parts of antioxidant were added to 100 parts of the polyurethane resin solution. 1 part and 0.1 part of an ultraviolet absorber were added and kneaded to obtain a colored polyurethane resin solution. To 150 parts of this colored resin solution, 11.8 parts of Voisocyanate (Dybracoat PU-E-hardener, manufactured by Dairo Seika Kogyo Co., Ltd.) was added to obtain a two-component coating composition of the present invention. The equivalent ratio of the isocyanate groups in the polyisocyanate to the OH groups in the polyurethane resin contained in this coating composition is 1.3.
この塗料組成物１００部をメチルイソブチルケトン／酢
酸ブチル／キシレン＝１／１／１（重量比）からなるシ
ンナー６０部で希釈し、塗料粘度が岩田カップＮＫ＃２
で２２秒及び不揮発分４６．５％のスプレー塗装液を得
た。100 parts of this paint composition was diluted with 60 parts of thinner consisting of methyl isobutyl ketone/butyl acetate/xylene = 1/1/1 (weight ratio), and the paint viscosity was Iwata Cup NK#2.
A spray coating liquid was obtained in 22 seconds and with a non-volatile content of 46.5%.
予めブライマーとしてレザロイドＲＩＭブライマー（大
日精化工業製）を塗装しておいたウレタンＲＩＭ成型物
の表面に前記スプレー塗装液を乾燥時膜厚が３０μｍに
なる様に塗装し、室温で１５分間セツティング後７０℃
で２０分間加熱硬化させた。この塗装物を室温で１０分
間放置し指触乾燥性を試験し、更にこの塗装物を５０℃
で４８時間加熱し、その後室温で１週間放置後、耐較性
試験（サンシャインウエザオメーター）及び耐薬品性試
験に供した。その結果を後記第１表に示す。本実施例の
塗料組成物は硬化速度が大であると同時に優れた耐候性
及び耐薬品性を示す。The above spray coating liquid was applied to the surface of the urethane RIM molded product, which had been previously coated with Retheroid RIM Brimer (manufactured by Dainichiseika Chemical Industry Co., Ltd.) as a brimer, to a dry film thickness of 30 μm, and set for 15 minutes at room temperature. After 70℃
It was heated and cured for 20 minutes. The coated product was left at room temperature for 10 minutes to test its dryness to the touch, and then the coated product was heated to 50°C.
The sample was heated for 48 hours, then left at room temperature for one week, and then subjected to a resistance test (Sunshine Weather-Ometer) and a chemical resistance test. The results are shown in Table 1 below. The coating composition of this example has a high curing speed and at the same time exhibits excellent weather resistance and chemical resistance.
実施例２
ジエチルカーボネート９４４部及び１，６−ヘキサンジ
オール１，１８０部を１２０℃乃至２００℃で１５時間
反応させ、その後１５０℃に冷却し、３０乃至５０ ｍ
ｍ Ｈｇに減圧して残留するエタノールを十分留去し
、１，３８８部のポリカーボネートポリオールを得た。Example 2 944 parts of diethyl carbonate and 1,180 parts of 1,6-hexanediol were reacted at 120°C to 200°C for 15 hours, then cooled to 150°C, and 30 to 50 m
The remaining ethanol was sufficiently distilled off by reducing the pressure to m Hg to obtain 1,388 parts of polycarbonate polyol.
このポリオールのＯＨ価は１６２である。このポリオー
ルの中にカプロラクトン６８４部を入れ、約２００乃至
２２０℃で８時間反応させ、３０乃至５０ｍｍＨｇで減
圧反応を行い、最終的に２，０７２部のポリカーボネー
トエステルポリオールを得た。このポリオールの分子量
は約１．０４０であり、ＯＨ価は約１０８であった。The OH number of this polyol is 162. 684 parts of caprolactone was added to this polyol and reacted at about 200 to 220°C for 8 hours, followed by a reduced pressure reaction at 30 to 50 mmHg to finally obtain 2,072 parts of polycarbonate ester polyol. The molecular weight of this polyol was about 1.040, and the OH number was about 108.
このポリオール１，０４０部、１，４−ブタンジオール
４５部及びトリメチロールプロパン６７部にメチルイソ
ブチルケトン４９５部及びトルエン４９５部を加え均一
に混合したものにイソホロンジイソシアネート３３３部
を添加し１１０乃至１１５℃で５時間反応させポリウレ
タン樹脂の有機溶剤溶液を得た。495 parts of methyl isobutyl ketone and 495 parts of toluene were added to 1,040 parts of this polyol, 45 parts of 1,4-butanediol, and 67 parts of trimethylolpropane, mixed uniformly, and 333 parts of isophorone diisocyanate was added to the mixture at 110 to 115°C. The mixture was reacted for 5 hours to obtain an organic solvent solution of polyurethane resin.
このポリウレタン樹脂溶液の不揮発分は６０％で粘度は
２．３００ｃｐｓであった。又、このポリウレタン樹脂
のＯＨ価は約５７で、分子１７ｔは約２．９５０であっ
た。This polyurethane resin solution had a nonvolatile content of 60% and a viscosity of 2.300 cps. Further, the OH value of this polyurethane resin was about 57, and the molecule 17t was about 2.950.
次いで前記のポリウレタン樹脂溶液１００部にルチル型
酸化チタン４５部、酸化防止剤０．１部及び紫外線吸収
剤０．１部を添加して混練し着色されたポリウレタン樹
脂溶液を得た。この着色樹脂溶液１５０部に対してポリ
イシシアネート（ダイブラコートＰＵ−Ｅ−ハードナー
、犬日蹟化工業製）２５．９部を添加し、２液型の本発
明の塗料組成物を得た。尚、この塗料組成物の中に含ま
れるポリウレタン樹脂のＯＨ基に対するポリイシシアネ
ート中のイソシアネート基の当量比は１．３である。こ
の塗料組成物１００部をメチルイソブチルケトン／酢酸
ブチル／キシレン＝１／１／１（重■比）からなるシン
ナー５０部で希釈し、塗料粘度が岩田カップＮＫ＃２で
２０秒及び不揮発分５１．０％のスプレー塗装液を得た
。Next, 45 parts of rutile titanium oxide, 0.1 part of an antioxidant and 0.1 part of an ultraviolet absorber were added to 100 parts of the polyurethane resin solution and kneaded to obtain a colored polyurethane resin solution. To 150 parts of this colored resin solution, 25.9 parts of polyisocyanate (Dybracoat PU-E-hardener, manufactured by Inunichi Seika Kogyo Co., Ltd.) was added to obtain a two-component coating composition of the present invention. The equivalent ratio of the isocyanate groups in the polyisocyanate to the OH groups in the polyurethane resin contained in this coating composition is 1.3. 100 parts of this paint composition was diluted with 50 parts of thinner consisting of methyl isobutyl ketone/butyl acetate/xylene = 1/1/1 (weight ratio), and the paint viscosity was 20 seconds with Iwata Cup NK #2 and the non-volatile content was 51. A spray coating solution of .0% was obtained.
予めブライマーとしてレザロイ、ドＲＩＭブライマー（
大日精化工業製）を塗装しておいたウレタンＲＩＭ成型
物の表面に前記スプレー塗装液を乾燥時膜厚が３０μｍ
になる様に塗装し、室温で１５分間セツティング後７０
℃で２０分間加熱硬化させた。この塗装物を室温で１０
分間放置し指触乾燥性を試験し、更にこの塗装物を５０
℃で４８時間加熱し、その後室温で１週間放置後、耐候
性試験（サンシャインウエザオメーター）及び耐薬品性
試験に供した。その結果を後記第１表に示す。本実施例
の塗料組成物も実施例１と同様に硬化速度が大であると
同時に優れた耐候性及び耐薬品性を示す。Reza Roy, De RIM Brimer (
The above spray coating liquid was applied to the surface of the urethane RIM molded product, which had been coated with urethane (manufactured by Dainichiseika Kagyo Kogyo) to a film thickness of 30 μm when dry.
After setting for 15 minutes at room temperature,
It was heat-cured at ℃ for 20 minutes. 10 minutes at room temperature.
The coated product was left for 50 minutes to test its dryness to the touch.
The sample was heated at ℃ for 48 hours, then left at room temperature for one week, and then subjected to a weather resistance test (Sunshine Weather-Ometer) and a chemical resistance test. The results are shown in Table 1 below. Similarly to Example 1, the coating composition of this example also exhibits a high curing speed and excellent weather resistance and chemical resistance.
実施例３
ジエチルカーボネート７０８部及び１．６−ヘキサンジ
オール８２６部を１２０℃乃至２００℃で１５時間反応
させ、その後１５０℃に冷却し、３０乃至５０ｍｍＨｇ
に減圧して残留するエタノールを充分に留去し、９８２
部のポリカーボネートポリオールを得た。このポリオー
ルの分子量は約９８０であり、ＯＨ価は１１５であった
。Example 3 708 parts of diethyl carbonate and 826 parts of 1,6-hexanediol were reacted at 120°C to 200°C for 15 hours, then cooled to 150°C, and heated at 30 to 50 mmHg.
The remaining ethanol was sufficiently distilled off by reducing the pressure to 982.
A polycarbonate polyol was obtained. This polyol had a molecular weight of about 980 and an OH value of 115.
このポリオール１，９６０部、１．４−ブタンジオール
９０部、トリメチロールプロパン６７部にメチルイソブ
チルケトン９２８部、トルエン９２８部を加え均一に混
合したものに、イソホロンジイソシアネート６６６部を
添加し、１１０乃至１１５℃で５時間反応させポリウレ
タン樹脂の有機溶剤溶液を得た。928 parts of methyl isobutyl ketone and 928 parts of toluene were added to 1,960 parts of this polyol, 90 parts of 1,4-butanediol, and 67 parts of trimethylolpropane, and mixed uniformly. To this, 666 parts of isophorone diisocyanate was added, The reaction was carried out at 115° C. for 5 hours to obtain an organic solvent solution of polyurethane resin.
このポリウレタン樹脂溶液の不揮発分は６０％、粘度は
３，６００ｃｐｓであった。又、このポリウレタン樹脂
のＯＨ価は約３０で、分子量は約５，５５０であった。This polyurethane resin solution had a nonvolatile content of 60% and a viscosity of 3,600 cps. Further, the OH value of this polyurethane resin was about 30, and the molecular weight was about 5,550.
次いで前記のポリウレタン樹脂溶液１００部にルチル型
酸化チタン４５部、酸化防止剤０． １部及び紫外線吸
収剤０．１部を添加して混練し着色されたポリウレタン
樹脂溶液を得た。この着色樹脂溶液１５０部に対してポ
リイシシアネート（ダイブラコートＰＵ−Ｅ−ハードナ
ー、大日精化工業製）１３．６部を添加し、ｚｔｉ型の
本発明の塗料組成物を得た。尚、この塗料０組成物の中
に含まれるポリウレタン樹脂のＯＨ基に対するポリイシ
シアネート中のイソシアネート基の当量比は１．３であ
る。Next, 45 parts of rutile titanium oxide and 0.0 parts of antioxidant were added to 100 parts of the polyurethane resin solution. 1 part and 0.1 part of an ultraviolet absorber were added and kneaded to obtain a colored polyurethane resin solution. To 150 parts of this colored resin solution, 13.6 parts of polyisocyanate (Dybracoat PU-E-hardener, manufactured by Dainichiseika Chemical Industry Co., Ltd.) was added to obtain a zti type coating composition of the present invention. The equivalent ratio of the isocyanate groups in the polyisocyanate to the OH groups in the polyurethane resin contained in this paint composition is 1.3.
この塗料組成物１００部をメチルエチルケトン／酢酸ブ
チル／キシレン＝ｌ／１／１からなるシンナー６０部で
希釈し、塗料粘度が岩田カップＮＫ＃２で２１秒及び不
揮発分４６６７％のスプレー塗装液を得た。100 parts of this coating composition was diluted with 60 parts of thinner consisting of methyl ethyl ketone/butyl acetate/xylene = 1/1/1 to obtain a spray coating liquid with a coating viscosity of Iwata Cup NK #2 of 21 seconds and a non-volatile content of 4667%. Ta.
予めブライマーとしてレザロイドＲＩＭブライマー（大
日精化工業製）を塗装しておいたウレンＲＩＭ成型物の
表面に前記スプレー塗装液を乾燥時膜厚が３０μｍとな
る様に塗装し、室温で１５分セツティング後７０℃２０
分加熱硬化させた。The spray coating liquid was applied to the surface of the urethane RIM molded product, which had been previously coated with Retheroid RIM Brimer (manufactured by Dainichiseika Chemical Industry Co., Ltd.), so that the dry film thickness was 30 μm, and the coating was allowed to set for 15 minutes at room temperature. After 70℃20
Cured by heating for 1 minute.
この塗装物を室温に１０分放置し指触乾燥性を試験し、
更にこの塗装物を５０℃で４８時間加熱し、その後室温
で１週間放置後、耐候性試験（サンシャインウエザオメ
ーター）及び耐薬品性試験に供した。その結果を後記第
１表に示す。本実施例の塗料組成物も実施例１及び２と
同様に硬化速度が大である。同時に優れた耐候性及び耐
薬品性を示す。This painted product was left at room temperature for 10 minutes and tested for dryness to the touch.
Further, this coated product was heated at 50° C. for 48 hours, then left at room temperature for one week, and then subjected to a weather resistance test (Sunshine Weatherometer) and a chemical resistance test. The results are shown in Table 1 below. Similarly to Examples 1 and 2, the coating composition of this example also has a high curing speed. At the same time, it exhibits excellent weather resistance and chemical resistance.
実施例４
ジエチルカーボネート１，１８０部及び１．６ヘキサン
ジオール１，２９８部を１２０℃乃至２００℃で１５時
間反応させ、その後１５０℃に冷却し、３０乃至５０ｍ
ｍＨｇに減圧して残留するエタノールを充分に留去し、
１，５５８部のポリカーボネートポリオールを得た。こ
のポリオールの分子量は約１．５６０であり、ＯＨ価は
１０８であった。Example 4 1,180 parts of diethyl carbonate and 1,298 parts of 1.6 hexanediol were reacted at 120°C to 200°C for 15 hours, then cooled to 150°C, and 30 to 50 m
The remaining ethanol was sufficiently distilled off by reducing the pressure to mHg.
1,558 parts of polycarbonate polyol were obtained. This polyol had a molecular weight of about 1.560 and an OH value of 108.
このポリオール１，５６０部、１．４−ブタフジオール
４５部及びトリメチロールプロパン６７部にメチルイソ
ブチルケトン６６．８部及びトルエン６６８部を加え均
一に混合したものに、イソホロンジイソシアネート３３
３部を添加し１１０乃至１１５℃で５時間反応させポリ
ウレタン樹脂のイＦ機溶剤溶液を得た。66.8 parts of methyl isobutyl ketone and 668 parts of toluene were added to 1,560 parts of this polyol, 45 parts of 1,4-butafdiol, and 67 parts of trimethylolpropane, and mixed uniformly, and 33 parts of isophorone diisocyanate was added.
3 parts were added and reacted at 110 to 115° C. for 5 hours to obtain a solution of polyurethane resin in organic solvent.
このポリウレタン樹脂溶液の不揮発分は６０％で粘度は
２，６００ｃｐｓであった。又、このポリウレタン樹脂
のＯＨ価は約４２−で、分子量は約４．０００であった
。The nonvolatile content of this polyurethane resin solution was 60% and the viscosity was 2,600 cps. Further, the OH number of this polyurethane resin was about 42-, and the molecular weight was about 4.000.
次いで＋ｉｆｆ記のポリウレタン樹脂溶液１００部にル
チル型酸化チタン４５部、酸化防止剤０．１部及び紫外
線吸収剤０．１部を添加して混練し着色されたポリウレ
タン樹脂溶液を得た。この着色樹脂溶液１５０部に対し
てポリイシシアネート（ダイブラコートＰＵ−Ｅ−ハー
ドナー、大口精化工業製）１７．６部を添加し、２液型
の本発明の塗料組成物を得た。尚、この塗料組成物の中
に含まれるポリウレタン樹脂のＯＨ基に対するポリイシ
シアネート中のイソシアネート基の当量比は１．２であ
る。Next, 45 parts of rutile titanium oxide, 0.1 part of an antioxidant, and 0.1 part of an ultraviolet absorber were added to 100 parts of the polyurethane resin solution described above and kneaded to obtain a colored polyurethane resin solution. To 150 parts of this colored resin solution, 17.6 parts of polyisocyanate (Dybracoat PU-E-hardener, manufactured by Oguchi Seika Kogyo Co., Ltd.) was added to obtain a two-component coating composition of the present invention. The equivalent ratio of the isocyanate groups in the polyisocyanate to the OH groups in the polyurethane resin contained in this coating composition is 1.2.
この塗料組成物１００部をメチルシソブチルケトン／酢
酸ブチル／キシレン＝１／１／１からなるシンナー６０
部で希釈し、塗料粘度が岩［ＨカップＮＫ＃２で１９秒
及び不揮発分４７．１％のスプレー塗装液を得た。100 parts of this coating composition was mixed with 60 parts of a thinner consisting of methyl shisobutyl ketone/butyl acetate/xylene = 1/1/1.
A spray coating liquid with a paint viscosity of 19 seconds (H cup NK #2) and a non-volatile content of 47.1% was obtained.
予めブライマーとしてレザロイドＲＩＭブライマー（大
口錆化工業製）を塗装しておいたウレンＲＩＭ成型物の
表面に前記スプレー塗装液を乾燥時膜厚が３０μｍにな
る様に塗装し、室温で１５分セツティング後７０℃２０
分加熱硬化させた。The above spray coating solution was applied to the surface of the urene RIM molded product, which had been previously coated with Retheroid RIM Brimer (manufactured by Oguchi Sakka Kogyo), so that the dry film thickness was 30 μm, and the coating was allowed to set at room temperature for 15 minutes. After 70℃20
Cured by heating for 1 minute.
この塗装物を室温に１０分放置し指触乾燥性を試験し、
更にこの塗装物を５０℃で４８時間加熱し、その後室温
で１週間放置後、耐候性試験（サンシャインウエザオメ
ーター）及び耐薬品性試験に供した。その結果を後記第
１表に示す。本実施例の塗料組成物も実施例１．２及び
３と同様に硬化速度が大である。This painted product was left at room temperature for 10 minutes and tested for dryness to the touch.
Further, this coated product was heated at 50° C. for 48 hours, then left at room temperature for one week, and then subjected to a weather resistance test (Sunshine Weatherometer) and a chemical resistance test. The results are shown in Table 1 below. The coating composition of this example also had a high curing speed, similar to Examples 1.2 and 3.
同時にａｈた耐候性及び耐薬品性を示す。At the same time, it exhibits excellent weather resistance and chemical resistance.
比較例１
アジピン酸及びフタル酸と多価アルコールとからなるポ
リエステルポリオール（バイエル製、Ｄｅｓｍｏｐｈｅ
ｎ６７０） １００部にルチル型酸化チタン７５部、メ
チルイソブチルケトン３３．３部及びトルエン３３．３
部、酸化防止剤０．２部及び紫外線吸収剤０．２部を添
加して混練し着色されたポリウレタン樹脂溶液を得た。Comparative Example 1 Polyester polyol consisting of adipic acid and phthalic acid and polyhydric alcohol (manufactured by Bayer, Desmophe
n670) 100 parts, 75 parts of rutile titanium oxide, 33.3 parts of methyl isobutyl ketone, and 33.3 parts of toluene.
0.2 parts of an antioxidant and 0.2 parts of an ultraviolet absorber were added and kneaded to obtain a colored polyurethane resin solution.
この着色樹脂溶液１５０部に対してポリイシシアネート
（ダイブラコートＰＵ−Ｅ−ハードナー、大口精化工業
製）３６．８部を添加し、２液型の比較例の塗料組成物
を得た。尚、この塗料組成物の中に含まわるポリウレタ
ン樹脂のＯＨ基に対するポリイシシアネート中のイソシ
アネート基の当量比は１．２である。この塗料組成物１
００部をメチルイソブチルケトン／酢酸ブチル／キシレ
ン＝１／１／１（重量比）からなるシンナー４５部で希
釈し、塗料粘度が岩田カップＮに＃２で２０秒及び不揮
発分６０．１％のスプレー塗装液を得た。To 150 parts of this colored resin solution, 36.8 parts of polyisocyanate (Dybracoat PU-E-hardener, manufactured by Oguchi Seika Kogyo) was added to obtain a two-component coating composition of a comparative example. The equivalent ratio of the isocyanate groups in the polyisocyanate to the OH groups in the polyurethane resin contained in this coating composition is 1.2. This paint composition 1
00 parts was diluted with 45 parts of thinner consisting of methyl isobutyl ketone/butyl acetate/xylene = 1/1/1 (weight ratio), and the paint viscosity was adjusted to Iwata Cup N for 20 seconds and non-volatile content of 60.1%. A spray coating solution was obtained.
予めブライマーとしてレザロイドＲＩＭプライマー（大
日錆化工業製）を塗装しておいたウレタンＲＩＭ成型物
の表面に前記スプレー塗装液を乾燥時膜厚が３０μｍに
なる様に塗装し、室温て１５分間セツティング後７０℃
で２０分間加熱硬化させた。この塗装物を室温で１０分
間放置し指触乾燥性を試験し、更にこの塗装物を５０℃
で４８時間加熱し、その後室温で１週間放置後、耐候性
試験（サンシャインウエザオメーター）及び耐薬品性試
験に供した。その結果を後記第１表に示す。The above spray coating solution was applied to the surface of the urethane RIM molded product, which had been previously coated with Retheroid RIM Primer (manufactured by Dainichi Sakai Kakogyo Co., Ltd.) as a brimer, so that the dry film thickness was 30 μm, and allowed to set at room temperature for 15 minutes. 70℃ after heating
It was heated and cured for 20 minutes. The coated product was left at room temperature for 10 minutes to test its dryness to the touch, and then the coated product was heated to 50°C.
The sample was heated for 48 hours, then left at room temperature for one week, and then subjected to a weather resistance test (Sunshine Weather-Ometer) and a chemical resistance test. The results are shown in Table 1 below.
比較例２
アジピン酸及びフタル酸と多価アルコールとからなるポ
リエステルポリオール（バイエル製、ＤｅｓＩｌｏｐｈ
ｅｎ６７０） １．００部、このポリエステルポリオー
ルと相溶性の良いアクリルポリオール（バイエル製、Ｄ
ｅｓｍｏｐｈｅｎ 八３６５） 、ルチル型酸化チタン
８９．６部、メチルイソブチルケトン３３．３部及びト
ルエン３３．３部、酸化防止剤０．２部及び紫外線吸収
剤０．２部を添加して混練し着色されたポリウレタン樹
脂溶液を得た。この着色樹脂溶液１５０部に対してポリ
イシシアネート（ダイブラコートＰＵ−Ｅ−ハードナー
、大口精化工業製）３０．８部を添加し、２液型の比較
例の塗料組成物を得た。尚、この塗料組成物の中に含ま
れるポリウレタン樹脂のＯＨ基に対するポリイシシアネ
ート中のイソシアネート基の当量比は１．０である。こ
の塗料組成物１００部をメチルイソブチルケトン／酢酸
ブチル／キシレン＝１／１／１（重量比）からなるシン
ナー５０部で希釈し、塗料粘度が岩１１カップＮＫ＃２
で２０秒及び不揮発分５７．５％のスプレー塗装液を得
た。Comparative Example 2 Polyester polyol consisting of adipic acid and phthalic acid and polyhydric alcohol (manufactured by Bayer, DesIloph
en670) 1.00 parts, acrylic polyol (manufactured by Bayer, D
esmophen 8365), 89.6 parts of rutile titanium oxide, 33.3 parts of methyl isobutyl ketone, 33.3 parts of toluene, 0.2 parts of an antioxidant, and 0.2 parts of an ultraviolet absorber, and then kneaded and colored. A polyurethane resin solution was obtained. To 150 parts of this colored resin solution, 30.8 parts of polyisocyanate (Dybracoat PU-E-hardener, manufactured by Oguchi Seika Kogyo Co., Ltd.) was added to obtain a two-component coating composition of a comparative example. The equivalent ratio of the isocyanate groups in the polyisocyanate to the OH groups in the polyurethane resin contained in this coating composition is 1.0. 100 parts of this paint composition was diluted with 50 parts of thinner consisting of methyl isobutyl ketone/butyl acetate/xylene = 1/1/1 (weight ratio), and the paint viscosity was 11 cups NK#2.
A spray coating liquid with a non-volatile content of 57.5% was obtained.
予めブライマーとしてレザロイドＲＩＭブライマー（大
口精化工業製）を塗装しておいたウレタンＲＩＭ成型物
の表面に前記スプレー塗装液を乾燥時膜がか３０μｍに
なる様に塗装し、室温で１５分間セツティング後７０℃
で２０分間加熱硬化させた。この塗装物を室温で１０分
間放置し指触乾燥性を試験し、更にこの塗装物を５０℃
で４８時間加熱し、その後室温で１週間放置後、耐候性
試験（サンシャインウエザオメーター）及び耐薬品性試
験に供した。その結果を後記第１表に示す。比較例１及
び２共に硬化速度が低く、耐候性も不十分であった。The above spray coating solution was applied to the surface of the urethane RIM molded product, which had been coated with Retheroid RIM Brimer (manufactured by Oguchi Seika Kogyo Co., Ltd.) so that the film had a thickness of 30 μm when dry, and was allowed to set for 15 minutes at room temperature. After 70℃
It was heated and cured for 20 minutes. The coated product was left at room temperature for 10 minutes to test its dryness to the touch, and then the coated product was heated to 50°C.
The sample was heated for 48 hours, then left at room temperature for one week, and then subjected to a weather resistance test (Sunshine Weather-Ometer) and a chemical resistance test. The results are shown in Table 1 below. Both Comparative Examples 1 and 2 had low curing speeds and insufficient weather resistance.
更に
シ１１−ｊ〈
エ ◎ ◎ ◎ ◎ Δ
△Ｈ８３１ｉｆｔ ８９ ８９ ７２
７８ＩＩＩ ２．６ ２．４ ２．３
２．３ ３．２ ２．９■ ◎ ◎
◎ ◎ ○ ＯＶ ◎ ◎ ◎
◎ ◎ ◎■ ◎ ◎ ◎
◎ ◎ ◎■ ＯＯＯ○ ○ ○
Ｉ；指触乾燥性（７０℃２０分間加熱硬化後）Ｔ二；サ
ンシャインウェザオシ−ター２．０００時間照射後の光
沢保持率
■；サンシャインウエザオメーター２，０００時間照射
後の色差（△Ｅ）
■；耐アルカリ性試験（４％ＮａＯＨに２４時間浸漬）
■：耐酸性試験（３％塩酸に２４時間浸漬）■：耐ガソ
リン性（ガーゼ５０回ラビング）■；耐メチルエチルケ
トン性（ガーゼ５０回ラビング）
＊指触乾燥性は、試験後の外観を目視で観察し下記の基
準で評価した。Furthermore, 11-j〈 ◎ ◎ ◎ ◎ Δ
△H831ift 89 89 72
78III 2.6 2.4 2.3
2.3 3.2 2.9■ ◎ ◎
◎ ◎ ○ OV ◎ ◎ ◎
◎ ◎ ◎■ ◎ ◎ ◎
◎ ◎ ◎■ OOO○ ○ ○ I; Dryness to the touch (after heat curing at 70°C for 20 minutes) T2; Sunshine Weather Otter 2. Gloss retention after 2,000 hours of irradiation ■; Sunshine Weather Omter 2,000 Color difference after time irradiation (△E) ■: Alkali resistance test (immersed in 4% NaOH for 24 hours) ■: Acid resistance test (immersed in 3% hydrochloric acid for 24 hours) ■: Gasoline resistance (rubbing with gauze 50 times) ■; Methyl ethyl ketone resistance (rubbing with gauze 50 times) *Dryness to the touch was evaluated using the following criteria by visually observing the appearance after the test.
◎；異常なし ○：Ｖｉ僅かに指の跡が認められる。◎;No abnormality ○: Vi Slight finger marks are observed.
△：指の跡が認められる。△: Finger marks are observed.
＊耐アルカリ性及び耐酸性は、試験後の外観を目視で観
察し下記の基準で評価した。*Alkali resistance and acid resistance were evaluated based on the following criteria by visually observing the appearance after the test.
◎；異常なし ０：極僅かに光沢の変化が認められる。◎;No abnormality 0: Very slight change in gloss is observed.
Δ：光沢の低下が認められる。Δ: Decrease in gloss is observed.
＊耐ガソリン性及び耐メチルエチルケトン性は試験後の
塗膜及びガーゼの外観を目視で観察し下記の基準で評価
した。*Gasoline resistance and methyl ethyl ketone resistance were evaluated based on the following criteria by visually observing the appearance of the coating film and gauze after the test.
◎；異常なし ０：極僅かに光沢の変化が認められる。◎;No abnormality 0: Very slight change in gloss is observed.
△；光沢の低下が認められると同時に僅かにガーゼに塗
料が付着する。Δ: A decrease in gloss was observed, and at the same time, the paint slightly adhered to the gauze.
Ｘ；著しい光沢の低下が認められると同時にガーゼに多
量の塗料が付着する。X: Significant reduction in gloss was observed, and at the same time, a large amount of paint adhered to the gauze.
（効 果）
以上の如き本発明によれば、被膜形成成分の主成分とし
て、ポリカーボネートポリオール又はポリカーボネート
エステルポリオールと、２価アルコール及び３価アルコ
ールの混合物と、ジイソシアネートとを重合反応させて
得られるＯＨＨ２Ｏ２至６０の末端氷酸基を有する分子
［２，０００乃至７，０００のポリウレタン樹脂を便用
することによって、可撓性、弾性及び耐久性を有する被
膜を与えると同時に塗膜形成速度が大であるプラスチッ
ク成型物用の塗料組成物が提供される。(Effects) According to the present invention as described above, OHH2O2 obtained by polymerizing polycarbonate polyol or polycarbonate ester polyol, a mixture of dihydric alcohol and trihydric alcohol, and diisocyanate as the main components of the film forming component. The use of polyurethane resins having molecules with terminal glacial groups of up to 60 [2,000 to 7,000] provides coatings with flexibility, elasticity, and durability, while at the same time increasing the rate of film formation. A coating composition for certain plastic molded articles is provided.
Claims (2)
トエステルポリオールと、２価アルコール及び３価アル
コールの混合物と、ジイソシアネートとを重合反応させ
て得られるＯＨ価２０乃至６０の末端氷酸基を有する分
子量２，０００乃至７，０００のポリウレタン樹脂の有
機溶剤溶液と、上記有機溶剤溶液中に含まれるポリウレ
タン樹脂の水酸基に対してイソシアネート基が０．８乃
至２．０当量となる割合でポリイシシアネートとを混合
してなるプラスチック成型物用塗料組成物。(1) Polycarbonate polyol or polycarbonate ester polyol, a mixture of dihydric alcohol and trihydric alcohol, and diisocyanate are polymerized and have an OH number of 20 to 60 and a molecular weight of 2,000 to 7, having a terminal glacial acid group, 000 polyurethane resin in an organic solvent and polyisocyanate at a ratio of 0.8 to 2.0 equivalents of isocyanate groups to the hydroxyl groups of the polyurethane resin contained in the organic solvent solution. Coating composition for molded objects.
させた請求項１に記載の塗料組成物。(2) The coating composition according to claim 1, wherein a pigment is dispersed in an organic solvent solution of a polyurethane resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63162575A JPH0749557B2 (en) | 1988-07-01 | 1988-07-01 | Paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63162575A JPH0749557B2 (en) | 1988-07-01 | 1988-07-01 | Paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0214272A true JPH0214272A (en) | 1990-01-18 |
| JPH0749557B2 JPH0749557B2 (en) | 1995-05-31 |
Family
ID=15757195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63162575A Expired - Lifetime JPH0749557B2 (en) | 1988-07-01 | 1988-07-01 | Paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749557B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214273A (en) * | 1988-07-01 | 1990-01-18 | Dainichiseika Color & Chem Mfg Co Ltd | Coating composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147721A (en) * | 1984-08-15 | 1986-03-08 | Toyobo Co Ltd | Preparation of polyurethane resin |
| JPH024736A (en) * | 1988-06-22 | 1990-01-09 | Hitachi Maxell Ltd | Polycarbonate polyol, aromatic polycarbonate polyurethane resin, coating material, cast film and magnetic recording medium |
| JPH0214273A (en) * | 1988-07-01 | 1990-01-18 | Dainichiseika Color & Chem Mfg Co Ltd | Coating composition |
-
1988
- 1988-07-01 JP JP63162575A patent/JPH0749557B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147721A (en) * | 1984-08-15 | 1986-03-08 | Toyobo Co Ltd | Preparation of polyurethane resin |
| JPH024736A (en) * | 1988-06-22 | 1990-01-09 | Hitachi Maxell Ltd | Polycarbonate polyol, aromatic polycarbonate polyurethane resin, coating material, cast film and magnetic recording medium |
| JPH0214273A (en) * | 1988-07-01 | 1990-01-18 | Dainichiseika Color & Chem Mfg Co Ltd | Coating composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0214273A (en) * | 1988-07-01 | 1990-01-18 | Dainichiseika Color & Chem Mfg Co Ltd | Coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0749557B2 (en) | 1995-05-31 |
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