JPH03100084A - Coating resin composition and coating method - Google Patents
Coating resin composition and coating methodInfo
- Publication number
- JPH03100084A JPH03100084A JP23556189A JP23556189A JPH03100084A JP H03100084 A JPH03100084 A JP H03100084A JP 23556189 A JP23556189 A JP 23556189A JP 23556189 A JP23556189 A JP 23556189A JP H03100084 A JPH03100084 A JP H03100084A
- Authority
- JP
- Japan
- Prior art keywords
- tertiary amine
- paint
- vapor
- resin composition
- parts
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 239000011248 coating agent Substances 0.000 title abstract description 6
- 239000003973 paint Substances 0.000 claims abstract description 28
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 23
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 thiol compound Chemical class 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 11
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007921 spray Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- 239000003595 mist Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 abstract description 2
- 229960002887 deanol Drugs 0.000 abstract description 2
- 239000012972 dimethylethanolamine Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 239000011527 polyurethane coating Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 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 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- QGBXUUSJOCLJNY-UHFFFAOYSA-N CC(=C)C1=CC=CC=C1.C1(=CC=CC=C1)CC=C Chemical compound CC(=C)C1=CC=CC=C1.C1(=CC=CC=C1)CC=C QGBXUUSJOCLJNY-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
- 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、速硬化性を有するポリウレタン系塗料用樹脂
組成物、及びその塗装方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition for polyurethane coatings having fast curing properties and a coating method thereof.
ポリウレタン塗料は、皮膜性能特に耐薬品性、弾性、強
靭性等に優れ塗料分野で汎用されているが、−８的には
ヒドロキシル基とイソシアネート基の反応が利用されて
いる。Polyurethane paints are widely used in the paint field due to their excellent film performance, particularly chemical resistance, elasticity, and toughness, and -8 uses the reaction between hydroxyl groups and isocyanate groups.
塗装後、短時間の内に被塗装物を取り扱う場合、かかる
反応系では、反応速度を上げるために多量の触媒が必要
であった。When the object to be coated is handled within a short period of time after coating, such a reaction system requires a large amount of catalyst to increase the reaction rate.
また、多量の触媒が存在するため、耐水性等の諸物性が
低下したり、塗料の可使時間が極端に短くなるという欠
点を有していた。Furthermore, since a large amount of catalyst is present, various physical properties such as water resistance are deteriorated, and the pot life of the paint is extremely shortened.
本発明者らは、可使時間が長く、かつ、速硬化であると
いう、相反する問題点を解決すべく、鋭意検討した結果
、アクリルポリオール、ジイソシアネート、及びメルカ
プトエタノールより誘導されるチオール基を含有する化
合物と、ウレタンポリマーからなる樹脂組成物は、可使
時間が長く、かつ、三級アミンの存在により直ちに硬化
する事を見出し、本発明を完成した。In order to solve the conflicting problems of long pot life and fast curing, the present inventors have made extensive studies and found that thiol groups derived from acrylic polyols, diisocyanates, and mercaptoethanol. The present invention was completed based on the discovery that a resin composition consisting of a urethane polymer and a urethane polymer has a long pot life and is immediately cured due to the presence of a tertiary amine.
［課題を解決するための手段］
本発明は、チオール基を含有する化合物（Ａ）とウレタ
ンプレポリマー（Ｂ）とを含有し、該チオール基を含有
する化合物（Ａ）は、アクリルポリオール、ジイソシア
ネート、及びメルカプトエタノールより誘導され、かつ
（Ａ）と（Ｂ）との配合割合が、活性水素及びイソシア
ネートの当量比で０．５ ： １．０〜１．Ｏｊ Ｏ，
５の範囲にある塗料用樹脂組成物である事を特徴とする
塗料用樹脂組成物である。[Means for Solving the Problems] The present invention contains a compound (A) containing a thiol group and a urethane prepolymer (B), and the compound (A) containing a thiol group is an acrylic polyol, a diisocyanate, etc. , and mercaptoethanol, and the blending ratio of (A) and (B) is 0.5:1.0-1.0 in equivalent ratio of active hydrogen and isocyanate. Oj O,
This is a resin composition for a paint, which is characterized in that it is a resin composition for a paint that falls within the range of 5.
更に、上記樹脂組成物よりなる塗料を塗装するに際して
、三級アミン蒸気、あるいは微粒化された三級アミンを
、噴霧エアー中に含有させ、塗料と混合させるか、塗装
後三級アミン蒸気と接触させる事を特徴とする塗装方法
に、関する。Furthermore, when applying a paint made of the above resin composition, tertiary amine vapor or atomized tertiary amine may be contained in the spray air and mixed with the paint, or brought into contact with the tertiary amine vapor after painting. It relates to a painting method characterized by
次に、本発明の構成要件の個々に関し詳細に説明する。Next, each component of the present invention will be explained in detail.
本発明に使用されるチオール基を含有する化合物（Ａ）
としては、アクリルポリオール、ジイソシアネート、及
びメルカプトエタノールより合成される化合物が適当で
ある。Compound (A) containing a thiol group used in the present invention
Suitable examples include compounds synthesized from acrylic polyols, diisocyanates, and mercaptoethanol.
メルカプトエタノール以外に、チオグリコール酸誘導体
、チオコールに代表されるチオール基を有する化合物は
、独特のメルカプタン臭が強く、かつ、ウレタンプレポ
リマーとの配合後の可使時間が２時間以内であり、塗料
用として使用する事が困難であった。In addition to mercaptoethanol, compounds with thiol groups, such as thioglycolic acid derivatives and thiol, have a strong unique mercaptan odor and have a pot life of less than 2 hours after blending with urethane prepolymers, making them difficult to use in paints. It was difficult to use it for personal purposes.
アクリルポリオール樹脂、ジイソシアネ−１・、及びメ
ルカプトエタノールより誘導されるチオール基を含有す
る化合物は、メルカプタン臭が殆どなく又、可使時間も
４時間以上であり、塗料用として好適である。A compound containing a thiol group derived from an acrylic polyol resin, diisocyanate-1, and mercaptoethanol has almost no mercaptan odor and has a pot life of 4 hours or more, making it suitable for use in paints.
アクリルポリオール樹脂、ジイソシアネーＩ・及びメル
カプトエタノールより誘導されるチオール基を含有する
化合物（Ａ）は、ヒドロキシル基に対し、過剰なイソシ
アネート基の存在下で、ジイソシアネートによるウレタ
ン化反応後、残存するイソシアネーＩ・とメルカプトエ
タノールのウレタン化反応する事によって得られる。The compound (A) containing a thiol group derived from an acrylic polyol resin, diisocyanate I, and mercaptoethanol is produced by urethanizing the remaining isocyanate I with diisocyanate in the presence of an excess of isocyanate groups relative to the hydroxyl group. Obtained by the urethanization reaction of mercaptoethanol with ・.
本発明に使用されるアクリルポリオールの種類としては
、例えば、ヒドロキシエチル（メタ）アクリレート、ヒ
ドロキシロビル（メタ）アクリレート、１．４−ブタン
ジオールモノ （メタ）アクリレート、ポリカプロラク
トン（メタ）アクリレート等のヒドロキシル基を有する
単量体とヒドロキシル基を有さない単量体を、有機溶媒
中で重合触媒を併用することにより、容易に得られる。Examples of the acrylic polyol used in the present invention include hydroxyethyl (meth)acrylate, hydroxylobil (meth)acrylate, 1,4-butanediol mono (meth)acrylate, and polycaprolactone (meth)acrylate. It can be easily obtained by using a monomer having a hydroxyl group and a monomer not having a hydroxyl group together with a polymerization catalyst in an organic solvent.
ヒドロキシル基を有さない単量体として、例えば、メチ
ル（メタ）アクリレート、エチル（メタ）アクリレート
、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）
アクリレート、イソブチル（メタ）アクリレート、ｔｅ
ｒｔ−ブチル（メタ）アクリレート、２−エチルヘキシ
ル（メタ）アクリレート、トリデシル（メタ）アクリレ
ート、シクロヘキシル（メタ）アクリレート、ベンジル
（メタ）アクリレート、フェニル（メタ）アクリレート
等ノアクリル酸及びメタアクリル酸のエステル類を用い
ることができる。Examples of monomers without hydroxyl groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate,
acrylate, isobutyl (meth)acrylate, te
Esters of noacrylic acid and methacrylic acid such as rt-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, etc. can be used.
なお、例えば、メチル（メタ）アクリレートはメチルメ
タアクリレート、及びメチルアクリレートを示す。Note that, for example, methyl (meth)acrylate refers to methyl methacrylate and methyl acrylate.
その他の共重合可能な単量体としては、α−メチルスチ
レンビニルトルエン、アクリルニトリル、メタアクリル
ニトリル、酢酸ビニル、プロピオン酸ビニル（アクリル
アミド、メタクリルアミド、メチロールアクリルアミド
、メチロールメタアクリルアミド）、塩化ビニル、プロ
ピレン、エチレン、炭素数４〜２０のα−オレフィン等
が挙げられる。Other copolymerizable monomers include α-methylstyrene vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate (acrylamide, methacrylamide, methylol acrylamide, methylol methacrylamide), vinyl chloride, propylene , ethylene, and α-olefin having 4 to 20 carbon atoms.
また、重合触媒（開始剤）として代表的なものは、アゾ
ビスイソブチルニトリル等のじあぞ化合物、ベンゾイル
パーオキサイド、ターシャリ・ブチルヒバレート、ター
シャリ・ブチルパーベンゾエート、ターシャリ・ブチル
パーカブ１／−ト等の過酸化物等が挙げられる。Typical polymerization catalysts (initiators) include diazo compounds such as azobisisobutylnitrile, benzoyl peroxide, tertiary butyl hibernate, tertiary butyl perbenzoate, tertiary butyl perbenzoate, etc. peroxides, etc.
アクリルポリオール樹脂とウレタン化反応を廿しめられ
るジイソシアネートの種類として、例えば、トリレンジ
イソシアネート、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、キシレンジイソシアネート
、 ジフェニルメタン４．４゛ −ジイソシアネート
等のジイソシアネートより誘導されるイソシアヌレート
体、前記の各種ポリオールで変性したグリコールアタリ
ト体、水アダクト体等が挙げられる。Types of diisocyanates that can undergo a urethanization reaction with an acrylic polyol resin include isocyanurates derived from diisocyanates such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and diphenylmethane 4.4'-diisocyanate; Examples thereof include glycol atalites and water adducts modified with the various polyols mentioned above.
ウレタンプレポリマー（Ｂ）としては、上記同様、例え
ば、トリレンジイソシアネート、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、キシレンジ
イソシアネート、ジフェニルメタン４．４′−ジイソシ
アネート等のジイソシアネートより誘導されるイソシア
ヌレート体、前記の各種ポリオールで変性したグリコー
ルアタリト体、水アダクト体などが例として挙げられる
。As the urethane prepolymer (B), as mentioned above, for example, isocyanurates derived from diisocyanates such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, diphenylmethane 4,4'-diisocyanate, and the various polyols mentioned above. Examples include glycol atalate modified with and water adduct.
又、これ等の誘導体は任意に混合して使用しても差し支
えない。Further, these derivatives may be used in any desired mixture.
上記塗料用樹脂組成物を塗料化するに際し、希釈溶剤、
炭酸カルシウム、酸化チタンに代表される顔料、各種カ
ップリング剤、レベリング剤の添加剤も当然ながら使用
して構わない。When making the above paint resin composition into a paint, a diluting solvent,
Of course, additives such as pigments such as calcium carbonate and titanium oxide, various coupling agents, and leveling agents may also be used.
又、チオール基を含有する化合物（Ａ）とアクリルポリ
オール樹脂、エポキシポリオール樹脂、ポリエステルポ
リオール樹脂等のポリオール樹脂或いは、グリコール類
の併用もできる。Further, the thiol group-containing compound (A) and polyol resins such as acrylic polyol resins, epoxy polyol resins, and polyester polyol resins, or glycols can also be used together.
ここで、活性水素を有するチオール基含有化合物（Ａ）
と、イソシアネート基を有するウレタンプレポリマー（
Ｂ）との配合割合は、当量比で、０．５ Ｆ １〜ｔ
：Ｏ，Ｓの範囲が適当である。Here, the thiol group-containing compound (A) having active hydrogen
and urethane prepolymer having isocyanate groups (
The blending ratio with B) is equivalent ratio, 0.5 F 1~t
:O, S range is appropriate.
（Ａ）に対する（Ｂ）の当量比が、０．５ ：１．ｏ
より高いと皮膜が固くなり折り曲げ性が低下する。The equivalent ratio of (B) to (A) is 0.5:1. o
If it is higher, the film becomes hard and bendability decreases.
一方（Ａ）に対する（Ｂ）の当量比が、１．０二０．５
より低いと密看性及び耐水性が低下する。On the other hand, the equivalent ratio of (B) to (A) is 1.020.5
If it is lower, the sealability and water resistance will decrease.
かかる塗料用樹脂組成物よりなる塗料は、可使時間が４
時間以上であるが、三級アミンがｘｓｐｐｍ存在するだ
けで、ウレタンプレポリマーの種類を問わず、３〜５分
で硬化してしまうため、特殊な塗装方法が必要になる。A paint made from such a paint resin composition has a pot life of 4.
However, the presence of xppm of tertiary amine will cure the urethane prepolymer in 3 to 5 minutes, regardless of the type of urethane prepolymer, so a special coating method is required.
一般的に、三級アミン蒸気を、噴霧エアー中に含有させ
る、ベーパーインジェクションキュアー（ＶＩＣ）方式
、三級アミンミストを、噴霧エアー中に含有させるミス
トインジェクションキュア（ＭＩＣ）方式、三級アミン
蒸気を満たしたチャンバー内に被塗物を通過させ、三級
アミン蒸気と接触させるペーボキュア一方式と呼称され
る塗装方法により、始めて本塗料は使用可能である。In general, there is a vapor injection cure (VIC) method in which tertiary amine vapor is contained in the atomizing air, a mist injection cure (MIC) method in which tertiary amine mist is contained in the atomizing air, and a tertiary amine vapor is contained in the atomizing air. This paint can be used for the first time by a coating method called pavocure, in which the object to be coated is passed through a filled chamber and brought into contact with tertiary amine vapor.
又、あらかじめ本塗料を塗装した後に、ＶＩＣ方式、Ｍ
ＩＣ方式で発生させた三級アミンを含むエアーを、塗装
物に吹き付ける事によって、あるいはアミン蒸気を硬化
炉内に存在させる（ベーポキュア一方式）によって、塗
膜を硬化させる事ができる。In addition, after applying this paint in advance, VIC method, M
The coating film can be cured by spraying air containing a tertiary amine generated by an IC method onto the coated object, or by allowing amine vapor to exist in a curing furnace (vapor cure one-sided method).
（実施例）
以下、本発明を、更に具体的に説明するため、実施例及
び比較例をあげて説明するが、本発明はこれらの実施例
に限定されるものではない。(Examples) Hereinafter, in order to explain the present invention more specifically, Examples and Comparative Examples will be given and explained, but the present invention is not limited to these Examples.
参考例１
− 「−８Ｈ八 の ゛１
攪拌機、温度計、還流冷却機、滴下槽などを備えたアク
リル樹脂製造装置に、トルエン及び酢酸ブチルを１４０
．３部を仕込み加熱撹拌し、リフラックスにおいて下記
の単量体混合物を５時間かけて滴下した。Reference Example 1 - 140% of toluene and butyl acetate was added to an acrylic resin manufacturing equipment equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, etc.
．． 3 parts were charged, heated and stirred, and the following monomer mixture was added dropwise over 5 hours during reflux.
メチルメタクリレート ２０部ｎ−ブ
チルメタクリレート６０部
β−ヒドロギシエチルメタクリレー） ２０部ター
シャリブチルパーオキサイド １．５部得られた
アクリルポリオールの不揮発分４２％、ＯＨ価３５．７
の樹脂が得られた。Methyl methacrylate 20 parts n-butyl methacrylate 60 parts β-hydroxyethyl methacrylate (20 parts) tert-butyl peroxide 1.5 parts Non-volatile content of the obtained acrylic polyol 42%, OH value 35.7
of resin was obtained.
上記の反応で得られたアクリルポリオール樹脂とジイソ
シアネート（ＴＤ １８０／ｂ学品を使用） ２６．
８部と、８０°Ｃでウレタン化反応を行う。Acrylic polyol resin and diisocyanate obtained by the above reaction (TD 180/b chemical product was used) 26.
8 parts and perform the urethanization reaction at 80°C.
上記ウレタン化反応で出来たプレポリマーと、該プレポ
リマー中に残存する一ＮＧＯ基の当量比で１＝１の一〇
Ｈ基に相当する、メルカプトエタノール（東洋化成工業
■製） １２．３部とを、反応温度８０°Ｃでウレタン
化反応を行う。12.3 parts of mercaptoethanol (manufactured by Toyo Kasei Kogyo ■), which corresponds to the prepolymer produced by the above urethanization reaction and the 10H group in an equivalent ratio of 1=1 NGO group remaining in the prepolymer. A urethane reaction is carried out at a reaction temperature of 80°C.
得られた樹脂溶液は、不揮発分が５０％、ＳＨ価が３１
．５ Ｗｏｆｆ／ｍｇであった。The resulting resin solution had a nonvolatile content of 50% and an SH number of 31.
．． It was 5 Woff/mg.
実施例１
上記の如くして得られたチオール基含有化合物（Ａ−１
）とする。又オレスターＰ−７５（三井東圧化学■製ト
リレンジイソシアネートのトリメチロールプロパンアダ
クト体、不揮発分７８％、イソシアネート基含有率１３
．５％）を、ウレタンプレポリマー（Ｂ−１）とし、下
記配合で塗料を作成した。Example 1 Thiol group-containing compound (A-1
). Orester P-75 (trimethylolpropane adduct of tolylene diisocyanate manufactured by Mitsui Toatsu Chemical Co., Ltd., non-volatile content 78%, isocyanate group content 13)
．． 5%) was used as the urethane prepolymer (B-1), and a paint was prepared with the following formulation.
化合物（Ａ−１） ４７．６部ウレ
タンプレポリマー（Ｂ−１） ８．１部酸化チタ
ン ３０．１部（石原産業■タ
イベークＣＲ−９０）
ＶＩＣ方式で発生させた三級アミンの噴霧エアー中の濃
度を、５ｏｐｐ＋ｍになるＩｌ！Ｊｉ！整した後、エア
ースプレーガンで、先に調合した塗料をリン酸亜鉛処理
板上に塗装した。Compound (A-1) 47.6 parts Urethane prepolymer (B-1) 8.1 parts Titanium oxide 30.1 parts (Ishihara Sangyo Taibake CR-90) Tertiary amine generated by VIC method in air atomization The concentration of Il! becomes 5opp+m! Ji! After the preparation, the previously prepared paint was applied onto the zinc phosphate treated board using an air spray gun.
三級アミンとして、ジメチルエタノールアミンを使用し
た。Dimethylethanolamine was used as the tertiary amine.
以後の実施例、比較例共金て酸化チタン、シンナーは実
施例１に例示した物を使用した。In the subsequent Examples and Comparative Examples, the titanium oxide and thinner used were those exemplified in Example 1.
なお、評価は、乾燥膜厚で、５０μ〜６０μで実施した
。The evaluation was conducted at a dry film thickness of 50 μm to 60 μm.
実施例２
オレスターＮＰ１００Ｏ（三井東圧化学■製；ヘキサメ
チレンジイソシアネートのビューレット体、不揮発分７
５％、イソシアネート基含有率１７．０％）をウレタン
プレポリマー（Ｂ−２）とし下記配合で塗料を作成した
。Example 2 Olester NP100O (manufactured by Mitsui Toatsu Chemical ■; biuret form of hexamethylene diisocyanate, non-volatile content 7
5%, isocyanate group content 17.0%) was used as urethane prepolymer (B-2), and a coating material was prepared with the following formulation.
化合物（Ａ−１） ４９．４部ウレ
タンプレポリマー（Ｂ−２） ６．７部酸化チタ
ン ２９．７部シンナー
１４．２部１００．０部
本塗料を実施例１と同様な方法で塗装を行なった。Compound (A-1) 49.4 parts Urethane prepolymer (B-2) 6.7 parts Titanium oxide 29.7 parts Thinner
14.2 parts 100.0 parts of this paint was applied in the same manner as in Example 1.
実施例３
化合物（Ａ−１） １００重量部にＰＰＧ−Ｄｉａｌｌ
ｏｏｏ （三井東圧化学■製、ポリプロピレンジオール
、分子ｆｆ１１０００）を、１００重量部混合し化合物
（Ａ−２）とした。又下記配合で塗料を作成し実施例１
と同様な方法で塗装した。Example 3 PPG-Dial to 100 parts by weight of compound (A-1)
100 parts by weight of ooo (manufactured by Mitsui Toatsu Chemical ■, polypropylene diol, molecule ff11000) were mixed to obtain a compound (A-2). In addition, a paint was prepared with the following composition and Example 1
Painted in the same way.
化合物（Ａ−２） ３４．９部ウレ
タンプレポリマー（Ｂ−１） １３．９部酸化チタ
ン ３６．９部シンナー
’ １４．２部１００．０部
実施例４
実施例１で作成した塗料を、エアースプレーガンで塗装
した後、ＶＩＣ方式で発生させた三級アミン蒸気を、５
０ｐｐ＋＊含有するエアー塗装物に噴霧し、塗膜を硬化
させた。Compound (A-2) 34.9 parts Urethane prepolymer (B-1) 13.9 parts Titanium oxide 36.9 parts Thinner
' 14.2 parts 100.0 parts Example 4 After applying the paint prepared in Example 1 with an air spray gun, tertiary amine vapor generated by the VIC method was added to
It was sprayed onto an air-coated product containing 0 pp+*, and the coating film was cured.
比較例１
実施例１で作成した塗料を三級アミンを含まない通常の
エアースプレーガンで塗装を行なった。Comparative Example 1 The paint prepared in Example 1 was applied using an ordinary air spray gun that does not contain tertiary amine.
比較例２
活性水素を有するチオール基音を化合物（Ａ−１）に対
する、イソシアネート基を有するウレタンプレポリマー
（Ｂ−１）の当量比が１．０ ： ０．４になる様に、
下記配合で塗料を作成し、実施例１と同様な方法で塗装
した。Comparative Example 2 The equivalent ratio of the urethane prepolymer (B-1) having an isocyanate group to the compound (A-1) containing a thiol radical having an active hydrogen group was 1.0:0.4.
A paint was prepared with the following formulation and applied in the same manner as in Example 1.
化合物（Ａ−１） ５２．９部ウ
レタンプレポリマー（Ｂ−１） ３．６部酸化チ
タン ２９．３部シンナー
１４．２部１００．０部
〔発明の効果〕
本発明のアクリルポリオール、ジイソシアネート、メル
カプトエタノールより誘導されるチオール基を含有する
化合物と、ウレタンプレポリマーを含有する樹脂組成分
は、可使時間が長く、かつ三級アミンの存在により直ち
に硬化することが、表−１から明らかである。Compound (A-1) 52.9 parts Urethane prepolymer (B-1) 3.6 parts Titanium oxide 29.3 parts Thinner
14.2 parts 100.0 parts [Effect of the invention] The resin composition containing the thiol group-containing compound derived from the acrylic polyol, diisocyanate, and mercaptoethanol of the present invention and the urethane prepolymer has a pot life of It is clear from Table 1 that it is long and cures quickly due to the presence of tertiary amine.
Claims (1)
ポリマー（Ｂ）とを含有し、該チオール基を含有する化
合物（Ａ）が、アクリルポリオール樹脂、ジイソシアネ
ート、及びメルカプトエタノールより誘導される化合物
であり、かつ（Ａ）と（Ｂ）との配合割合が、活性水素
とイソシアネート基の当量比で０．５：１．０〜１．０
：０．５の範囲にあることを特徴とする塗料用樹脂組成
物。 ２、請求項１記載の塗料用樹脂組成物よりなる塗料を塗
装するに際して、三級アミン蒸気あるいは、微粒化され
た三級アミンを噴霧エアー中に含有させ塗料と混合させ
るか、塗装後三級アミン蒸気と接触させる事を特徴とす
る塗装方法。[Claims] 1. Contains a thiol group-containing compound (A) and a urethane prepolymer (B), wherein the thiol group-containing compound (A) is an acrylic polyol resin, diisocyanate, and mercaptoethanol. and the compounding ratio of (A) and (B) is 0.5:1.0 to 1.0 in equivalent ratio of active hydrogen to isocyanate group.
: A resin composition for paint, characterized in that it is in the range of 0.5. 2. When applying a paint made of the resin composition for paint according to claim 1, tertiary amine vapor or atomized tertiary amine is contained in spray air and mixed with the paint, or tertiary amine vapor or atomized tertiary amine is mixed with the paint after painting. A coating method characterized by contact with amine vapor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23556189A JPH03100084A (en) | 1989-09-13 | 1989-09-13 | Coating resin composition and coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23556189A JPH03100084A (en) | 1989-09-13 | 1989-09-13 | Coating resin composition and coating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03100084A true JPH03100084A (en) | 1991-04-25 |
Family
ID=16987814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23556189A Pending JPH03100084A (en) | 1989-09-13 | 1989-09-13 | Coating resin composition and coating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03100084A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005722A1 (en) * | 1996-08-01 | 1998-02-12 | Chugoku Marine Paints, Ltd. | Coating composition, method for coating with the same, and article coated by said method |
| US10711086B2 (en) | 2014-10-08 | 2020-07-14 | Basf Se | Phosphate ester-modified acrylic polyols |
-
1989
- 1989-09-13 JP JP23556189A patent/JPH03100084A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005722A1 (en) * | 1996-08-01 | 1998-02-12 | Chugoku Marine Paints, Ltd. | Coating composition, method for coating with the same, and article coated by said method |
| US10711086B2 (en) | 2014-10-08 | 2020-07-14 | Basf Se | Phosphate ester-modified acrylic polyols |
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