JPH02163160A - Molded polyurethane product - Google Patents
Molded polyurethane productInfo
- Publication number
- JPH02163160A JPH02163160A JP63317342A JP31734288A JPH02163160A JP H02163160 A JPH02163160 A JP H02163160A JP 63317342 A JP63317342 A JP 63317342A JP 31734288 A JP31734288 A JP 31734288A JP H02163160 A JPH02163160 A JP H02163160A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- polyurethane product
- molded polyurethane
- aluminum powder
- polyurethane molded
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 abstract description 17
- 150000003077 polyols Chemical class 0.000 abstract description 17
- 238000002845 discoloration Methods 0.000 abstract description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003431 cross linking reagent Substances 0.000 abstract description 8
- 229920000728 polyester Polymers 0.000 abstract description 7
- 239000005056 polyisocyanate Substances 0.000 abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012970 tertiary amine catalyst Substances 0.000 abstract description 4
- 239000003112 inhibitor Substances 0.000 abstract description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004088 foaming agent Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 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 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OXDOANYFRLHSML-UHFFFAOYSA-N dimethoxyphosphorylbenzene Chemical compound COP(=O)(OC)C1=CC=CC=C1 OXDOANYFRLHSML-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- -1 jetanolamine Chemical compound 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- 229940029284 trichlorofluoromethane Drugs 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- MKGIQRNAGSSHRV-UHFFFAOYSA-N 1,1-dimethyl-4-phenylpiperazin-1-ium Chemical compound C1C[N+](C)(C)CCN1C1=CC=CC=C1 MKGIQRNAGSSHRV-UHFFFAOYSA-N 0.000 description 1
- 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 1
- AEYNYHSOGNVQRY-UHFFFAOYSA-N 1-n,1-n-diethyl-4-methylbenzene-1,3-diamine Chemical compound CCN(CC)C1=CC=C(C)C(N)=C1 AEYNYHSOGNVQRY-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- VKABKQBHBBROCU-UHFFFAOYSA-N 2-(2,2,3-trimethylpiperazin-1-yl)ethanamine Chemical compound CC1NCCN(CCN)C1(C)C VKABKQBHBBROCU-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000143957 Vanessa atalanta Species 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- KTOCGRDHTCKGRC-UHFFFAOYSA-N [hydroxy(methoxy)phosphoryl] dimethyl phosphate Chemical compound COP(O)(=O)OP(=O)(OC)OC KTOCGRDHTCKGRC-UHFFFAOYSA-N 0.000 description 1
- BHUMZHDFNOXAMC-UHFFFAOYSA-N [methoxy(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(OC)C1=CC=CC=C1 BHUMZHDFNOXAMC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HAXBLJDZJKJLHZ-UHFFFAOYSA-N dimethylphosphoryloxymethane Chemical compound COP(C)(C)=O HAXBLJDZJKJLHZ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- YLJRCXSSKLWCDE-UHFFFAOYSA-N methyl ethanesulfonate Chemical compound CCS(=O)(=O)OC YLJRCXSSKLWCDE-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアルミ粉を含有する塗膜（メタリック塗膜）を
表面に形成してなるポリウレタン成形品に係るものであ
り、特にメタリック塗膜の耐変色性の改善されたポリウ
レタン成形品に係るものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyurethane molded product having a coating film containing aluminum powder (metallic coating film) formed on the surface thereof, and particularly relates to a polyurethane molded product having a coating film containing aluminum powder (metallic coating film) formed on the surface. This relates to a polyurethane molded product with improved discoloration resistance.
塗膜を表面に形成してなるポリウレタン成形品はその物
理的性状に応して自動車用部品、電子・電気機器用部品
などに利用されており、近年自動車のバンパー、エア・
スポイラ−、フェンダ−ドア・パネルなどの自動車外装
部品、コンピューターや空調機のハウジングなどの電子
・電気機器用部品への応用が進んでいる。Polyurethane molded products with a coating film formed on their surfaces are used for automotive parts, electronic and electrical equipment parts, etc., depending on their physical properties, and in recent years they have been used for automotive bumpers, air, air, etc.
Applications are progressing to automotive exterior parts such as spoilers, fender doors and panels, and electronic and electrical equipment parts such as housings for computers and air conditioners.
ポリウレタン成形品は、通常は第３級アミン系触媒の存
在下にポリイソシアネート、ポリオール、架橋剤および
添加剤からなる反応混合物を密閉できる金型に導入して
製造されている。Polyurethane molded articles are usually produced by introducing a reaction mixture of polyisocyanate, polyol, crosslinking agent and additives into a sealable mold in the presence of a tertiary amine catalyst.
自動車部品や電子電気機器用部品としてのポリウレタン
成形品は意匠上の目的と耐候性向上の目的のために通常
その表面に塗装が行われている。Polyurethane molded products used as parts for automobiles or electronic and electrical equipment are usually coated on their surfaces for design purposes and to improve weather resistance.
しかしアルミ粉を含有する塗膜を表面に形成した従来の
ポリウレタン成形品は、高湿度雰囲気に暴露されたり、
水との接触を受けた場合、ポリウレタン成形品中の第３
級アミン（ウレタン化反応の触媒）と水との作用によっ
て塗膜中のアルミ粉が腐食を受けて塗膜が変色するとい
う欠点があった。However, conventional polyurethane molded products that have a coating film containing aluminum powder formed on their surfaces are exposed to high humidity environments,
When exposed to water, the tertiary material in polyurethane moldings
The drawback was that the aluminum powder in the coating film was corroded by the action of the amine (catalyst for the urethanization reaction) and water, resulting in discoloration of the coating film.
本発明者は、メタリック塗膜を表面に形成してなるポリ
ウレタン成形品の耐変色性の改善について鋭意検討を重
ねた結果、本発明に到達した。The present inventor has arrived at the present invention as a result of intensive studies on improving the discoloration resistance of polyurethane molded products formed by forming a metallic coating film on the surface.
すなわち、本発明は、ポリイソシアネート、ポリオール
、第３級アミン触媒、必要により発泡剤その他の添加剤
の存在下に金型内で反応させて発泡又は非発泡のポリウ
レタン樹脂を成形し、その成形品の表面にアルミ粉を含
有する塗膜を形成したものを製造する際に、変色防止剤
として下記一般式（１）または（２）で表わされる化合
物を配合することを特徴とするポリウレタン成形品であ
る。That is, the present invention involves molding a foamed or non-foamed polyurethane resin by reacting it in a mold in the presence of a polyisocyanate, a polyol, a tertiary amine catalyst, and optionally a blowing agent and other additives, and producing a molded product thereof. A polyurethane molded product characterized in that a compound represented by the following general formula (1) or (2) is blended as a discoloration preventive agent when producing a polyurethane molded product with a coating film containing aluminum powder formed on the surface of the polyurethane molded product. be.
（Ｃ）ｌ：１０） １ＩＰＲ１−１゜
・・−・・・・・・−・・−−−・−−一・−・（１）
ＣＨｆｆＯ−５−Ｒ−一・・・−・・・・・・−・・・
・−・・・・（２）（一般式中、１≦ｎ≦３であり、Ｒ
は置換基を有していてもよいアルキル基またはフェニル
基を表わす。）
このような一般式（１）で表わされる化合物としては、
例えばリン酸トリメチル、メチルホスホン酸ジメチル、
フェニルホスホン酸ジメチル、トリルホスホン酸ジメチ
ル、ジメチルホスフィン酸メチル、ジフェニルホスフィ
ン酸メチルなどが挙げられる。(C)l:10) 1IPR1-1゜・・・・・・・・・−・・−−・−−１・−・(1)
CHffO-5-R-1・・・・・・・・・・・・・・・
...(2) (in the general formula, 1≦n≦3, and R
represents an alkyl group or a phenyl group which may have a substituent. ) As a compound represented by such general formula (1),
For example, trimethyl phosphate, dimethyl methylphosphonate,
Examples include dimethyl phenylphosphonate, dimethyl tolylphosphonate, methyl dimethylphosphinate, and methyl diphenylphosphinate.
また一般式（２）で表わされる化合物としては、例えば
ベンゼンスルホン酸メチル、ｐ−）ルエンスルホン酸メ
チル、エタンスルホン酸メチルなどが挙げられる。Examples of the compound represented by the general formula (2) include methyl benzenesulfonate, methyl p-)luenesulfonate, and methyl ethanesulfonate.
これらの変色防止剤はそれぞれ単独で用いてもよいし、
それらの混合物で用いてもよい。本発明における変色防
止剤の使用量は以下にのべるポリウレタン成形品に対し
て通常０．２〜２重１％、好ましくは０．３〜１．５重
量％である。These discoloration inhibitors may be used alone, or
A mixture thereof may also be used. The amount of discoloration inhibitor used in the present invention is usually 0.2 to 2% by weight, preferably 0.3 to 1.5% by weight, based on the polyurethane molded article described below.
本発明において使用するポリイソシアネートとしては、
従来からポリウレタン製造に使用されているものが使用
できる。このようなポリイソシアネートとしては、芳香
族ポリイソシアネート（例えば２．４−および／または
２．６−トリレンジイソシアネート（ＴＤＩ）、粗製Ｔ
ＤＩ、２．４’−および／または４．４′−ジフェニル
メタンジイソジシアネート（ＭＤＩ）、粗製ＭＤＩなど
）、脂肪族ポリイソシアネート（例えばヘキサメチレン
ジイソシアネート、イソホロンジイソシアネート、ジシ
クロヘキシルメタンジイソシアネートなど）、芳香脂肪
族イソシアネート（例えばキシリレンジイソシアネート
など）、これらの変性物（ウレタン基、カルボジイミド
基、ウレトンイミン基、イソシアヌレート基、オキサゾ
リドン基含有変性物など）、およびこれら２種以上の混
合物が挙げられる。The polyisocyanate used in the present invention includes:
Those conventionally used in polyurethane production can be used. Such polyisocyanates include aromatic polyisocyanates such as 2,4- and/or 2,6-tolylene diisocyanate (TDI), crude T
DI, 2.4'- and/or 4.4'-diphenylmethane diisocyanate (MDI), crude MDI, etc.), aliphatic polyisocyanates (e.g. hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc.), aromatic fats Examples include group isocyanates (for example, xylylene diisocyanate, etc.), modified products thereof (modified products containing a urethane group, a carbodiimide group, a uretonimine group, an isocyanurate group, an oxazolidone group, etc.), and mixtures of two or more of these.
本発明において使用するポリオールは、従来からポリウ
レタン製造に使用されているものが使用できる。このよ
うなポリオールとしては、例えばポリエーテルポリオー
ル、ポリエステルポリオールおよびポリマーポリオール
などを挙げることができる。これらのポリオールは、１
分子中に通常２〜８個の水酸基を有しており、０旧直は
２０〜５００ｍｇＫＯＨ／ｇ程度である。As the polyol used in the present invention, those conventionally used in polyurethane production can be used. Examples of such polyols include polyether polyols, polyester polyols, and polymer polyols. These polyols are 1
It usually has 2 to 8 hydroxyl groups in its molecule, and its concentration is about 20 to 500 mgKOH/g.
本発明において使用する架橋剤としては、低分子ジオー
ル（例えば、エチレングリコール、ジエチレングリコー
ル、プロピレングリコール、ジプロピレングリコール、
１，４−ブタンジオール、１．６−ヘキサンジオールな
ど）、アルカノールアミン（例えばモノエタノールアミ
ン、ジェタノールアミン、トリエタノールアミン、モツ
プロバノールアミン、トリプロパツールアミンなど）、
脂肪族ポリアミン（例えば、エチレンジアミン、トリメ
チレンジアミン、テトラメチレンジアミン、ジエチレン
トリアミンなど）、芳香族ポリアミン（例えば、フェニ
レンジアミン、トリレンジアミン、ジエチルトリレンジ
アミン、ジフェニルメタンジアミン、メチレンビス（０
−クロロアニリン）など）およびこれらの２種以上の混
合物が挙げられる。The crosslinking agent used in the present invention includes low molecular weight diols (e.g., ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
1,4-butanediol, 1,6-hexanediol, etc.), alkanolamines (e.g. monoethanolamine, jetanolamine, triethanolamine, motuprobanolamine, tripropaturamine, etc.),
Aliphatic polyamines (e.g., ethylenediamine, trimethylenediamine, tetramethylenediamine, diethylenetriamine, etc.), aromatic polyamines (e.g., phenylenediamine, tolylenediamine, diethyltolylenediamine, diphenylmethanediamine, methylenebis(0)
-chloroaniline) and mixtures of two or more thereof.
架橋剤の使用量はポリオールの重量に基づいて、通常５
〜４０重世％、好ましくは１０〜３００〜３０重世。The amount of crosslinking agent used is usually 5% based on the weight of the polyol.
-40%, preferably 10-300-30%.
本発明において使用するポリウレタン化反応の触媒とし
ては第３級アミンが使用されこの他に錫系触媒等を併用
しても良い。As the catalyst for the polyurethanization reaction used in the present invention, a tertiary amine is used, and a tin-based catalyst or the like may also be used in combination.
第３級アミン系触媒としては、例えばトリエチルアミン
、トリエチレンジアミン、２−メチルトリエチレンジア
ミン、Ｎ、Ｎ、Ｎ ’ 、Ｎ ’−テトラメチルエチレ
ンジアミン、Ｎ、Ｎ、Ｎ ’ 、Ｎ ’−テトラメチル
へキサメチレンジアミン、Ｎ、Ｎ、Ｎ ’ 、Ｎ ’−
テトラメチルプロピレンジアミン、Ｎ、Ｎ、Ｎ ’ 、
Ｎ ’ Ｎ“ペンタメチルジエチレントリアミン、トリ
メチルアミノエチルピペラジン、Ｎ、Ｎ’−ジメチルシ
クロへキシルアミン、Ｎ、Ｎ’−ジメチルベンジルアミ
ン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン、お
よびそれらの混合物を使用することができる。Examples of tertiary amine catalysts include triethylamine, triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylene Diamine, N, N, N', N'-
Tetramethylpropylene diamine, N, N, N',
Using N'N'pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, N,N'-dimethylcyclohexylamine, N,N'-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, and mixtures thereof Can be done.
第３級アミン触媒の使用量はポリオールと架橋剤の重量
の合計に基づいて通常０．１〜５重量％である。The amount of tertiary amine catalyst used is usually 0.1 to 5% by weight based on the total weight of polyol and crosslinker.
錫系触媒としては、ジプチル錫ジラウレート、オクチル
酸第１錫などを使用することができ、その使用量はポリ
オールと架橋剤の重量の合計に基づいて通常０．０ Ｏ
５〜１重足％である。As the tin-based catalyst, diptyltin dilaurate, stannous octylate, etc. can be used, and the amount used is usually 0.0 O based on the total weight of the polyol and crosslinking agent.
It is 5 to 1%.
また、本発明においてはポリウレタンの製造に際し、必
要により発泡剤（例えばトリクロロモノフルオロメタン
、ジクロロメタン、水など）を使用することができる。Further, in the present invention, a blowing agent (for example, trichloromonofluoromethane, dichloromethane, water, etc.) can be used if necessary during the production of polyurethane.
発泡剤の使用量は、ポリオールと架橋剤の重■の合計に
基づいて、トリクロロモノフルオロメタン又はジクロロ
メタンの場合は１〜１０重世％、水の場合は０．１〜２
重量％である。The amount of blowing agent used is based on the total weight of polyol and crosslinking agent, in the case of trichloromonofluoromethane or dichloromethane, it is 1 to 10 weight percent, and in the case of water, it is 0.1 to 2 weight percent.
Weight%.
本発明においてポリウレタンの成形に際してＮＧＯイン
デックス（ＮＣＯ基／活性水素原子含有基の当量比Ｘ１
００）は通常８０〜１２０、好ましくは９５〜１０８で
ある。In the present invention, when molding polyurethane, NGO index (equivalent ratio of NCO group/active hydrogen atom-containing group
00) is usually 80-120, preferably 95-108.
本発明に用いるアルミ粉を含有する塗膜を形成するため
の塗料としては通常、１〜５重量％のアルミ粉を含有す
る硬化用樹脂からなり、硬化用樹脂としては二液型ポリ
エステルウレタン、二液型アクリルウレタン、メラミン
硬化ウレタンポリエステルなどを使用することができる
。具体的にはエラストマー用塗料Ｒ２５７／Ｒ２３０（
日本ビー・ケミカル０荀）、ソフレソクス１４００（関
西ペイント掬）、プラニットＵ１６０ （大日本塗料■
）、プラニソ）Ｍ１３０（大日本塗料０１）などの塗料
を使用することができる。The paint for forming the coating film containing aluminum powder used in the present invention usually consists of a curing resin containing 1 to 5% by weight of aluminum powder, and the curing resin is two-component polyester urethane, two-component polyester urethane, two-component polyester urethane, two-component polyester urethane, Liquid type acrylic urethane, melamine-cured urethane polyester, etc. can be used. Specifically, elastomer paint R257/R230 (
Nippon B Chemical 0x), Sofre Sox 1400 (Kansai Paint Kiki), Planit U160 (Dainippon Paint)
), Planiso) M130 (Dainippon Paint Co., Ltd. 01) and the like can be used.
このような塗料は前記ポリウレタン成形品の表面に吹き
付は等によって塗布したのち焼き付は硬化を行って塗膜
を形成する。Such a paint is applied to the surface of the polyurethane molded article by spraying or the like, and then cured by baking to form a coating film.
以下に本発明を実施例により具体的に説明するが、本発
明はこれらの実施例に限定されるものではない。尚実施
例中「部」は「重量部」を示す。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In the examples, "parts" indicate "parts by weight."
実施例、比較例に使用した原料は次の通りである。The raw materials used in the Examples and Comparative Examples are as follows.
（１）変色防止剤
ＴＭＰ ニリン酸トリメチル
ＤＭＭＰ：メチルホスポン酸ジメチル
ＤＭＰＰ：フェニルホスホン酸ジメチルＭＢＳ ：ベ
ンゼンスルホン酸メチル（２）触媒
ＤＢＴＤＬ ニジブチル錫ジラウレートＤＡＢＣＯ３３
ＬＶ ： Ｉ−リエチレンジアミンの３３％ジプロピレ
ングリコール
（３）ポリオールＡ：グリセリン９２部にプロピレンオ
キシド４７００部、次いでエチレンオキシド１２００部
を付加させた叶価２８ｍｇにＯｌ／ｇの３官能ポリオー
ル。(1) Anti-discoloration agent TMP Trimethyl diphosphate DMMP: Dimethyl methylphosponate DMPP: Dimethyl phenylphosphonate MBS: Methyl benzenesulfonate (2) Catalyst DBTDL Nidibutyltin dilaurate DABCO33
LV: 33% dipropylene glycol (3) of I-lyethylenediamine Polyol A: A trifunctional polyol with a weight of 28 mg and Ol/g, which is obtained by adding 4,700 parts of propylene oxide to 92 parts of glycerin, and then 1,200 parts of ethylene oxide.
（４１ 架橋剤：エチレングリコール（５） イソ
シア名−ト
Ｉｓｏｎａｔｅ １ ４ ３ Ｌ ：カルボジイミド変
性ＭＤＩ （ＮＧＯ含打率２８．３％）（６）塗料
塗料Ａ：二液型ポリエステルウレタン塗料アルミ粉含有
量４％
塗料Ｂニー成型メラミン硬化アクリル系塗料アルミ粉含
有量４％
実施例１〜９、比較例１．２
第１表に記載の処方に従って下記の成形条件で、ポリオ
ール、架橋剤および触媒からなるポリオールプレミック
スとイソシアネートとを、それぞれ高圧発泡機の原料タ
ンクに仕込み、ミキシングヘッドにて１ｉｉ突混合して
得られた反応混合物を、厚み３．Ｏｍｍｘ巾５５０ｍｍ
ｘ長さ６００ｍｍの温度調節可能な密閉モールドに注入
してポリウレタン成形品を成形した。変色防止剤は実施
例１および２においては、ポリオールプレミックス中に
、実施例３〜９においてはイソシアネート中に添加して
成形品を得た。(41 Crosslinking agent: Ethylene glycol (5) Isonate 1 4 3 L: Carbodiimide modified MDI (NGO content 28.3%) (6) Paint Paint A: Two-component polyester urethane paint Aluminum powder content 4 % Paint B Knee molded melamine cured acrylic paint Aluminum powder content 4% Examples 1 to 9, Comparative Examples 1.2 A polyol consisting of a polyol, a crosslinking agent and a catalyst was molded according to the recipe listed in Table 1 under the following molding conditions. The premix and isocyanate were each placed in the raw material tank of a high-pressure foaming machine, and the reaction mixture obtained by 1ii thrust mixing with a mixing head was heated to a thickness of 3.0 mm x width of 550 mm.
A polyurethane molded article was molded by injecting it into a temperature-adjustable closed mold with a length of 600 mm. The anti-discoloration agent was added to the polyol premix in Examples 1 and 2, and to the isocyanate in Examples 3 to 9 to obtain molded articles.
高圧発泡機 ＨＤ５００（アドミラル社製高圧発泡機）
吐出速度 ５００ ｇ ／ ｓ ｅ ｃ吐出圧力 １５
０〜１７０ｋｇ／ｃＪ
原料温度 原料上２℃
金型温度 ７０±２℃
得られたポリウレタン成形品から巾７０龍×長さ１５０
１のサンプルを作成しトリクロロエタン藤気槽中で１分
間洗浄したあと１０分間室温で乾燥したのち、実施例１
〜９および比較例１．２のサンプルを同時に並べて前記
塗料Ａ又は塗料Ｂをエア・スプレーガンで吹き付けたあ
と約１０分間のセツティングののち塗膜の加熱焼き付け
を行って塗装サンプルを得た。なお塗料へを使用した場
合は１００℃で３０分間、塗料Ｂを使用した場合は１２
０°Ｃで３０分間の焼き付けを行った。High-pressure foaming machine HD500 (High-pressure foaming machine manufactured by Admiral) Discharge speed: 500 g/sec Discharge pressure: 15
0~170kg/cJ Raw material temperature: 2℃ above the raw material Mold temperature: 70±2℃ The resulting polyurethane molded product has a width of 70 mm x length of 150 mm.
A sample of Example 1 was prepared, washed for 1 minute in a trichloroethane vacuum tank, and dried at room temperature for 10 minutes.
9 and Comparative Example 1.2 were lined up at the same time, the paint A or paint B was sprayed with an air spray gun, and after setting for about 10 minutes, the paint film was baked by heating to obtain a painted sample. In addition, when using paint B, it is heated at 100℃ for 30 minutes, and when using paint B, it is heated for 12 minutes.
Baking was performed at 0°C for 30 minutes.
得られた塗装サンプルの耐変色性は、塗装サンプルを４
０℃に調節したイオン交換水中に２４０時間浸せきした
のち、浸せきの前と後の塗膜の変色の度合を測色色差計
を用いてハンター色差ΔＥ（Ｌａｂ）を測定することと
目視判定を行うことによって評価した。耐変色性の評価
結果は第１表に示す。The color fastness of the obtained paint sample was 4.
After immersing in ion-exchanged water adjusted to 0°C for 240 hours, the degree of discoloration of the paint film before and after immersion is determined by measuring the Hunter color difference ΔE (Lab) using a colorimeter and visual judgment. It was evaluated by The evaluation results of color fastness are shown in Table 1.
本発明の特定の化合物を配合したポリウレタン成形品は
アルミ粉を含有する塗膜を形成してもメタリック塗膜の
耐変色性のすぐれたものである。A polyurethane molded article containing the specific compound of the present invention has excellent discoloration resistance of a metallic coating film even when a coating film containing aluminum powder is formed.
出 願 人applicant
Claims (1)
ンの成形品表面にアルミ粉を含有する塗膜を形成してな
るポリウレタン成形品において、ポリウレタン成形品中
に下記一般式（１）または（２）で表わされる化合物を
配合することを特徴とするポリウレタン成形品。 ▲数式、化学式、表等があります▼……………………（
１） ▲数式、化学式、表等があります▼……………………（
２） （一般式中、１≦ｎ≦３であり、Ｒは置換基を有してい
てもよいアルキル基またはフェニル基を表わす。）(1) In a polyurethane molded product formed by forming a coating film containing aluminum powder on the surface of a polyurethane molded product produced using a tertiary amine as a catalyst, the polyurethane molded product contains the following general formula (1) or (2). ) A polyurethane molded product characterized by blending the compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………………(
1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………………(
2) (In the general formula, 1≦n≦3, and R represents an alkyl group or a phenyl group that may have a substituent.)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63317342A JPH02163160A (en) | 1988-12-15 | 1988-12-15 | Molded polyurethane product |
| PCT/JP1989/001255 WO1990006973A1 (en) | 1988-12-15 | 1989-12-14 | Polyurethane molding |
| KR1019900701766A KR910700314A (en) | 1988-12-15 | 1989-12-14 | Polyurethane molded products |
| AU47427/90A AU4742790A (en) | 1988-12-15 | 1989-12-14 | Polyurethane molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63317342A JPH02163160A (en) | 1988-12-15 | 1988-12-15 | Molded polyurethane product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02163160A true JPH02163160A (en) | 1990-06-22 |
Family
ID=18087152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63317342A Pending JPH02163160A (en) | 1988-12-15 | 1988-12-15 | Molded polyurethane product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH02163160A (en) |
| KR (1) | KR910700314A (en) |
| AU (1) | AU4742790A (en) |
| WO (1) | WO1990006973A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03100050A (en) * | 1989-09-13 | 1991-04-25 | Nippon Polyurethane Ind Co Ltd | Heat-stable polyurethane resin composition |
| WO2022034151A1 (en) * | 2020-08-14 | 2022-02-17 | Huntsman International Llc | Additive for reducing polyurethane foam degradation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100832103B1 (en) * | 2006-10-19 | 2008-05-27 | 이상수 | The drssing pad polyurethan |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1694142C3 (en) * | 1967-03-25 | 1975-10-23 | Bayer Ag, 5090 Leverkusen | Process for the production of foams |
| ATE23722T1 (en) * | 1982-10-12 | 1986-12-15 | Ciba Geigy Ag | FIRE RETARDANT COMPOSITIONS. |
-
1988
- 1988-12-15 JP JP63317342A patent/JPH02163160A/en active Pending
-
1989
- 1989-12-14 WO PCT/JP1989/001255 patent/WO1990006973A1/en unknown
- 1989-12-14 KR KR1019900701766A patent/KR910700314A/en not_active Application Discontinuation
- 1989-12-14 AU AU47427/90A patent/AU4742790A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03100050A (en) * | 1989-09-13 | 1991-04-25 | Nippon Polyurethane Ind Co Ltd | Heat-stable polyurethane resin composition |
| WO2022034151A1 (en) * | 2020-08-14 | 2022-02-17 | Huntsman International Llc | Additive for reducing polyurethane foam degradation |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990006973A1 (en) | 1990-06-28 |
| KR910700314A (en) | 1991-03-14 |
| AU4742790A (en) | 1990-07-10 |
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