JPH04220424A - Resin used for dispersing pigment - Google Patents
Resin used for dispersing pigmentInfo
- Publication number
- JPH04220424A JPH04220424A JP2418124A JP41812490A JPH04220424A JP H04220424 A JPH04220424 A JP H04220424A JP 2418124 A JP2418124 A JP 2418124A JP 41812490 A JP41812490 A JP 41812490A JP H04220424 A JPH04220424 A JP H04220424A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- paints
- modified polyester
- resins
- test
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 56
- 239000011347 resin Substances 0.000 title claims abstract description 56
- 239000000049 pigment Substances 0.000 title claims abstract description 34
- 229920000728 polyester Polymers 0.000 claims abstract description 24
- 229920001225 polyester resin Polymers 0.000 claims abstract description 20
- 239000004645 polyester resin Substances 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims description 13
- -1 isocyanate compound Chemical class 0.000 claims description 12
- 150000001414 amino alcohols Chemical class 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 150000007519 polyprotic acids Polymers 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229920001228 polyisocyanate Polymers 0.000 abstract 1
- 239000005056 polyisocyanate Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 48
- 238000012360 testing method Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 25
- 239000002966 varnish Substances 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 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 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HCYSJBICYOIBLS-UHFFFAOYSA-N 2-(dodecylamino)ethanol Chemical compound CCCCCCCCCCCCNCCO HCYSJBICYOIBLS-UHFFFAOYSA-N 0.000 description 1
- NWPCFCBFUXXJIE-UHFFFAOYSA-N 2-(hydroxymethylamino)ethanol Chemical compound OCCNCO NWPCFCBFUXXJIE-UHFFFAOYSA-N 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- MVVQNBYRSDXHRF-UHFFFAOYSA-N 2-[2-hydroxyethyl(2-methylpropyl)amino]ethanol Chemical compound CC(C)CN(CCO)CCO MVVQNBYRSDXHRF-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004990 dihydroxyalkyl group Chemical group 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 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
- 150000002576 ketones Chemical class 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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 1
- 238000012345 traction test Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、顔料の分散性にすぐれ
ると共に、塗料用の各種樹脂と良好に相溶する顔料分散
用樹脂に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for dispersing pigments which has excellent pigment dispersibility and is well compatible with various resins for paints.
【０００２】0002
【従来の技術】現在、塗料のベースとして目的に応じて
用いられている樹脂の種類は多い。たとえば外観を重視
する場合には、アクリル系、アルキド系などの樹脂が用
いられ、その各々に焼付け型、常温乾燥型があり、さら
に目的に応じて焼き付け型アクリル塗料でも、性質の異
なる樹脂を用いることもある。また、その他にエポキシ
系、ビニル系などの樹脂も使用されている。BACKGROUND OF THE INVENTION At present, there are many types of resins used as bases for paints depending on the purpose. For example, if appearance is important, acrylic and alkyd resins are used, and each of these has a baking type and room temperature drying type, and depending on the purpose, baking type acrylic paint uses resins with different properties. Sometimes. In addition, epoxy resins, vinyl resins, and other resins are also used.
【０００３】塗料で色合わせを行う場合には、同等の樹
脂をベースとした複数の原色塗料を混合して色合わせを
行うのが通常の方法である。仮に、互いに異なる樹脂系
の塗料を混合することは、樹脂同志の相溶性がよくない
場合があり、その場合には、塗面の光沢が低下したり、
その他塗料本来の物理的化学的性能が少なからず損なわ
れることになる。[0003] When performing color matching using paints, the usual method is to mix a plurality of primary color paints based on the same resin. If paints made of different resins are mixed together, the compatibility of the resins may not be good, and in that case, the gloss of the painted surface may decrease, or
In addition, the original physical and chemical properties of the paint will be impaired to some extent.
【０００４】したがつて、ひとつの樹脂系塗料に何種類
かの原色塗料が必要であり、同様に他の樹脂系塗料毎に
それぞれ何種類かの原色塗料が必要であるなどで、原色
塗料の種類は膨大な数になり、生産効率上好ましくなく
、また生産管理上のトラブルの原因にもなつている。[0004] Therefore, one resin-based paint requires several types of primary-color paints, and similarly, each resin-based paint requires several types of primary-color paints. The number of types is enormous, which is not desirable in terms of production efficiency, and also causes trouble in production management.
【０００５】一方、比較的広い範囲の樹脂と相溶性のあ
る低分子の樹脂、たとえば尿素系、トリアジン系、ポリ
グリコール系、アクリル系などの低分子の樹脂を用い、
これに顔料を分散させた原色塗料を調製することにより
、上記の如き生産効率上などの問題を回避することが考
えられている。しかしながら、このような低分子の樹脂
では、これと塗料用の各種樹脂と混ぜ合わせたときに、
その塗膜物性や塗膜耐久性が一般に悪くなるという欠点
を免れなかつた。On the other hand, using low-molecular resins that are compatible with a relatively wide range of resins, such as urea-based, triazine-based, polyglycol-based, and acrylic-based resins,
It is considered that the above-mentioned problems in terms of production efficiency can be avoided by preparing primary color paints in which pigments are dispersed. However, when such low-molecular resins are mixed with various resins for paints,
However, the physical properties of the coating film and the durability of the coating film were generally poor.
【０００６】〔発明が解決しようとする課題〕このよう
に、従来においては、塗料用の各種樹脂とよく相溶して
、かつ良好な塗膜特性を発揮しうるような顔料分散用樹
脂は、ほとんど見い出されておらず、その出現が強く望
まれていた。[Problems to be Solved by the Invention] As described above, in the past, resins for pigment dispersion that are compatible with various resins for paints and can exhibit good coating properties are It had hardly been discovered, and its appearance was strongly desired.
【０００７】本発明は、上記従来の事情に鑑み、顔料の
分散性にすぐれると共に、アルキド系、アクリル系、ビ
ニル系、エポキシ系などの各種塗料用の樹脂と良好に相
溶して、これら樹脂に混合したときに各樹脂本来の性能
を損なうことなく良好な塗膜特性を付与しうるような顔
料分散用樹脂を提供することを目的としている。In view of the above-mentioned conventional circumstances, the present invention provides pigments that have excellent dispersibility and are well compatible with resins for various paints such as alkyd, acrylic, vinyl, and epoxy paints. The object of the present invention is to provide a resin for pigment dispersion which, when mixed with a resin, can impart good coating film properties without impairing the inherent performance of each resin.
【０００８】〔課題を解決するための手段〕本発明者ら
は、上記の目的を達成するために鋭意検討した結果、ア
ルコール成分の一種としてアミノアルコールを用いた特
定のポリエステルプレポリマーを中間原料とし、これに
多官能イソシアネート化合物を反応させて得られるウレ
タン変性ポリエステル樹脂が広範囲の樹脂と良好に相溶
し、かつ良好な顔料分散性を示すことを見い出し、本発
明を完成した。[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have developed a specific polyester prepolymer using amino alcohol as a type of alcohol component as an intermediate raw material. The present invention was completed based on the discovery that a urethane-modified polyester resin obtained by reacting this with a polyfunctional isocyanate compound is well compatible with a wide range of resins and exhibits good pigment dispersibility.
【０００９】すなわち、本発明は、多塩基酸および多価
アルコールのほかにポリエステルプレポリマーの原料中
０．５〜７．０重量％となる割合のアミノアルコールを
必須成分として用いて縮合反応させて得た数平均分子量
が３５０〜１５００、水酸基価が１００〜３００のアミ
ン変性ポリエステルプレポリマーに、このプレポリマー
の水酸基１当量に対してイソシアネート基が０．１〜０
．７当量となる割合の多官能イソシアネート化合物を反
応させて得られる、水酸基価が４０〜２４０、数平均分
子量が７００〜２０００のウレタン変性ポリエステル樹
脂からなることを特徴とする顔料分散用樹脂に係るもの
である。That is, the present invention involves a condensation reaction using, in addition to a polybasic acid and a polyhydric alcohol, an amino alcohol in a proportion of 0.5 to 7.0% by weight in the raw material of the polyester prepolymer as an essential component. The obtained amine-modified polyester prepolymer having a number average molecular weight of 350 to 1500 and a hydroxyl value of 100 to 300 has an isocyanate group of 0.1 to 0 per equivalent of hydroxyl group in this prepolymer.
．． A resin for pigment dispersion characterized by comprising a urethane-modified polyester resin having a hydroxyl value of 40 to 240 and a number average molecular weight of 700 to 2,000, obtained by reacting a polyfunctional isocyanate compound in a proportion of 7 equivalents. It is.
【００１０】0010
【発明の構成・作用】本発明において中間原料として用
いられるアミン変性ポリエステルプレポリマーは、多塩
基酸および多価アルコールのほかに、アミノアルコール
を必須成分として用い、さらに必要に応じてその他の有
機酸をも出発原料として、これらを周知の方法で縮合反
応させることにより、得ることができる。Structure and operation of the invention The amine-modified polyester prepolymer used as an intermediate raw material in the present invention contains an amino alcohol as an essential component in addition to a polybasic acid and a polyhydric alcohol, and further contains other organic acids as necessary. It can be obtained by subjecting these to a condensation reaction using a well-known method as a starting material.
【００１１】多塩基酸としては、ヘキサヒドロ無水フタ
ル酸、無水フタル酸、イソフタル酸、テトラヒドロ無水
フタル酸、無水トリメリツト酸、アジピン酸、セバシン
酸などのポリエステル製造用として一般に用いられてい
る各種の多塩基酸が挙げられ、これらの中からその１種
または２種以上が用いられる。物性、耐候性、相溶性な
どの点からすると、ヘキサヒドロ無水フタル酸が特に好
ましい。Examples of polybasic acids include various polybasic acids commonly used for producing polyesters, such as hexahydrophthalic anhydride, phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, trimellitic anhydride, adipic acid, and sebacic acid. Examples include acids, and one or more of these may be used. From the viewpoint of physical properties, weather resistance, compatibility, etc., hexahydrophthalic anhydride is particularly preferred.
【００１２】多価アルコールとしては、エチレングリコ
ール、プロピレングリコール、ジエチレングリコール、
ポリプロピレングリコール、ネオペンチルグリコール、
ヘキシレングリコールなどの２価アルコールのほか、グ
リセリン、トリメチロールエタン、トリメチロールプロ
パン、ペンタエリスリトールなどの３価ないしそれ以上
の多価アルコールが挙げられ、これらの中からその１種
または２種以上が用いられる。[0012] Polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol,
polypropylene glycol, neopentyl glycol,
In addition to dihydric alcohols such as hexylene glycol, trivalent or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol may be mentioned, and one or more of these may be used. used.
【００１３】アミノアルコールとしては、つぎの一般式
；Ｎ（Ｒ１）（Ｒ２）（Ｒ３）〔式中、Ｒ１，Ｒ２，Ｒ
３は水素原子、炭素数１〜１８のアルキル基、炭素数１
〜１８のヒドロキシアルキル基または炭素数２〜１８の
ジヒドロキシアルキル基の中から選ばれた基であつて、
互いに同一であつても異なる基であつてもよいが、少な
くともひとつは炭素数１〜１８のヒドロキシアルキル基
である〕で表される１価〜３価のアミノアルコールが好
ましく用いられる。The amino alcohol has the following general formula; N(R1)(R2)(R3) [wherein R1, R2, R
3 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, 1 carbon number
A group selected from a hydroxyalkyl group having ~18 carbon atoms or a dihydroxyalkyl group having 2 to 18 carbon atoms,
The groups may be the same or different, but at least one is a hydroxyalkyl group having 1 to 18 carbon atoms. Monovalent to trivalent amino alcohols are preferably used.
【００１４】このようなアミノアルコールの具体例とし
ては、アミノプロパノール、Ｎ−ジメチルアミノプロパ
ノール、Ｎ−ドデシルアミノエタノールなどのモノアル
コールアミン、２−（Ｎ−ヒドロキシメチルアミノ）エ
タノール、Ｎ−イソブチルジエタノールアミン、Ｎ−メ
チルジブタノールアミンなどのジアルコールアミン、ト
リエタノールアミン、トリブタノールアミンなどのトリ
アルコールアミンなどが挙げられ、これらの中からその
１種または２種以上が用いられる。Specific examples of such amino alcohols include monoalcohol amines such as aminopropanol, N-dimethylaminopropanol, and N-dodecylaminoethanol, 2-(N-hydroxymethylamino)ethanol, N-isobutyldiethanolamine, Dialcoholamines such as N-methyldibutanolamine, triethanolamine, tributanolamine, and the like may be mentioned, and one or more of these may be used.
【００１５】アミノアルコールの使用量は、アミン変性
ポリエステルプレポリマーを得るための原料全体中、０
．５〜７．０重量％の範囲内とすることが必要で、特に
好ましくは１．０〜５．０重量％の範囲内とするのがよ
い。０．５重量％に満たないときは顔料の分散性に劣り
、７．０重量％を超えると塗膜の耐久性が悪くなり、ま
た塗膜の着色の原因ともなる。The amount of amino alcohol used is 0 in the total raw materials for obtaining the amine-modified polyester prepolymer.
．． It is necessary to set it within the range of 5 to 7.0 weight%, and it is particularly preferable to set it within the range of 1.0 to 5.0 weight%. If it is less than 0.5% by weight, the dispersibility of the pigment will be poor, and if it exceeds 7.0% by weight, the durability of the coating film will be poor and it may also cause discoloration of the coating film.
【００１６】必要に応じて用いられるその他の有機酸と
しては、炭素数８〜１８の脂肪酸、ダイマー酸、安息香
酸などを使用することができる。これらの有機酸の使用
量としては、アミン変性ポリエステルプレポリマーを得
るための原料全体中、１０重量％以下に抑えられている
のがよい。Other organic acids that may be used as necessary include fatty acids having 8 to 18 carbon atoms, dimer acid, benzoic acid, and the like. The amount of these organic acids used is preferably suppressed to 10% by weight or less based on the total raw materials for obtaining the amine-modified polyester prepolymer.
【００１７】このような出発原料を縮合反応させて得ら
れる、本発明の中間原料であるアミン変性ポリエステル
プレポリマーは、その数平均分子量が３５０〜１５００
、水酸基価が１００〜３００であることが必要で、特に
好ましくは数平均分子量が５００〜１０００、水酸基価
が１１０〜２５０であるのがよい。また、酸価としては
、通常１５以下であるのがよい。数平均分子量が３５０
未満では、最終目的とするウレタン変性ポリエステル樹
脂の物性や耐候性などが悪くなり、１５００を超えると
、上記樹脂と他の塗料用の各種樹脂との相溶性が悪くな
る。また、水酸基価が１００未満かあるいは３００を超
えてしまうと、いずれも上記ウレタン変性ポリエステル
樹脂の耐久性や他の塗料用の各種樹脂との相溶性が悪く
なる。The amine-modified polyester prepolymer, which is the intermediate raw material of the present invention, obtained by condensation reaction of such starting materials has a number average molecular weight of 350 to 1500.
It is necessary that the hydroxyl value is 100 to 300, particularly preferably a number average molecular weight of 500 to 1000 and a hydroxyl value of 110 to 250. Further, the acid value is preferably 15 or less. Number average molecular weight is 350
If it is less than 1,500, the physical properties and weather resistance of the final target urethane-modified polyester resin will deteriorate, and if it exceeds 1,500, the compatibility between the resin and various resins for other paints will be poor. Furthermore, if the hydroxyl value is less than 100 or more than 300, the durability of the urethane-modified polyester resin and the compatibility with various resins for other paints will deteriorate.
【００１８】本発明においては、上記のアミン変性ポリ
エステルプレポリマーを中間原料として、これに多官能
イソシアネート化合物を反応させることにより、ウレタ
ン変性ポリエステル樹脂を生成する。In the present invention, a urethane-modified polyester resin is produced by using the above-mentioned amine-modified polyester prepolymer as an intermediate raw material and reacting it with a polyfunctional isocyanate compound.
【００１９】ここで用いる多官能イソシアネート化合物
としては、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、トリレンジイソシアネートおよび
これらの２量体や３量体のほか、これらのイソシアネー
ト化合物と水、エチレングリコール、プロピレングリコ
ールなどの多価アルコールとの反応物などが挙げられ、
その１種または２種以上が用いられる。これらの各化合
物は、いずれも１分子当り２個または３個のイソシアネ
ート基を有するものである。Examples of the polyfunctional isocyanate compounds used here include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, dimers and trimers thereof, and combinations of these isocyanate compounds with water, ethylene glycol, propylene glycol, etc. Examples include reactants with polyhydric alcohols,
One or more of these may be used. Each of these compounds has two or three isocyanate groups per molecule.
【００２０】このような多官能イソシアネート化合物の
使用量は、アミン変性ポリエステルプレポリマーの水酸
基１当量に対してイソシアネート基が０．１〜０．７当
量となる割合にすベきであり、特に好ましくは０．２〜
０．６当量となる割合とするのがよい。０．１当量未満
ではは、顔料の分散性、塗膜の物性、耐候性などが悪く
なり、０．７当量を超えると、反応物であるウレタン変
性ポリエステル樹脂の分子量が高くなりすぎて、他の塗
料用の各種樹脂との相溶性が悪くなる。The amount of such a polyfunctional isocyanate compound to be used should be such that the amount of isocyanate group is 0.1 to 0.7 equivalent per equivalent of hydroxyl group of the amine-modified polyester prepolymer, and is particularly preferable. is 0.2~
It is preferable to set the ratio to be 0.6 equivalent. If the amount is less than 0.1 equivalent, the dispersibility of the pigment, physical properties of the coating film, weather resistance, etc. will deteriorate, and if it exceeds 0.7 equivalent, the molecular weight of the urethane-modified polyester resin, which is the reactant, will become too high, and other The compatibility with various resins for paints deteriorates.
【００２１】このようにして得られる本発明のウレタン
変性ポリエステル樹脂は、その水酸基価が４０〜２４０
で、数平均分子量が７００〜２０００に設定されている
ことが重要で、特に好ましくは水酸基価が５０〜１５０
で、数平均分子量が１０００〜１９００に設定されてい
るのがよい。また、酸価としては、通常１５以下である
のが望ましい。水酸基価が４０未満となつたり２４０を
超えてしまうと、塗膜の耐久性が悪くなつたり、塗料用
の各種樹脂との相溶性が悪くなる。また、数平均分子量
が７００未満では、塗膜の物性や耐候性などが悪くなり
、２０００を超えると、塗料用の各種樹脂との相溶性が
悪くなる。The urethane-modified polyester resin of the present invention thus obtained has a hydroxyl value of 40 to 240.
It is important that the number average molecular weight is set to 700 to 2000, and particularly preferably the hydroxyl value is set to 50 to 150.
The number average molecular weight is preferably set to 1,000 to 1,900. Further, the acid value is preferably 15 or less. When the hydroxyl value is less than 40 or exceeds 240, the durability of the coating film becomes poor and the compatibility with various resins for paints becomes poor. If the number average molecular weight is less than 700, the physical properties and weather resistance of the coating film will be poor, and if it exceeds 2000, the compatibility with various resins for paints will be poor.
【００２２】このようなウレタン変性ポリエステル樹脂
は、骨格がポリエステル樹脂からなるため、他の樹脂に
較べて本来低粘度で顔料の分散性にすぐれ、かつ他の樹
脂との相溶性も良好であるが、さらにこの分子内にアミ
ノ基と共にウレタン結合を導入し、併せて水酸基価が４
０〜２４０となる最適の溶解性パラメータ値に設定し、
またその分子量を塗膜形成機能と他の樹脂との相溶性と
を考慮した最適の範囲に設定していることにより、上記
本来の特性がさらに助長されて、顔料分散用として望ま
れるすぐれた性能を発揮する。[0022] Since such a urethane-modified polyester resin has a skeleton made of polyester resin, it has an inherently low viscosity and excellent pigment dispersibility compared to other resins, and also has good compatibility with other resins. Furthermore, a urethane bond is introduced into this molecule along with an amino group, and the hydroxyl value is 4.
Set the optimum solubility parameter value between 0 and 240,
In addition, by setting its molecular weight to an optimal range that takes into account film-forming function and compatibility with other resins, the above-mentioned original properties are further enhanced, and the excellent performance desired for pigment dispersion is achieved. demonstrate.
【００２３】本発明において、上記のウレタン変性ポリ
エステル樹脂を顔料分散用樹脂として用いる場合、一般
にこの樹脂をベースとして、着色顔料、有機溶剤および
必要に応じて流動性調整剤、表面張力調整剤、顔料分散
剤などを配合して、各インター（単独顔料を分散させた
着色用原色塗料）を調製することができる。In the present invention, when the above-mentioned urethane-modified polyester resin is used as a resin for pigment dispersion, this resin is generally used as a base, and a colored pigment, an organic solvent, and if necessary, a fluidity regulator, a surface tension regulator, and a pigment are added. Each inter (primary color paint for coloring in which a single pigment is dispersed) can be prepared by blending a dispersant and the like.
【００２４】着色顔料としては、酸化チタン、弁柄、ク
ロムイエローなどの無機顔料、フタロシアニンブルー、
キナクリドン系、ペリレン系、アゾ系などの有機顔料、
カーボンブラツクなどが挙げられるが、これらに限定さ
れることなく、塗料用として一般に用いられている着色
顔料のすべてを使用できる。Coloring pigments include inorganic pigments such as titanium oxide, Bengara, chrome yellow, phthalocyanine blue,
Organic pigments such as quinacridone, perylene, and azo pigments,
Examples include, but are not limited to, carbon black, and all color pigments commonly used for paints can be used.
【００２５】有機溶剤としては、炭化水素系、エステル
系、ケトン系、アルコール系、グリコール系などの溶剤
が挙げられるが、これらに限定されず、塗料用として一
般に用いられている各種の有機溶剤を広く使用できる。Examples of organic solvents include, but are not limited to, hydrocarbon-based, ester-based, ketone-based, alcohol-based, and glycol-based solvents. Can be used widely.
【００２６】[0026]
【発明の効果】本発明の顔料分散用樹脂は、各種の有機
顔料、無機顔料に対して良好な分散性を示し、また塗料
用に用いられる樹脂の多くと良好な相溶性を示すので、
この樹脂に顔料を分散させたインターは、常温乾燥型ア
ルキド塗料、焼き付け型アルキド塗料、常温乾燥型アク
リル塗料、焼き付け型アクリル塗料、塩化ビニル系塗料
、エポキシ系塗料、ニトロセルローズ系塗料などの塗料
の着色用として使用することができ、その結果インター
の種類を大幅に減少させ、塗料の生産性を著しく向上さ
せることができる。Effects of the Invention The pigment dispersing resin of the present invention exhibits good dispersibility for various organic pigments and inorganic pigments, and also exhibits good compatibility with many resins used for paints.
Inter, which has pigments dispersed in this resin, can be used for paints such as room temperature drying alkyd paints, baking type alkyd paints, room temperature drying type acrylic paints, baking type acrylic paints, vinyl chloride paints, epoxy paints, and nitrocellulose paints. It can be used for coloring, and as a result, the number of interspersions can be greatly reduced, and the productivity of paints can be significantly improved.
【００２７】[0027]
【実施例】つぎに、実施例および比較例により、本発明
の内容をより具体的に説明する。なお、例中の部は、重
量部である。また、以下の実施例および比較例で用いた
アミン変性または未変性のポリエステルプレポリマー溶
液Ｅ１〜Ｅ８、ウレタン変性ポリエステル樹脂溶液ＵＥ
１〜ＵＥ７、試験用アクリルワニスＡＣ９は、それぞれ
つぎの方法で調製した。[Examples] Next, the content of the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that parts in the examples are parts by weight. In addition, amine-modified or unmodified polyester prepolymer solutions E1 to E8, urethane-modified polyester resin solutions UE used in the following Examples and Comparative Examples
1 to UE7 and test acrylic varnish AC9 were each prepared in the following manner.
【００２８】＜ポリエステルプレポリマー溶液の調製＞
撹拌機、精留塔、水分離器冷却管、温度計および窒素ガ
ス吹き込み口を備えたフラスコに、つぎの表１，表２に
示す配合に基づき、多塩基酸および多価アルコール、ま
たはこれらとアミノアルコールとを仕込み、窒素ガス雰
囲気中で加熱撹拌し、１６０℃から２３０℃まで、生成
する縮合水を系外へ留去させながら、４時間かけて一定
昇温速度で昇温させた。<Preparation of polyester prepolymer solution>
Into a flask equipped with a stirrer, a rectification column, a water separator cooling tube, a thermometer, and a nitrogen gas inlet, add polybasic acids and polyhydric alcohols, or their combinations, based on the formulations shown in Tables 1 and 2 below. The mixture was heated and stirred in a nitrogen gas atmosphere, and the temperature was raised from 160°C to 230°C at a constant temperature increase rate over 4 hours while distilling the condensed water produced out of the system.
【００２９】その後、キシレン１．５部を徐々に添加し
、温度２３０℃に維持して縮合反応を続けた。酸価１０
以下になつたとき反応を終了し、残りのキシレンにて希
釈し、８種類のポリエステルプレポリマー溶液Ｅ１〜Ｅ
８を得た。このうち、試料番号Ｅ６はアミン未変性のポ
リエステルプレポリマー溶液で、他はすべてアミン変性
のポリエステルプレポリマー溶液である。Thereafter, 1.5 parts of xylene was gradually added, and the condensation reaction was continued while maintaining the temperature at 230°C. Acid value 10
When the following is reached, the reaction is terminated, diluted with the remaining xylene, and 8 types of polyester prepolymer solutions E1 to E are prepared.
I got 8. Among these, sample number E6 is an amine-unmodified polyester prepolymer solution, and all the others are amine-modified polyester prepolymer solutions.
【００３０】得られた各ポリエステルプレポリマーの数
平均分子量、水酸基価および酸価を測定し、その結果を
、各ポリエステルプレポリマーの製造に用いたアミノア
ルコールの原料全体中に占める割合（重量％）および各
ポリエステルプレポリマー溶液の固形分濃度と共に、表
１，表２に併記した。なお、ポリエステルプレポリマー
溶液Ｅ８の粘度（ガードナー；２５℃）は、Ｚ３であつ
た。The number average molecular weight, hydroxyl value and acid value of each polyester prepolymer obtained are measured, and the results are calculated as the proportion (wt%) of the amino alcohol used in the production of each polyester prepolymer in the total raw material. and the solid content concentration of each polyester prepolymer solution are also listed in Tables 1 and 2. The viscosity (Gardner; 25° C.) of the polyester prepolymer solution E8 was Z3.
【００３１】[0031]
【表１】[Table 1]
【００３２】[0032]
【表２】[Table 2]
【００３３】＜ウレタン変性ポリエステル樹脂溶液の調
製＞上記で調製したポリエステルプレポリマー溶液Ｅ１
〜Ｅ７を、それぞれ８０℃に冷却したのち、下記の表３
，表４に示す多官能イソシアネート化合物を加え、８０
℃で３時間撹拌を続けながら、赤外級吸収スペクトル分
析で未反応のイソシアネート基を追跡した。イソシアネ
ート基が消失した時点で反応を終了し、７種類のウレタ
ン変性ポリエステル樹脂溶液ＵＥ１〜ＵＥ７を得た。<Preparation of urethane-modified polyester resin solution> Polyester prepolymer solution E1 prepared above
~E7, respectively, after cooling to 80°C, the following Table 3
, the polyfunctional isocyanate compounds shown in Table 4 were added, and 80
While stirring was continued for 3 hours at °C, unreacted isocyanate groups were monitored by infrared absorption spectrum analysis. The reaction was terminated when the isocyanate group disappeared, and seven types of urethane-modified polyester resin solutions UE1 to UE7 were obtained.
【００３４】得られた各ウレタン変性ポリエステル樹脂
の水酸基価、数平均分子量および酸価を測定し、その結
果を、各ウレタン変性ポリエステル樹脂溶液の固形分濃
度および粘度（ガードナー；２５℃）と共に、表３，表
４に併記した。The hydroxyl value, number average molecular weight and acid value of each of the obtained urethane-modified polyester resins were measured, and the results are tabulated along with the solid content concentration and viscosity (Gardner; 25°C) of each urethane-modified polyester resin solution. 3. Also listed in Table 4.
【００３５】[0035]
【表３】[Table 3]
【００３６】[0036]
【表４】[Table 4]
【００３７】＜試験用アクリルワニスの調製＞キシレン
４０部およびブチルアルコール１０部を投入し、１３５
℃に昇温してこれら溶剤を還流させている反応容器中に
、メタクリル酸メチル２８部、アクリル酸ブチル１３部
、メタクリル酸β−ヒドロキシエチル５部、アクリル酸
１部およびクメンハイドロパーオキサイド１部の混合液
を、３時間かけて滴下し、さらに同温度で２時間撹拌を
続けて、試験用アクリルワニスＡＣ９を得た。<Preparation of acrylic varnish for testing> Add 40 parts of xylene and 10 parts of butyl alcohol,
28 parts of methyl methacrylate, 13 parts of butyl acrylate, 5 parts of β-hydroxyethyl methacrylate, 1 part of acrylic acid, and 1 part of cumene hydroperoxide are placed in a reaction vessel heated to ℃ and refluxing these solvents. The mixed solution was added dropwise over 3 hours, and stirring was continued for 2 hours at the same temperature to obtain test acrylic varnish AC9.
【００３８】実施例１〜３および比較例１〜５表３に示
すウレタン変性ポリエステル樹脂溶液ＵＥ１〜ＵＥ３を
本発明の顔料分散用樹脂溶液（実施例１〜３）とし、ま
た表４に示すウレタン変性ポリエステル樹脂溶液ＵＥ４
〜ＵＥ７および表２に示すアミン変性ポリエステルプリ
ポリマー溶液Ｅ８を比較用の顔料分散用樹脂溶液（比較
例１〜５）とした。Examples 1 to 3 and Comparative Examples 1 to 5 The urethane modified polyester resin solutions UE1 to UE3 shown in Table 3 were used as the resin solutions for pigment dispersion of the present invention (Examples 1 to 3), and the urethane modified polyester resin solutions UE1 to UE3 shown in Table 4 were used as the resin solutions for pigment dispersion of the present invention (Examples 1 to 3). Modified polyester resin solution UE4
~UE7 and the amine-modified polyester prepolymer solution E8 shown in Table 2 were used as comparative pigment dispersion resin solutions (Comparative Examples 1 to 5).
【００３９】これらの各顔料分散用樹脂溶液を用いて、
以下の相溶性試験（試験Ｉ）、塗料調合試験（試験ＩＩ
）および調色試験（試験ＩＩＩ）を行つた。Using each of these pigment dispersion resin solutions,
The following compatibility test (Test I), paint formulation test (Test II)
) and a color toning test (Test III) were conducted.
【００４０】＜試験Ｉ；相溶性試験＞下記の表５に示す
４種類の一般的な塗料用ワニスと、各顔料分散用樹脂溶
液とを、樹脂固形分の重量比が８／２となるように混合
し、この混合液をガラス板上に塗布したのち、乾燥塗膜
の濁りの具合を調べた。透明なものを○（合格）、濁り
のあるものを×（不合格）、で表した。結果を表５に併
記した。<Test I; Compatibility test> Four types of general paint varnish shown in Table 5 below and each resin solution for pigment dispersion were mixed so that the weight ratio of the resin solid content was 8/2. After applying this mixture onto a glass plate, the degree of turbidity of the dried coating film was examined. Transparent samples were marked with ○ (pass), and cloudy samples were marked with × (fail). The results are also listed in Table 5.
【００４１】[0041]
【表５】[Table 5]
【００４２】なお、表５中、「常温乾燥型アルキドワニ
ス」は油長６０％大豆油脂肪酸変性フタル酸ワニス（固
形分５５重量％）、「メラミン／アルキドワニス」はｎ
−ブタノール変性メラミン樹脂ワニスと油長４０％大豆
油脂肪酸変性フタル酸ワニスとの固形分重量比２／８の
混合ワニス（固形分５０重量％）、「メラミン／アクリ
ルワニス」はｎ−ブタノール変性メラミン樹脂ワニスと
試験用アクリルワニスＡＣ９との固形分重量比２／８の
混合ワニス（固形分５０重量％）、「塩化ビニルワニス
」は塩化ビニル−酢酸ビニル共重合体ワニス（ユニオン
カーバイド社製のビニライトＶＡＧＨ；固形分２０重量
％）、である。In Table 5, "room temperature drying alkyd varnish" is 60% oil length soybean oil fatty acid modified phthalic acid varnish (solid content 55% by weight), "melamine/alkyd varnish" is n
-Mixture varnish (solid content 50% by weight) of butanol-modified melamine resin varnish and 40% oil length soybean oil fatty acid-modified phthalic acid varnish (solid content 50% by weight), "melamine/acrylic varnish" is n-butanol-modified melamine A mixed varnish (solid content 50% by weight) of resin varnish and test acrylic varnish AC9 at a solid content weight ratio of 2/8, "vinyl chloride varnish" is a vinyl chloride-vinyl acetate copolymer varnish (Vinylite VAGH manufactured by Union Carbide) ; solid content 20% by weight).
【００４３】＜試験ＩＩ；塗料調合試験＞§インター白
の調製
各顔料分散用樹脂溶液をベースにして、その各２０部に
対し酸化チタンＲＣＲ３（ＢＴＰ社）を６０部、キシレ
ンを１５部、メトキシプロピルアセテート（以下、ＭＰ
Ａという）を５部混合し、サンドミルにより粒度が１０
μｍ以下となるまで分散して、８種類のインター白Ｗ１
〜Ｗ８を調製した。<Test II; Paint formulation test> Preparation of interwhite Based on each pigment dispersion resin solution, for each 20 parts, 60 parts of titanium oxide RCR3 (BTP), 15 parts of xylene, and methoxy Propyl acetate (hereinafter referred to as MP
5 parts of A) were mixed and sand milled to a particle size of 10.
8 types of inter white W1 are dispersed until it becomes less than μm.
~W8 was prepared.
【００４４】§白塗料の調製
上記のインター白Ｗ１〜Ｗ８の各３０部と、試験用アク
リルワニスＡＣ９（固形分５０重量％）５８部と、メラ
ミンワニス〔日立化成工業（株）製のメラン＃２８；固
形分６０重量％〕１２部とを混合し、８種類の白塗料Ｗ
Ｐ１〜ＷＰ８を調製した。この各塗料を、キシレンとＭ
ＰＡとの重量比７／３の混合シンナーを用いて、スプレ
ー可能な粘度にまで希釈した。§ Preparation of white paint 30 parts each of the above Interwhites W1 to W8, 58 parts of test acrylic varnish AC9 (solid content 50% by weight), and melamine varnish [Melan # manufactured by Hitachi Chemical Co., Ltd.] 28; Solid content 60% by weight] 12 parts and 8 types of white paint W
P1 to WP8 were prepared. These paints are mixed with xylene and M
It was diluted to a sprayable viscosity using a mixed thinner with PA in a 7/3 weight ratio.
【００４５】§塗膜の形成
上記の如く希釈した白塗料ＷＰ１〜ＷＰ８を、燐酸亜鉛
処理をした０．８ｍｍ×７０ｍｍ×１５０ｍｍの鋼板（
以下、処理鋼板という）に、乾燥膜厚が３０μｍとなる
ようにスプレー塗装し、１４０℃，２０分の焼き付けを
行つたのち、塗面状態、塗膜物性および耐久性を評価し
た。その結果を下記の表６に示した。§ Formation of coating film The white paints WP1 to WP8 diluted as above were applied to a 0.8 mm x 70 mm x 150 mm steel plate (
The coated steel sheet (hereinafter referred to as treated steel sheet) was spray coated to a dry film thickness of 30 μm, baked at 140° C. for 20 minutes, and then the coated surface condition, coated film physical properties, and durability were evaluated. The results are shown in Table 6 below.
【００４６】[0046]
【表６】[Table 6]
【００４７】なお、表６中、「６０度鏡面光沢度」はＪ
ＩＳ−Ｋ−５４００（１９７９）６．７にしたがい、８
０以上を合格とした。「鉛筆引つかき試験」はＪＩＳ−
Ｋ−５４００（１９７９） ６．１４にしたがい、Ｈ
Ｂより硬いものを合格とした。「碁盤目試験」はＪＩＳ
−Ｋ−５４００（１９７９） ６．１５にしたがい、
１０点を合格、８点以下を不合格とした。また、「耐衝
撃性」はＪＩＳ−Ｋ−５４００（１９７９） ６．１
３．３ Ｂ法にしたがい、４０ｃｍ以上を合格とした
。「促進耐候試験」はＪＩＳ−Ｋ−５４００（１９７９
） ６．１７にしたがい、８００時間試験後の６０度
鏡面光沢度の保持率（％）として、〔（試験後の光沢度
）／（初期光沢度）〕×１００を測定し、７０％以上を
合格とした。[0047] In Table 6, "60 degree specular gloss" is J
According to IS-K-5400 (1979) 6.7, 8
A score of 0 or more was considered a pass. "Pencil traction test" is JIS-
According to K-5400 (1979) 6.14, H
Those harder than B were accepted. "Checker board test" is JIS
-K-5400 (1979) 6.15,
A score of 10 points was considered a pass, and a score of 8 or less was considered a fail. In addition, "impact resistance" is JIS-K-5400 (1979) 6.1
3.3 According to method B, a length of 40 cm or more was considered to be a pass. "Accelerated weathering test" is JIS-K-5400 (1979
) According to 6.17, the retention rate (%) of the 60 degree specular gloss after the 800-hour test was determined as [(gloss after test)/(initial gloss)] x 100, and 70% or more was determined. Passed.
【００４８】＜試験ＩＩＩ；調色試験＞§９インター黒
の調製
各顔料分散用樹脂溶液をベースにして、その各６０部に
対しカーボンブラツク（ＣＯＬＯＲ ＢＬＡＣＫ
ＦＷ２００：デクサ社）を５部、キシレンを２５部、Ｍ
ＰＡを１０部混合し、サンドミルで粒度が１０μｍ以下
となるまで分散して、８種類のインター黒Ｂ１〜Ｂ８を
調製した。<Test III; Toning test> §9 Preparation of inter black Based on the resin solution for dispersing each pigment, add carbon black (COLOR BLACK) to 60 parts of each resin solution.
FW200: Dexa) 5 parts, xylene 25 parts, M
Eight types of interblacks B1 to B8 were prepared by mixing 10 parts of PA and dispersing the mixture in a sand mill until the particle size became 10 μm or less.
【００４９】§インター青の調製
各顔料分散用樹脂溶液をベースにして、その各５０部に
対しフタロシアニンプルー〔リオノールブルーＰＲＸ；
東洋インキ製造（株）製〕を３０部、キシレンを１５部
、ＭＰＡを５部混合し、サンドミルで粒度が１０μｍ以
下となるまで分散して、８種類のインター青Ｆ１〜Ｆ８
を調製した。Preparation of Inter Blue Based on each pigment dispersion resin solution, 50 parts of each are mixed with phthalocyanine blue [Lionol Blue PRX;
Toyo Ink Mfg. Co., Ltd.], 30 parts of xylene, 15 parts of MPA, and 5 parts of MPA were mixed and dispersed in a sand mill until the particle size was 10 μm or less to produce 8 types of Inter Blue F1 to F8.
was prepared.
【００５０】§調色塗料の調製
試験ＩＩで調製した前記８種の白塗料ＷＰ１〜ＷＰ８の
各９０部と、上記のインター黒Ｂ１〜Ｂ８の各５部と、
上記のインター青Ｆ１〜Ｆ８の各５部とを、下記の表７
に示す組み合わせで混合し、８種類の調色塗料Ｐ１〜Ｐ
８を調製した。§90 parts each of the eight types of white paints WP1 to WP8 prepared in the toning paint preparation test II, and 5 parts each of the above interblacks B1 to B8,
5 parts each of Inter Blue F1 to F8 above, and Table 7 below.
Eight types of toning paints P1 to P are mixed in the combinations shown below.
8 was prepared.
【００５１】[0051]
【表７】[Table 7]
【００５２】§塗膜物性および放置安定性上記の調色塗
料Ｐ１〜Ｐ８について、以下のラビングテスト、６０度
鏡面光沢度テストおよびスタンデイングテストに供した
。結果を表７に併記した。§Coating film properties and storage stability The above-mentioned toning paints P1 to P8 were subjected to the following rubbing test, 60 degree specular gloss test and standing test. The results are also listed in Table 7.
【００５３】〔ラビングテスト〕上記の調色塗料Ｐ１〜
Ｐ８をキシレンとＭＰＡとの重量比７／３の混合シンナ
ーでスプレー可能な粘度にまで希釈し、この希釈塗料を
、５０ｍｍ×１５０ｍｍブリキ板に流し塗りし、室温で
３分間室内に静置したのち、塗面を指でこすつて、こす
らない部分との色の差を比較した。色差のほとんどない
ものを○、色差の大きいものを×とした。[Rubbing test] The above color toning paints P1~
P8 was diluted to a sprayable viscosity with a thinner mixture of xylene and MPA in a weight ratio of 7/3, and this diluted paint was poured onto a 50 mm x 150 mm tin plate, left to stand indoors for 3 minutes at room temperature, and then , I rubbed the painted surface with my finger and compared the difference in color with the part that was not rubbed. A sample with almost no color difference was graded ○, and a sample with a large color difference was graded x.
【００５４】〔６０度鏡面光沢度テスト〕ラビングテス
トに使用したブリキ板を、さらに１４０℃，２０分焼き
付けて乾燥させ、塗膜の光沢度を測定した。８０以上を
合格とした。[60 degree specular gloss test] The tin plate used in the rubbing test was further baked and dried at 140° C. for 20 minutes, and the gloss of the coating film was measured. A score of 80 or higher was considered a pass.
【００５５】〔スタンデイングテスト〕ラビングテスト
で調製した各希釈塗料を試験管に入れ、３日後に色分か
れの状態を観察した。色分かれ、色浮きのほとんどない
ものを○、色分かれ、色浮きのはげしいものを×とした
。[Standing Test] Each diluted paint prepared in the rubbing test was placed in a test tube, and the state of color separation was observed after 3 days. Those with almost no color separation or color floating were rated as ○, and those with severe color separation or color floating were rated as ×.
【００５６】以上の表５〜表７の結果から明らかなよう
に、本発明の顔料分散用樹脂は、塗料用の各種樹脂と良
好な相溶性があり、かつすぐれた顔料分散性を示すもの
であることがわかる。As is clear from the results in Tables 5 to 7 above, the pigment dispersing resin of the present invention has good compatibility with various resins for paints and exhibits excellent pigment dispersibility. I understand that there is something.
Claims (1)
にポリエステルプレポリマーの原料中０．５〜７．０重
量％となる割合のアミノアルコールを必須成分として用
いて縮合反応させて得た数平均分子量が３５０〜１５０
０、水酸基価が１００〜３００のアミン変性ポリエステ
ルプレポリマーに、このプレポリマーの水酸基１当量に
対してイソシアネート基が０．１〜０．７当量となる割
合の多官能イソシアネート化合物を反応させて得られる
、水酸基価が４０〜２４０、数平均分子量が７００〜２
０００のウレタン変性ポリエステル樹脂からなることを
特徴とする顔料分散用樹脂。Claim 1: A number average obtained by a condensation reaction using, in addition to a polybasic acid and a polyhydric alcohol, an amino alcohol in a proportion of 0.5 to 7.0% by weight in the raw material of the polyester prepolymer as an essential component. Molecular weight is 350-150
0. Obtained by reacting an amine-modified polyester prepolymer with a hydroxyl value of 100 to 300 with a polyfunctional isocyanate compound in a proportion of 0.1 to 0.7 equivalents of isocyanate groups per 1 equivalent of hydroxyl groups in this prepolymer. with a hydroxyl value of 40 to 240 and a number average molecular weight of 700 to 2.
A resin for pigment dispersion characterized by comprising a urethane-modified polyester resin of No. 000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418124A JP2861402B2 (en) | 1990-12-21 | 1990-12-21 | Pigment dispersion resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2418124A JP2861402B2 (en) | 1990-12-21 | 1990-12-21 | Pigment dispersion resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04220424A true JPH04220424A (en) | 1992-08-11 |
| JP2861402B2 JP2861402B2 (en) | 1999-02-24 |
Family
ID=18526064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2418124A Expired - Fee Related JP2861402B2 (en) | 1990-12-21 | 1990-12-21 | Pigment dispersion resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2861402B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151874A (en) * | 1999-12-01 | 2001-06-05 | Toyobo Co Ltd | Lactic acid-based copolyester |
| KR20050035208A (en) * | 2005-02-22 | 2005-04-15 | 주식회사 청우 씨에프씨 | A high molecule urethane rebirth ester paint dispersing agant |
-
1990
- 1990-12-21 JP JP2418124A patent/JP2861402B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151874A (en) * | 1999-12-01 | 2001-06-05 | Toyobo Co Ltd | Lactic acid-based copolyester |
| JP4565289B2 (en) * | 1999-12-01 | 2010-10-20 | 東洋紡績株式会社 | Lactic acid type copolyester |
| KR20050035208A (en) * | 2005-02-22 | 2005-04-15 | 주식회사 청우 씨에프씨 | A high molecule urethane rebirth ester paint dispersing agant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2861402B2 (en) | 1999-02-24 |
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