CN1132772A - Pigment dispersion composition for electrodiposition coating for coloring - Google Patents
Pigment dispersion composition for electrodiposition coating for coloring Download PDFInfo
- Publication number
- CN1132772A CN1132772A CN95119894A CN95119894A CN1132772A CN 1132772 A CN1132772 A CN 1132772A CN 95119894 A CN95119894 A CN 95119894A CN 95119894 A CN95119894 A CN 95119894A CN 1132772 A CN1132772 A CN 1132772A
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- CN
- China
- Prior art keywords
- pigment
- dispersion
- water
- painted
- pigment dispersion
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
Abstract
The invention relates to a copolymer or a metamorphic body which contains styrene or derivant thereof and one or more than two monomers that can polymerize with the styrene. Organic pigment is dispersed in water or water containing water-soluble organic solvent to form a pigment dispersion compound used in colored electrophoretic finishing. The dispersity of the pigment and the intermiscibility of pigment particles and emulsion particles of the electrophoretic finishing are excellent.
Description
The present invention relates to the pigment dispersion composition that painted electrophoretic painting is used.
About electrophoretic painting, existing many for improving adhesivity, the painted scheme that proposes on coated article.The Japanese patent gazette specification sheets is this scheme 1975 No. 1137 and 1985 the 36796th, No. 124298, but as described in the Japanese Patent prospectus 1992 No. 154999, not perfect.
The Japanese Patent prospectus discloses for 1992 No. 154999 a kind of by at the particle surface of pigment dyestuff coating acrylic polymers or multipolymer, thus improve pigment particles in coating dispersiveness and boldness, tint retention, transparency, the weathering resistance of electroplating film and improve the scheme of operability, pattern aesthetic feeling and film performance.
Promptly, the Japanese Patent prospectus discloses for 1992 No. 154999 a kind of by using the proportion pigment dyestuff lighter than existing mineral dye, thereby it is different during with the use mineral dye, do not need in painted groove, to stir etc. always and improved operability, improved the distinctiveness of mineral dye simultaneously and improved the scheme of pattern aesthetic feeling etc.
Yet, the generation of color spot when hardening for preventing to cure, and when leaving standstill in the painted groove midium or long term pigment particles sedimentation with prevent that pigment particles from separating with the electrophoretic painting emulsion particle, need two kinds of particles that very excellent intermiscibility and dispersing of pigments be arranged in dispersion medium.The sedimentation of the pigment of the dispersion of painted usefulness self is self-evident, if bad dispersibility when prolonged preservation, pigment sedimentation in dispersion can take place, makes the operability variation.
In this, the invention that the Japanese Patent prospectus is 1992 No. 154999 is not perfect, need improve dispersing of pigments and with the intermiscibility of electrophoretic painting emulsion particle.
The pigment dispersion composition that the object of the present invention is to provide a kind of dispersing of pigments, pigment particles in dispersion medium, to use with the painted electrophoretic painting of the intermiscibility excellence of electrophoretic painting emulsion particle.
When being in dry powder state, pigment particles is cohesion mutually, therefore, for improving dispersiveness, need make very small particle.If the particle diameter of dispersion is below 0.6 μ m, be preferably in below the 0.3 μ m, even place 1 month, the cohesion or the sedimentation of pigment also can not take place, also have,, do not add and stir ground placement 1 month even mix with the electrophoretic painting emulsion, do not see obvious sedimentation in the electrophoresis chamber yet, show that pigment has secular dispersion stabilization.
Making hydrophobic pigment particles dispersive dispersion agent in water is very important for obtaining good dispersiveness.The present inventor has done research repeatedly to this, found that it is effective to dispersion, the micronize of pigment dyestuff to contain cinnamic polymkeric substance, and good with the intermiscibility of electrophoretic painting emulsion particle.
This may be because the phenyl that imports in the multipolymer by vinylbenzene is lipophilicity, pigment and emulsion particle and this not mutual exclusion of multipolymer, thus dispersiveness, intermiscibility are improved.
As can with the monomer of the styrene derivatives copolymerization of vinylbenzene or alpha-methyl styrene and so on, can use and contain α such as being selected from vinylchlorid, vinyl-acetic ester, vinylformic acid, at least one monomer in β-vinyl-type monomer and derivative thereof, maleic anhydride and the derivative thereof.
Adding monomer in vinylbenzene or styrene derivatives, mainly is for polymer water being dissolved, if will import the stronger part of wetting ability, being preferably in and importing carboxylic acid group, sulfonic group, hydroxyl in the polymkeric substance.When the monomer in the multipolymer had than poly-hydroxy, sodium sulfonate group etc., sometimes, multipolymer itself was water-soluble.
The importing of hydroxyl can be by using vinylformic acid 2-hydroxyethyl ester as above-mentioned monomer or the polymkeric substance that has imported ethyl acetate is carried out saponification realize.The importing of sodium sulfonate group can realize by using monomers such as sodium allyl sulfonate, sodium methallyl sulfonate, Sodium styrene sulfonate to carry out polymerization.
After importing the carboxylic acid group, will have carboxylic acid groups' such as vinylformic acid, maleic anhydride monomer polymerization, add sodium hydroxide, ammoniacal liquor, sulfonamide derivatives neutralization again, polymer water is dissolved.If the organic solvent that uses in above-mentioned polymkeric substance is synthetic is water miscible, it all might not be removed.As mentioned above, make colo(u)rant dispersion by being used in the multipolymer that has imported hydrophilic water-solubleization group in the styrol copolymer, pigment particles after the dispersion all has affinity to hydrophobic electrophoretic painting emulsion particle and dispersion medium water, thereby makes the modulation of the very excellent coloring liquid of intermiscibility become possibility.
Be used for pigment dyestuff dispersive molecular weight of copolymer and be preferably weight-average molecular weight 5,000-500,000.Control molecular weight such as amount that can be by regulating polymerization starter, polymerization temperature.
If the molecular weight of multipolymer is less than 5,000, it is residual to have a large amount of water insoluble active ingredients, causes the dispersing of pigments bad stability.And if greater than 500,000, the viscosity that then has dispersion is excessive, when dispersed color, can not micronize etc. problem.
To this, if the weight-average molecular weight of multipolymer is between 5,000-500,000, and addition is the 10-100% (weight) of pigment, then can obtain dispersion low viscous, below micronize to the 0.3 μ m, that have good stability.
As spendable pigment dyestuff, phthualocyanine pigment, dioxazine series pigments, indanthrone series pigments, isoindoline ketone series pigments, diketopyrrolopyrrolecocrystals series pigments, quinoline a word used for translation ketone series pigments, perylene pigments, anthraquione pigmentss etc. being arranged and closing how ring-like pigment of photostabilization excellence can be suitable for, certainly, without any exception, also can use azo pigment of being widely used, have rich colors etc.
Pigment dyestuff (trade(brand)name: シ ゲ ノ Star Network ス, Ha Star コ-Le ケ ミ カ Le company production) to white is also studied, and it and colored pigment dyestuff similarly can be suitable for.
As the method for dispersed color, can use methods such as the ball milling commonly used, sand milling, roll-type grinding.
In the dispersion process, can use di-alcohols and water-miscible organic solvents such as their ester or alkanolamine such as alcohols such as methyl alcohol, ethanol, ethylene glycol, propylene glycol aptly, carry out the adjusting of evaporation rate of the solvent of painted bath or painted thing.
Also can use various tensio-active agents, carry out the adjusting of the painted bath of dispersion or the surface tension of painted thing etc.
Get final product if mix the electrophoretic paint anionic of pigment dispersion of the present invention, representational example has vinylformic acid-trimeric cyanamide emulsion coatings, fluoro-trimeric cyanamide emulsion coatings etc.
The resinous principle that contains in the electrophoretic paint is preferably 5-40% (weight), when painted, preferably adds this dispersion, making pigment concentration is 0.5-20% (weight), yet electrophoresis can be regulated color thus being changed along with addition by the amount of pigment on filming.
The present invention is owing to be a kind of by making pigment dyestuff be dispersed in water with the two or more monomeric multipolymer that contains the vinylbenzene or derivatives thereof or its sex change body or containing the painted electrophoretic painting pigment dispersion composition that forms in the water of water-miscible organic solvent; dispersion, micronize to pigment dyestuff have useful effect, can improve the intermiscibility of pigment dyestuff and electrophoretic paint emulsion particle.
In addition, use α, β-vinyl-type monomer and/or its derivative or maleic anhydride and/or its derivative can make water-solubleization of multipolymer as with vinylbenzene or derivatives thereof blended monomer the time, improve its dispersion stabilization.
Also have,, add, can obtain the dispersion that has good stability low viscous, below micronize to the 0.3 μ m with the addition of the 10-100% (weight) that is equivalent to pigment if the weight-average molecular weight of multipolymer is adjusted between 5,000-500,000.
Embodiment 1
Press the resin (multipolymer) of the synthetic various colo(u)rant dispersion body and functions of condition shown in the table 1, press the pigment preparation of matching requirements shown in the table 2 dispersion composite, with each pigment dispersion composition practical application, carry out electrophoretic painting, estimate the state of electrophoresis chamber and the color spot after the roasting.(synthesizing of the resin of colo(u)rant dispersion body and function)
Monomer, polymerization starter with table 1 are formed, with ethylene glycol monobutyl ether, diox, tetrahydrofuran (THF) is solvent, reacts elimination reppd material in hexane by common solution polymerization process (method of dripping) down at 80-150 ℃, drying obtains resin (multipolymer) solid substance.
This solid substance with the dissolving that neutralize of the water solvation of regulation, is prepared resinous principle and is 6 kinds of 30% resin aqueous solutions in water.
Table 1
Unit: mole %
Polymkeric substance 1 | Polymkeric substance 2 | Polymkeric substance 3 | Polymkeric substance 4 | Polymkeric substance 5 | Polymkeric substance 6 | |
Vinylbenzene | ????60 | ????70 | ????50 | ????10 | ????60 | |
Vinylformic acid | ????20 | ????20 | ????20 | ????30 | ||
Vinylformic acid 2-hydroxyethyl ester | ????20 | ????10 | ????10 | ????20 | ????20 | ????20 |
Maleic anhydride | ????20 | ????10 | ||||
Styrene sulfonic acid | ????60 | |||||
Methyl methacrylate | ????10 | ????50 | ||||
Ethyl propenoate | ????10 | ????10 | ||||
The polymerization starter amount | ????2.5 | ????2 | ????1.5 | ????1 | ????0.1 | ????1.5 |
Weight-average molecular weight | 5,000 | 20,000 | 70,000 | 400,000 | 600,000 | 80,000 |
The water solvation | ????NaOH | Ammoniacal liquor | Triethylamine | Do not have | ????NaOH | Ammoniacal liquor |
(preparation of pigment dispersion)
Press the pigment preparation of proportioning shown in the table 2 dispersion.
Table 2
Unit: mole %
Dispersion 1 polymkeric substance 1 | Dispersion 2 polymkeric substance 2 | Dispersion 3 polymkeric substance 3 | Dispersion 4 polymkeric substance 4 | Dispersion 5 polymkeric substance 5 | Dispersion 6 polymkeric substance 6 | |
The blue TGB of Off ア ス ト ゲ Application 1) | ????15 | ????15 | ||||
The red BL of イ Le ガ ジ Application DPP 2) | ????25 | |||||
イルガジンエロ-2RLT 3) | ????20 | ????20 | ||||
シゲノツクスOWP 4) | ????10 | |||||
Resin aqueous solution | ????50 | ????25 | ????30 | ????50 | ????50 | ????30 |
Triethylamine | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 |
Propylene glycol | ????10 | ????20 | ????20 | ????15 | ????10 | ????20 |
Ion exchanged water | ????20 | ????25 | ????25 | ????20 | ????20 | ????25 |
[dispersion characteristic] 5) | Dispersion 1 | Dispersion 2 | Dispersion 3 | Dispersion 4 | Dispersion 5 | Dispersion 6 |
Initial stage viscosity [cP] | ????12 | ????14 | ????18 | ????32 | ????130 | ????27 |
Initial stage particle diameter [μ m] | ????0.12 | ????0.26 | ????0.18 | ????0.35 | ????0.62 | ????0.26 |
1 month postprecipitation 6) | ????○ | ????△ | ????○ | ????△ | ????× | * (aggegation) |
In the table 2,
1) big Japanese ink company product, phthualocyanine pigment
2) Ciba-Geigy company product, the diketopyrrolopyrrolecocrystals series pigments
3) Ciba-Geigy company product, isoindoline ketone series pigments
4) Ha Star コ-Le ケ ミ カ Le company product, white pigment dyestuff
5) being diluted to pigment concentration is 10%, measures after Sharples (Scharples) is handled
6) enclose in the closed type test tube, place and measure precipitation thickness after 1 month
Zero: do not find △: less than 5mm *: greater than 5mm
Being formulated in the granulated glass sphere grinding machine (beads mill) of pigment dispersion carried out, and proportioning and characteristic thereof during preparation also are illustrated in the table 2 in the lump.(electrophoretic painting test)
To have the aluminium sheet of anode oxide film of thickness 9 μ m after treatment as anode, carbon-point is as negative electrode, in the electrophoresis chamber of being furnished with above-mentioned anode and negative electrode, be full of with solution that contains vinylformic acid-trimeric cyanamide electrophoretic painting and the solution that contains pigment, making vinylformic acid-trimeric cyanamide electrophoretic painting concentration is 10%, and pigment concentration is 1%.After volts DS 120V energising 5 minutes, aluminium sheet 180 ℃ of baking processing 30 minutes, is finished japanning.
The state of this moment is as shown in table 3.
Table 3
Dispersion 1 polymkeric substance 1 | Dispersion 2 polymkeric substance 2 | Dispersion 3 polymkeric substance 3 | Dispersion 4 polymkeric substance 4 | Dispersion 5 polymkeric substance 5 | Dispersion 6 polymkeric substance 6 | |
The state of electrophoresis chamber (initial stage) | Homogeneous | Homogeneous | Homogeneous | Homogeneous | Homogeneous | Homogeneous |
〃 (do not have and stir painted back 10 times) | Homogeneous | Homogeneous | Homogeneous | Homogeneous | Homogeneous | Homogeneous |
〃 (do not have and stir after 1 month) | Homogeneous | Homogeneous | Homogeneous | Homogeneous | Precipitation is arranged | Precipitation is arranged |
Color spot after the baking | Do not have | Do not have | Do not have | Do not have | Have | Have |
Pigment dispersion composition of the present invention even with himself long-term placement, also the pigment sedimentation can not occur, mixes the back life-time service with electrophoretic paint shown in above-mentioned table 2 and table 3, electrophoresis liquid non-uniform phenomenon can not occur yet.In addition, because the emulsion particle in the electrophoretic paint and the intermiscibility of pigment improve, after the baking, the color spot of not finding to have been filmed takes place.In addition, the weight-average molecular weight of multipolymer is greater than 500,000 o'clock, shown in dispersion 5, the initial stage particle diameter of pigment particles is greater than 0.6 μ m, and the weight-average molecular weight of multipolymer is less than 500,000 o'clock, and the initial stage particle diameter of pigment particles can keep secular dispersion stabilization less than 0.6 μ m.Also have, especially at the initial stage of pigment particles particle diameter during less than 0.3 μ m, can obtain pigment particleization, disperse the secular dispersion that has good stability.
The present invention is owing to be that two or more monomeric multipolymers or its sex change body that a kind of usefulness contains the vinylbenzene or derivatives thereof is dispersed in water with pigment dyestuff or contains the painted electrophoretic painting pigment dispersion composition that forms in the water of water-miscible organic solvent, the intermiscibility excellence of dispersing of pigments, the pigment particles in dispersion medium and electrophoretic painting emulsion particle, color spot takes place in the time of can preventing baking hardening, also can prevent the sedimentation of pigment particles when leaving standstill, can not take place separating of pigment particles and electrophoretic painting emulsion particle in the painted groove midium or long term.
Claims (4)
1. pigment dispersion composition that painted electrophoretic painting is used, it is characterized in that, by with the vinylbenzene or derivatives thereof and can with one or two or more kinds monomeric multipolymer or its sex change body of its polymeric, make pigment dyestuff be dispersed in water or contain in the water of water-miscible organic solvent to form.
2. the pigment dispersion composition that painted electrophoretic painting as claimed in claim 1 is used is characterized in that, described monomer is for being selected from α, at least a in β-vinyl-type monomer and derivative thereof, maleic anhydride and the derivative thereof.
3. the pigment dispersion composition that painted electrophoretic painting as claimed in claim 1 or 2 is used is characterized in that, multipolymer or its sex change body contain any in carboxylic acid group, sulfonic group, the hydroxyl at least.
4. the pigment dispersion composition of using as each described painted electrophoretic painting among the claim 1-3 is characterized in that, the weight-average molecular weight of multipolymer or its sex change body is between 5,000 to 500,000.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP33829494A JP3386910B2 (en) | 1994-12-14 | 1994-12-14 | Pigment dispersion composition for colored electrodeposition coating |
JP338294/1994 | 1994-12-14 | ||
JP338294/94 | 1994-12-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1132772A true CN1132772A (en) | 1996-10-09 |
CN1060495C CN1060495C (en) | 2001-01-10 |
Family
ID=18316787
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95119894A Expired - Fee Related CN1060495C (en) | 1994-12-14 | 1995-12-13 | Pigment dispersion composition for electrodiposition coating for coloring |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP3386910B2 (en) |
KR (1) | KR960022891A (en) |
CN (1) | CN1060495C (en) |
TW (1) | TW336948B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7672265B2 (en) | 2001-08-24 | 2010-03-02 | Interdigital Technology Corporation | Method for physical layer automatic repeat request for a base station |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6596793B2 (en) * | 2000-06-13 | 2003-07-22 | Kansai Paint Co., Ltd. | Copolymer excelling in pigment dispersibility |
JP2002069144A (en) * | 2000-06-13 | 2002-03-08 | Kansai Paint Co Ltd | Copolymer excellent in pigment dispersibility |
CN106554683A (en) * | 2016-11-21 | 2017-04-05 | 郑州源冉生物技术有限公司 | A kind of compound propylene material of drawing |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6092360A (en) * | 1983-10-27 | 1985-05-23 | Kansai Paint Co Ltd | Aqueous pigment dispersion |
-
1994
- 1994-12-14 JP JP33829494A patent/JP3386910B2/en not_active Expired - Fee Related
-
1995
- 1995-10-27 TW TW084111441A patent/TW336948B/en active
- 1995-12-13 CN CN95119894A patent/CN1060495C/en not_active Expired - Fee Related
- 1995-12-13 KR KR1019950049383A patent/KR960022891A/en not_active Application Discontinuation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7672265B2 (en) | 2001-08-24 | 2010-03-02 | Interdigital Technology Corporation | Method for physical layer automatic repeat request for a base station |
US8102801B2 (en) | 2001-08-24 | 2012-01-24 | Interdigital Technology Corporation | User equipment for physical layer automatic repeat request |
Also Published As
Publication number | Publication date |
---|---|
JPH08165446A (en) | 1996-06-25 |
JP3386910B2 (en) | 2003-03-17 |
TW336948B (en) | 1998-07-21 |
KR960022891A (en) | 1996-07-18 |
CN1060495C (en) | 2001-01-10 |
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