TW201219504A - Aqueous white color paste and preparation method thereof - Google Patents

Abstract

The present invention relates to an aqueous white color paste and a preparation method thereof. Based on the mass of the color paste, the color paste comprises 5 to 8% of wetting agent, 50 to 65% of titanium white, 35 to 40% of dispersant, 0.3 to 0.6% of fungicide, 0.4 to 1% of defoaming agent and 1 to 5% of deionized water. The color paste has advantages such as good flowability, excellent storage stability, good compatibility and the like. It does not contain volatile organic compounds, nonyl, octyl phenol or ethoxylates, which is environment-friendly.

Description

201219504: Lai [Technical Field of Invention] The present invention relates to an environmentally-friendly water-based color paste and a preparation method thereof, in particular, a white water-based color paste y. The color paste is suitable for coloring of white paint on interior and exterior walls and &quot;ν&quot; ν <Preparation:. -· [Prior Art] In recent years, the exterior wall coatings are mainly made of hydrophilic coatings, and the hydrophilic color pastes are easy to obtain better storage in the aqueous system. ^ . . . ' . : .. .. ..... ........ ................................... Nearly all pigment pastes on the market are hydrophilic. At present, many companies developed by the company have focused on the development and development of environmentally friendly products, and the control of low volatile organic compounds and sulfhydryl groups, #phenol and their ethoxylates are not strictly controlled. In the sense of meeting environmental protection requirements; 丨 With the improvement of people's living standards, for the purpose of human health and environmental protection 'how to develop a good hydrophilicity, and in the product stability and environmental protection has a clear superiority Pigment color has always been a technical problem that is difficult to solve in the coloring field. . . . 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . High in nature, good in compatibility, free of volatile organic compounds and mercapto, octylphenol and its ethoxylates' environmentally friendly, to meet the environmental needs of current and future customers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 ....... ·. . ... .... .... .... . . : . ' . ' : …. ..… ... ...... . . 159079.doc 201219504 Now. Accordingly, the present invention includes the following: 1. An aqueous white color paste comprising, based on the mass of the color paste, a wetting agent of from 5% to 8%, such as 5.6%, 6.2% or 7.2%; titanium dioxide 50% to 65%, such as 52%, 54%, 56%, 57.5% or 61%; dispersant 35% to 40% 'eg 35%, 35.5%, 36% or 37%; fungicide 0.3% to 0.6% %, for example 0.4% or 0.5%; defoamer 0.4% to 1%, such as 0.5%, 0.7% or 0.9〇/〇; deionized water 1% to 5% 'eg 1%, 2%, 2_8% or 4 %. 2. The aqueous white color paste of the above 1, wherein the wetting agent is selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether and triethylene glycol butyl sulphate. At least one of them. 3. The aqueous white color paste according to the above 1 or 2, wherein the dispersing agent is at least two selected from the group consisting of a vinyl block copolymer, a propylene-based block copolymer, and an epoxy block copolymer. And other block copolymers having hydrophobic groups. 4. The aqueous white color paddle according to the above 3, wherein: the vinyl block copolymer is formed by polymerizing styrene monomer and ethylene monomer in the styrene monomer and the ethylene monomer to form the ethylene monomer. Substituted, or by F, Cl, Br, I ' -N02, -OH, -S03H, -C02H 'methyl, ethyl, propyl, isopropyl, butyl, t-butyl, tert-butyl Substituting at least one substituent for one or more times, the vinyl block copolymer having a weight average molecular weight of 15〇〇159079.doc 201219504 to 3000, preferably 2〇〇〇 to 25〇0; the propylene-based block copolymerization The polymer is formed by polymerizing at least one of a styrene monomer and an isobutylene monomer with a propylene monomer, which is unsubstituted or passed through . . . . . . . . . . . . F, Cl · at least one substituent of Br, hydrazine, -NOS, _〇H, -S03H, -C02H, decyl, ethyl, propyl, isopropyl, butyl, decylbutyl, and tert-butyl Substituting - or multiple times 'The acryl block copolymer has 15 〇〇.... . &quot; .......... ...... .... .. ;. ... .... . . . to 3 000, weighing from 2〇〇〇 to 25〇0 The average amount of breaks; .. ..... ... .. . 1 . . . . . . . . . . ... ..... ... . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. ...... .............. Formed together, with a weight average of 15〇0 to M00, preferably 2〇〇〇 to 25〇〇. ... ... ... ....... .... .. ·. . . . ----- . : ............. A block copolymer having a hydrophobic group consists of a clumsy monomer and an isobutylene..+++. . . . . . + ...+. .+... . : + ++ : ... + .+ .+. + .... .... ... at least one of the olefin monomers and (mercapto) propylene or its C1-C8 decyl vinegar, preferably C1, Cl, C3, C4 At least one of the base vinegars is formed by polymerization, with .....,.....'.: ... ........ .. . . - .. . A water-based white color paste of the above-mentioned 3 or 4, wherein: the vinyl block copolymer comprises A1B1, a 1 b 1A1, H A1B1, ... . &quot; ' ' - . I . ..... . . - A IB 1A1B1 at least one of the block concomitants, wherein ai Free

At least one of n1 in the shown segment, a block represented by Bl R3卩4, where r3, r4, ultra 5, and r6 | j are respectively -G-^-G-

Ll ι· R5 R6 ' ' ..... . . ... is independently Η, F, Cl, Br, I, -ν〇2, ·〇η, _S〇3H, ... . . . . -C〇2H, methyl, ethyl, propyl, isopropyl, butyl, second butyl or 159079.doc 201219504 tert-butyl, preferably, R3, R4, R5 and R6 are all hydrogen; Wherein ml is 5-15, m2 is 10-20, and nl is 15-25; and the propylene-based block copolymer comprises at least one of block copolymers represented by A2B2, A2B2A2, B2A2B2, and A2B2A2B2, wherein A2 is selected from

C—C is a block represented by at least one of the blocks represented by ml and r7 I r8 I 1 1 c- I 1 —c-1 Rg F , Cl C—c- n2 m2 , and B2, wherein R 7 , R8 and R9 are each independently -NO, -OH, -S03H, -C02H, methyl, ethyl, propyl, isopropyl, butyl, t-butyl or t-butyl, preferably, hydrazine 7. R8 and Rs&gt; are all in which m 1 is 5-15, m2 is 10-20, and n2 is 15-25; the epoxy block copolymer includes A3B3, A3B3 A3, B3A3B3, A3B3 A3B3 At least one of the block copolymers, wherein A3 is a block represented by -C-C-0--C-C-〇-m3, and B3 is a block represented by n3, wherein m3 is 20 -40, η3 is 10-30; the other hydrophobic group-containing block copolymer comprises at least one of 嵌段4Β4, Α4Β4Α4, Β4Α4Β4, Α4Β4Α4Β4 block copolymer, Α4 is selected as C-C ml -c-c - and at least one of the blocks shown by LI m2, 0 159079.doc -6 - 201219504, B4 is a block represented by c-c- n4 o=c I 0 1 r12, where R, 2 is hydrogen Having [to 8, preferably 1 to 4 carbon atoms, such as ruthenium, 2, 3, 4 carbons The sub-group burning 'wherein ml is 5-15, m2 is 10-20, n4 10-20. 6. The aqueous white color paddle according to the above 5, wherein: at least 5% by weight of the vinyl block copolymer, at least 7 〇 by weight, at least 8% by weight, preferably at least 9 〇. Weight, preferably at least 95% by weight of the block copolymer of A1玖1辧; at least 5% by weight, preferably at least 7% by weight, preferably at least 8 〇 by weight of the acryl-based bulk copolymer %, more than 9% by weight, preferably to weight % | Α 2 Β 2 block copolymer; ..... ... . . . . . . . . . . ................... . ' . ; '·' ... . . . of the epoxy group copolymer At least 50% by weight, more than at least 7% by weight, preferably at least 8% by weight, preferably at least 90% by weight, preferably at least 95 ........... ................................. % by weight of the block copolymer shown in Α3Β3; At least 5 〇% by weight, preferably at least 7% by weight, and more fortunately to (4) 8 〇% of the child. ... + ·..' .................. .... at least 95% by weight of the segment copolymer shown by Α4Β4. 7. The aqueous white color crack according to any one of the above 3 to 6, wherein: the ethylene-based enemy copolymer has end groups 1 and r2, respectively, .... .. . .... ..... ... ... . . . is the methyl, propyl or ethyl carboxyl group; : .... ......... ............................... The propylene-based block copolymer has a terminal group R1iR2, and the heart is separated from each other _ . . . . _: ____ _ ... . . . . . The ground is methyl, allyl or ethyl carboxyl; .: ..... ..-. .... .... eight. .. . . . . . ;.': ^V;'.; V', 159079.doc 201219504 The epoxy group copolymer has terminal groups 111() and Rn, wherein R1G and Ru are each independently hydroxyethyl or hydroxy The propyl group or the ethyl carboxyl group; the other hydrophobic group-containing block copolymer has a terminal group core and a ruler 2, and R and 2 are each independently a fluorenyl group, a fluorenyl group or a benzyl group. 8. The aqueous white color paste of any one of the above, wherein the dispersing agent is Lutensol® isomeric alcohol ether of B ASF. 9. The aqueous white color paste of any one of the above, wherein the dispersing agent is a Lutensol® isomeric alcohol ether AT series of BASF, a Tex series, an xl series, an XP series or a Sokalan CP series of BASF. 10. The aqueous white color paste according to any one of the preceding claims, wherein the bactericide is at least one selected from the group consisting of 2_mercapto-4-isothiazol-3-one, 1,2-benziso Thiazolin-3-ol, 4,4-dimethyloxazol and its tridecyl homolog. 11. The aqueous white color paste according to any one of the preceding claims, wherein the antifoaming agent is tri-n-butyl phosphate and/or propylene glycol polyoxypropylene polyoxyethylene ether. 12. The aqueous white color paste of any one of the above, wherein the wetting agent and/or dispersing agent is a liquid at normal temperature. 13. A method of preparing an aqueous white color paste according to any of the preceding claims, comprising the steps of: a) adding said wetting agent, dispersing agent, antifoaming agent and at least a portion thereof to said container according to said ratio Deionized water, and stirred; b) adding titanium dioxide to the slurry obtained in step a) with stirring until the slurry is completely mixed and infiltrated; C) uniformly dispersing the slurry obtained in step b) to obtain semi-finished color; 159079 .doc

I I201219504 and depending on the amount of deionized water, magnetic enamel finished color paste. 14. The method of the above 13 wherein one or more of recording, ball milling and sanding in step e) are carried out. [Embodiment:] 丨丨 to the titanium fertilizer, P. 4 to 1% 々 々 及 及 and complex (1) titanium dioxide.: V _ .: . · - · ........ ''. Reading reference materials (4) Umbilical and sharp-type titanium dioxide. :|'P rotation, but preferably 0.1 to 10 mm. The titanium dioxide which can be used in the present invention can be (iv) a product, for example, k-four, R-104, R-706 and R-93. • ............................................ 159079.doc

-9- S 201219504 » The content of titanium dioxide in the paste of the present invention is preferably from about 5 至 to 65 ° / of the mass of the paste. For example 52% to 65%, 53% to 61°/. , 55°/. Up to 60°/. Or 56% to 5 8%. (2) Wetting agent Wet agent is used to make the solid material more easily wetted by water. By reducing its surface tension or interfacial tension, water can be spread on the surface of solid material or penetrated into its surface. Wetting. The wetting agent which can be used in the paste of the present invention may be anionic or nonionic, and an anionic/nonionic complex type may also be used. Its hydrophilic-lipophilic balance (HLB value) can be 9 or higher. Preferably, the wetting agent is a liquid at normal temperature. A preferred wetting agent is at least one selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and triethylene glycol monobutyl ether. Preferably, the ratio of diethylene glycol dimethyl ether, diethylene glycol monobutylene, diethylene glycol monoethyl ether and triethylene glycol monobutyl ether can be 1 to 1 based on the weight of the total wetting agent, respectively. 99% or 5% to 95% by weight, for example, by weight, 1%, 15%, 20% ' 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80 % or 90%. Useful wetting agents are commercially available, such as Dow's anti-white water, BASF's Ethylene Glycol. The content of the wetting agent in the paste of the present invention is preferably from 5 to 8%, for example from 5 6% to 8%, or from 6.2% to 7.5%. (3) Dispersant dispersant can improve and improve the dispersion performance of solid or liquid materials. Its main 159079.doc •10- 201219504 ......:.. ·.: To reduce liquid-liquid friendliness, The boundary between the two is known as anionic, cationic, nonionic, v-type and polymeric. Preferably, the dispersant is a liquid at normal temperature. The dispersing agent used in the present invention is a composite dispersing agent, and is selected from at least two of the following copolymers: a vinyl block copolymer, a propylene-based block copolymer, an epoxy group, and a monolithic copolymer. . The basic copolymer of water-based polyester's compounding agent: a compounded dispersing agent v or a copolymerized surface composed of a compounding agent::: or an ethylene-binding block dance polymer composed of an epoxy group block copolymer a composite dispersant, or a composite dispersant composed of an inner-base copolymer and an epoxy block copolymer, or a 4-stage co-existing material and an epoxy block copolymer and other hydrophobic hydrocarbons Segmental copolymer 4 consists of a ritual divergence. By using these compound dance powders, the obtained color groups can be made to have higher color strength, while maintaining good dispersion and stability: . . . . V .. . -:........ 隹 隹 'in the composite dispersant, based on the weight of the total dispersant, the ethylene dance rank copolymer V C-based group without a common congregation _ The syllabus of the shovel of the hoofed water group is 1_mouth, or _琴95 夺曼^15% &gt; 20% ' 25% ^ 30% ^ 35% - 40% V 45% v 50% - 60%; 70%, 〇% or 9〇k. :..........................--.. . . ' . . '·' : ....... ... . . . ............................. In a preferred embodiment, the vinyl block copolymer is composed of a stupid monomer and an isobutyl monomer. At least one of them is formed by polymerization of an ethylene monomer which is unsubstituted or F, Cl, Br, I,

N〇2 ' -OH 159079:doc -Π- ...:s 201219504 S03H ·ς:〇2Η, mercapto, ethyl, propyl, isopropyl, butyl, first butyl, second butyl The vinyl block copolymer has a weight average molecular weight of 1,500 to 3,000, preferably 2,000 to 2,500, in which at least one of the substituents is substituted one or more times. In a preferred embodiment, the propylene-based block copolymer is formed by polymerizing at least one of a styrene monomer and an isobutylene monomer with a propylene monomer which is unsubstituted or passed through F, Cl, Substituting at least one substituent of I, _Ν〇2, _〇Η, -so3h, -C〇2h, methyl, ethyl, propyl, isopropylbutyl, t-butyl, and t-butyl Alternatively or more, the propylene-based block copolymer has a weight average molecular weight of from 1,500 to 3,000, preferably from 2,000 to 250,000. In a preferred embodiment, the epoxy block copolymer is formed by polymerizing an ethylene oxide monomer and an epoxy propylene monomer having a weight of from 15 Å to 3 Å, preferably from 2,000 to 2,500. Average molecular weight. In a preferred embodiment, the other block copolymer having a hydrophobic group is composed of at least one of a phenethyl monomer and an isobutyl monomer, and (mercapto)acrylic acid or a C1-C8 alkyl group thereof. The ester, preferably at least one of Cl, C2, C3, C4 alkyl esters is formed by polymerization, having a weight average molecular weight of from 1,500 to 3,000, preferably from 2,000 to 250,000. In the present invention, the weight average molecular weight of the above polymer is measured by gel permeation chromatography (GPC, Gel Permeation Chromatography). Preferably, the vinyl block copolymer of the present invention comprises at least 159079.doc • 12· 201219504 of the block copolymers represented by A1B1, A1B1A1, B1A1B1, and A1B1A1B1, wherein A1 is selected from

C-c- m1 and -c-c- m2 are as r3 1 ? 4 1 C - 1 -c- 1 1 r5 I block only 6 n1, at least one of the segments, B1 is R3 , R4, 115 and 尺6分分&gt;J ^ ' ν Ι -0仗, -S03H, :C02H, methyl, ethyl, propyl, . . . . . . . . . . .................................................... base, second butyl or tert-butyl, preferably, R3, 政4 , heart and sputum are all .... hydrogen; where ml is 5-15, such as 6, 7, 8, 9, 10, 11, 12, 13, - . · · . . - 14 ; m2 is: Ο - 20, for example 11, 12, 13, 14, 15, 16, 17, . . . : ..... . . . . . . . . . . . - 18, 19; nl is 15-25 ' For example, 16, 17, 18, 19, 20^ . ..... - .... . . . . . . . . . . . . . . , ... 22 &gt;23 '24 ° Preferably, the acryl-based block copolymer comprises Α2Β2, Α2Β2Α2, . . . . . . . . . . . . . . . . . . . at least one of the block copolymers represented by Β2Α2Β2, Α2Β2Α2Β2, wherein Α2 is selected from at least Β2 of blocks represented by _ . . -C-C-ml and -c-c- m2 is II -c-^-c I r9 n2 , wherein R7, R8 and R9 are independently Η, F, ei, Br, I, -NO], -OH, -S03H, . . . . . . . . . . . . . . . . . . . . . -C02H, methyl, ethyl, propyl, isopropyl, butyl, t-butyl or tert-butyl, Preferably, R7, 118 and 119 are all hydrogen, wherein ml is 5-15, . . . . . . . . . such as 6, 7, 8, 9, 10, 11, 12, 13, 14; m2 10-20, example 159079.doc 13. 201219504 such as 11, 12, 13, 14, 15, 16, 17, 18, 19; n2 is 15-25, such as 16, 17, 18, 19, 20, 21, 22, 23, 24. The epoxy group copolymer comprises at least one of the block copolymers represented by A3B3, A3B3A3, B3A3B3, and A3B3A3B3, wherein A3 is a block 'B3' represented by -f C-~C-〇~]^3 For the block represented by -[~C—C—〇七3, where m3 is 20-40 3〇, 32, 34, 35, 36, 38, 39; Π3 is 10-30, such as 12 14 , 15 , 16, 18, 20, 21, 23, 25, 26, 27, 28, 29. The other hydrophobic group-containing copolymer comprises at least one of the block copolymers represented by A4B4, A4B4A4 B4A4B4, and A4B4A4B4, and A-C-C- is selected.

Ml and -C-C-m2 at least - C-C-

'B4 is a block represented by 〇=〒 Ο IR 12 n4, wherein R1Z is hydrogen, has 3, 4 carbons 10, 11, 14, 15, 13' 14' to 8 carbon atoms, preferably 1 An alkyl group of up to 4 carbon atoms, for example 1, 2 atoms, wherein ml*5_15, for example 6, 7, 8, 9 14, m2 is 1 〇-20, such as 11, 12, 13 16, 17, 18, 19 ; think 1 〇 2 〇, such as u, 12 15, 16, π, 18, 19. The above ml, m2, m3 'nl, n2, n3 or n4 may not be an integer. In a preferred embodiment of the invention, the vinyl block copolymer #159079.doc 201219504 •. . . . . . . . . . . . . . . . . . - - ^ at least 50% by weight Preferably, at least 7% by weight, preferably at least 80% by weight, . . . . . . . . . . . . . . . . . . For example, 5 〇 to 1 〇〇 重量 % is a block copolymer represented by A1B1. . . . - ' - . . . - In a preferred embodiment of the invention, the - propylene matrix copolymer has a . - - . . . . .. at least 5% by weight, green preferably at least 7% by weight, preferably at least 8% by weight, preferably less than 9% by weight, preferably at least 95% by weight, for example 5 〇 to 1 〇〇 children. &quot; :- - , -.· % is a block copolymer of A2 body. In a tamping embodiment, the at least 5 〇 wt% V of the epoxy block copolymer is preferably less than 7 〇 wt%; preferably at least the weight 吣V is at least 90 wt%, which is fortunate At least 95% by weight, for example 50 to 1% by weight, of the segmented copolymer represented by A1B3. . . . . . . . . . . . . . . in the preferred embodiment of the present invention, the other hydrophobic group; the segment copolymer is at least 5% by weight, preferably at least 70% by weight, preferably 80% by weight of the Emperor, 90% by weight of the 敕♦, and at least 95% by weight of 50 to 100% by weight of the block copolymer represented by A4B4. 1 -: . . . . . . . . . . . . . . in the above aqueous white color sound of the present invention, the 'ethylene' block copolymer has a base and a ruthenium See anti 2 'for private and private foods p carboxy: base friends: / or _ _ _ ......... . . . . _____: 弋 $ 辣 多 多The winter dance spheroids R _ and r, and the ground are methyl, allyl salty ethyl carboxyl groups; and γ or:,: The epoxy group copolymer has terminal groups Rla and Rii, wherein Ri. And the knife: not independently. B. Base: propyl or . B. Enemy. and / or • · . . . . . . . . - - - · Other hydrophobic groups The block copolymer has a terminal group core, and Ri and I are each independently a methyl group, an allyl group or a ethyl carboxyl group. 159079.doc : ί5· 201219504 In the present invention, the dispersing agent may be used as it is or, if necessary, after being blended with a suitable auxiliary. In the present invention, the dispersing agent used is Lutensol® isomeric alcohol ether of BASF Corporation, and among them, BASF's Lutensol® isomeric alcohol ether AT series, Tex series, XL series, XP series or BASF's Sokalan CP series are preferably used. Products, better use AT-18, AT-18 solution, XP-90 and / or XP-99. Preferably, their proportion in the total dispersant may be from 1 to 99%, or from 5% to 95% by weight, for example, 10%, 15%, 20%, 25%, 30%, 35% by weight. 40%, 45%, 50%, 60%, 70%, 80% or 90%. The content of the dispersing agent in the paste of the present invention is preferably from 35 to 40%, for example, 36% or 37% or 38% or 40%. (4) Fungicide Any type of bactericide can be used in the present invention as long as it is compatible with other components of the color paste of the present invention. Preferably, the bactericide is at least one selected from the group consisting of 2-mercapto-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 4,4- Dinonyl oxazolidine and its trimethyl homologue. Preferably, they may be present in the total bactericide in a weight ratio of from 1 to 99%, or from 5% to 95% by weight, for example, by weight, 10%, 15%, 20%, 25%, 30%, 35 %, 40%, 45%, 50%, 60%, 70%, 80% or 90%. Useful fungicides are commercially available, for example, Dehygant LFM available from Cognis, Anticide available from Thor, and the like. 159079.doc -16- 201219504 ;v... . :...... ,...... ..... .. . :. . ... ..... : ... ....: . . . ... . . . . . . . . . . . . . . . . . . . . . . The content of the stimulating is preferably from 0:3 to 〇.6%, #丨^ 〇.4%, 0.5% or 0.6% 八^^^ &quot; (5) Elimination of the foaming agent. . . ... faint.. - .... Useful antifoaming agents include natural oils such as soybean oil, corn oil, etc.; poly' 趟 济 济 ;; high carbon alcohol; hydrazines, such as polydimethyl methoxy oxane; Sexual cockroaches: with a polyoxyalkylene defoamer. Oxygen in the interior of the polyoxyethylene oxime. The antifoaming agent which can be used in the present invention is particularly suitable for bYK, 012, BYK_6 and its class of anti-emergence agents which are commercially available from Bm Company in the color paste of the present invention in an amount of 0.4 to w, for example, 0.5%, 0.6. %, 0.7%, 0, 8% or 0 i (6) The amount of deionized water in the paste of the present invention is preferably from about 丨 to ice, for example about 1.5%, 2%, 2.5%, 2_8%, 4 % or 4.5%. Preparation of water-based white color paste The color paste of the present invention can be prepared by the method comprising the following steps: 4 according to the tb '4 container and at least a part of deionized water, and stirred; .V: .. .. v'' End:. Full mix and merge: Infiltration. ..... ..... : . . . . ........ .. .... ... . . . ......... - ' Enter c) Add the bactericide to the semi-finished color ruin obtained in the step illusion by the slurry obtained in step b) 1 amount of deionized water, to obtain finished color paste, . . . . . . . . . The above steps can be carried out at room temperature and normal pressure, if necessary, can be in the warming temperature _ Degree or decrease: temperature: carried out: _ 〇 159079.doc 201219504 In the preparation method of the present invention, the above description about the aqueous white color paddle, including the description of each component and the respective ratio, structure, etc., Suitable for the preparation method. When the composite dispersant of the present invention is added in the step a), the dispersants may be added sequentially, or the dispersants may be premixed and added together, or if necessary, the dispersants and optional additives may be pre-mixed. Add them together after mixing. The water added in step a) may be all water or a part of all water, such as 30%, 5%, 7%, 9%, etc. of the total amount of water. If only a portion of the water is added in step a), the remainder of the water required by the present invention is added in step d). The apparatus which can be used in the production method of the present invention is conventionally used in the art, and is not particularly limited. The step in the step c) is carried out by one or more of high speed dispersion, ball milling and sanding. Such dispersion methods are known to those skilled in the art. EXAMPLES The invention is illustrated by the following examples, but the invention is not limited to the examples. Comparative Example According to the Chinese Patent Application CN1478830A, Example 3, a comparative color paste of 200 g was prepared for comparison, and the ingredients thereof were: white powder: 50.5 wt%, wherein 〇5 wt% was nano-scale titanium dioxide; Amine: 2 weight 〇 / 0 ; Amino - 2-methylpropanol: 2% by weight; Ethylene glycol: 8 〇 / 〇; 1, 1, 2- benzothiazoline _ 3 ketone: 〇〇 5 weight 159079 .doc 201219504 Tri-n-butyl phthalate: 0.01% by weight; Methyl hydroxyethyl cellulose: 2% by weight; Deionized water: 35.5 % by weight. Example 1 A color poly 2 gram was prepared according to the following mass percentage: : Wetting agent 5.6%; :...V . . : ' ·.....' ..... . . Titanium dioxide 53% ; Disperse 36% of the agent; 0.6% of the fungicide; 0.8% of the antifoaming agent; &gt; 0 ^ 4% 〇. . . . , . . . , 72 grams of dispersant Lutensol® isomeric alcohol bond AT-18 (BASF company), .... .... .... ... ............................................... .................................... - 1:6 grams of defoamer βγΚ-016 (ΒΥΚ company), 11.2 grams of wetting agent 1 ..... : .... ... ... ...................... .. glycol monobutyl ether ( BASF product) and 8 grams of deionized water mixed, mixing conditions .... ..... . . , .... under the addition and 1 〇 6 gram weight of white powder R_l〇4 (Dupond company ), 高连.... - .. . . .. ..... ..... .......... .... - &quot; 30 minutes 'transfer the components of the mixture to the grinder within the grinder 6_ ..... ..... .... .....' ...: .. ..... . . ...............................10 Small: # LF_C〇gnis Company) 'After stirring the sample, it is the pigment color prepared by the finished ride. Pulp and the aforementioned comparative color paste Line teaching, its salty data such as: 乂: 159079.doc -19- 201219504 Table I sample name intensity data # viscosity test data &quot; fresh preparation 24 hours after 48 hours and 1 week after the color paste 100% 86.4 ku 86.9 Ku 87.4 ku 92.0 ku The color paste of the invention is 124% 90.1 ku 90.2 ku 90.2 ku 90.8 ku adopts the DIN 6174 method; # uses the GB 9269-88 method. The prepared pigment paste was compared with the above comparative paste for stability test. The results are as follows: Table 1-2 Sample name viscosity test data Freshly prepared 24 hours after 48 hours and 1 week after the color paste 86.4 ku 87.9 ku1/ 87.5 ku2 89.4 ku1/ 88.9 ku2 95.3 ku1/ 93.2 ku2 The color paste of the present invention 90.1 ku 90.5 ku1/ 90.3 ku2 90.6 ku1/ 90.5 ku2 91.1 ku1/ 90.9 ku2 1 The sample is placed in a 50-degree oven and allowed to stand at intervals. Sampling was tested for viscosity according to the method of GB 9269-88. 2 Place the sample in a refrigerator with a degree of humidity, and sample it at intervals to test its viscosity according to the method of GB 9269-88. The prepared sample was tested, and the presence of any nonylphenol, nonylphenol ethoxylate, octylphenol, octylphenol ethoxylate compound was not detected by HPLC-MS. Example 2 A color paste of 200 g was prepared according to the following mass percentage: 159079.doc -20- 201219504 Wetting agent 6.2%; .... . . , .. ...... · ..... .... .. · Titanium Dioxide 54%; . '- - .. Dispersant 35%; .... ... .. -. · . . . . - . . . ; . . . . . . . . . . . . . . . . . . . . . . . . . Defoamer 0.5%; Deionized rice.: Move ' ........ .......... .......................................; . . Destroy 70 gram dispersion view Luteftsol® isomerized alcohol AT-1 $ solution (BASF) 1: gram defoamer BYK, 012 (feYit4 division), 12.4 gong ^ &quot; ..... .. ... -- ..... reading agent Sanji Erqi Weng (DOW company) Friends 7. Shigong sergeant ^ . ....... .......... . 1 • . . . - ............... .. .. ..... .... ... , ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ' ' ' . Company) 'High-speed mixing and dispersing for 35 minutes' to transfer the mixed slurry components to the research ..... - . - . . . . . . . . Grinding in the machine 5--amp; hour:; After the grinding is completed, add 铋 to the ♦: 丨 gram bactericide.. . . . . ............................... ...... :An tieideCThor branch) After the stirring, the material is the finished color paste. The pigmented color paste obtained by the tanning process is compared with the above-mentioned comparative color paste, and the test thereof is as follows:::.ϊ心.... . : . . . .. ... calendar preparation: 24_;:丨_^ After:: Na 864ku 86.9ku »7/ΐ ι Λ, 89.4 ku 89.6 ku ^ ^ The name of today, the strength of secret * - ^ : viscosity ah test number 裱 ** 100% 120%:, contrast color paste this invention The color 蕞 adopts the DIΝ 617 4 method; &quot; · ····• adopts the GB 9269-88 method.-.· ... :. .:............. The prepared pigment paste Compared with the above-mentioned comparative color paste, the results are as follows: stability test ratio |59079.dpc 21- 201219504 Table II-2 Sample name viscosity test data freshly prepared 24 hours after 48 hours and 1 week later, comparative color paste 86.4 ku 87.9 ku1/ 87.5 ku2 89.4 ku1/ 88.9 ku2 95.3 ku1/ 93.2 ku2 The color paste of the present invention 89.4 ku 89.7 ku1/ 89.5 ku2 90.1 ku1/ 90.0 ku2 90.7 ku1/ 90.4 ku2 159079.doc • 22- 1 The sample is placed in a 50 degree oven and allowed to stand. Samples were tested at intervals of time according to the method of GB 9269-88. The sample was placed in a refrigerator at 0 ° C and allowed to stand at intervals, and the viscosity was measured according to the method of GB 9269_88. 2 The prepared sample was tested. The presence of any mercaptophenol, nonylphenol ethoxylate, octylphenol, octylphenol ethoxylate compound was not detected by HPLC-MS. Example 3 200 g of color paste was prepared according to the following mass percentages: 5% of wetting agent; 57.5% of titanium dioxide; 35.5% of dispersant; 0.5% of fungicide; 0.5% of defoamer; 1% of deionized water. 71 grams of dispersant Lutensol® isomeric alcohol ether XP-90 (BASF), 1 gram defoamer tri-n-butyl phosphate (Bayer), 10 grams of wetting agent diethylene glycol dimethyl ether (BASF) And 2 g of deionized water was mixed, and 115 g of titanium dioxide R-706 (DuPond) was added under stirring to disperse and disperse for 5 minutes at high speed, and the mixed slurry component was transferred to a grinder for grinding for about 201219504 8 hours; Finished by adding 1 gram of bactericide to the genus and isoindolin-3-one (DuPond), after mixing, it is the finished color. The prepared pigment color paste was compared with the aforementioned comparative color enamel, and the test data was as follows: . . . . . . . . . . . . Table III-1 Sample name strength data 'Contrast color paste The color paddle 100% 122% viscosity test data of the present invention" B6.4ku 86.9ku 87.4 ku 90.0 ku 90.2 ku 90.3 ku 92,0 ku 90.9 ku adopts the DIN 6174 method; . - . . _ . - . ... .. . ..... . . "Use the GB 9269-88 method. . ....... :..: ..... ... ................................. .. . . . . . . .:.... . . . . .:..' .. : .. . . ............. .. .... ..:. ....

The prepared pigment paste was compared with the above-mentioned comparative color paste for stability test, and the results are as follows. Table III-2 Viscosity test data freshly prepared 24 hours after 48 hours and 1 week later, the comparative color paste of the base color paste is... ... .&quot; 86.4 ku . , . 90.0 ku . ..... ..: .... 87.9Ί011/ 87.5 ku2 ....... . . 90.1 ku1 / 90.1 ku2 89.41οι1/ 88.9 ku2 90.4 ku1/ 90.3 ku2 95.3 ku1/ 93.2 ku2 90.7 ku1/ 90.9 ku2 ... ^ Place the sample ..... . . . . . . in the 50-degree chess box and stand still.. .. + - ' . +..... . . : . . . : : Every other ... . ' Segment time respectively ... .. .. .: . ... ..... .. :

The sampling plate was tested for viscosity V 2 according to the method of GB 9269_88. The sample was placed in a refrigerator at 0 ° C. The sample was placed at intervals of time to test the viscosity according to the method of GB 9269-88. · . . . 1 . . . . . The test sample was tested and no sulfhydryl group S was detected by HPLC-MS: 159079.doc •23- 201219504 Phenol, nonylphenol ethoxylate The presence of a base compound, octylphenol, octylphenol ethoxylate. Example 4 200 g of color paste was prepared according to the following mass percentages: humectant 8%; titanium dioxide 52%; dispersant 37%; bactericide 0.5%; defoamer 0.5%; deionized water 2%. 74 grams of dispersant Lutensol® isomeric alcohol ether XP-99 (BASF), 1 gram defoamer propylene glycol ethoxylate N-220, 16 gram wetting agent triethylene glycol monoethyl ether (BASF) and 4 Mixing grams of deionized water, adding 104 grams of titanium dioxide R-931 (DuPond) under stirring, dispersing and dispersing at high speed for 30 minutes, transferring the mixed slurry components to the mill for about 6-8 hours; grinding is completed. 1 g of the bactericide 2-mercapto-4-isothiazolin-3-one (KMZ Co., Ltd.) was added thereto, and the mixture was discharged to obtain a finished color paste. The prepared pigment paste was compared with the above comparative paste, and the test data was as follows: Table IV-1 Sample name strength data # Viscosity test data" Freshly prepared 24 hours after 48 hours and 1 week after the color paste 100% 86.4 ku 86.9 Ku 87.4 ku 92.0 ku The color paste of the invention is 128% 89.7 ku 90.0 ku 90.2 ku 90.6 ku 159079.doc -24- 201219504 ...... ........' ...... . . . . . . . . . . . + DIN 6174 method; "The GB 9269-88 method stability test is compared with the prepared pigment paste compared with the above comparative color, the result As follows: Table IV-2

Contrast color paste 86.4 ku 87.9^/ 89.410^/95.310^/ 87.5 ku2 88.9 ku2 93.2 ku2 .... . . . . . . . . . . . . . . . . .... .... . . The color paste of the present invention 89.7 ku 89.7 such as 1/90.1 ku1/ 90.8 ku1 / - 90.1 ku2 90.3 ku2 90.7 ku2 The sample is placed in a box of SO degrees and allowed to stand at intervals. The time was sampled separately and tested for viscosity according to the method of GB 9269-88. .-.-.. ....... 2 Place the sample in a freezer in the refrigerator and take it at regular intervals... . . . . . . . . . The viscosity was tested according to the method of GB 9269-88. ' .... . . . - ....... ..: . ... : ... . . - ... . . . . . . . . . .. .............. . . - &quot; . . . ' Test the prepared sample and measure any sulfhydryl group by HPLC-MS._ _ ' . . . ..... .. . . ........................................................................... The presence of stupid enzyme, mercaptobenzene 6 oxy-i compound, octyl benzene powder, octyl benzene ethoxylate compound. Real_Example 5 Prepare 200 g of color paste according to the following mass percentage: Wetting agent 7.2%; . . : ........ ... ... ..... ... ... ... .. ... .. . . . . . . . . . . titanium dioxide 53%; dispersant 37%; fungicide 0.5%; 159079.doc 201219504 defoamer 0.5%; deionized water 1.8%. 74 grams of dispersant propylene-based block copolymer Sokalan CP (BASF product), 1 gram defoamer propylene glycol ethoxylate N-220, 14.4 grams of wetting agent triethylene glycol monoethyl ether (BASF) and 3.6 grams Deionized water was mixed, and 106 g of titanium dioxide R-706 (DuPond) was added under stirring, and the mixture was dispersed by high speed stirring for 30 minutes, and the mixed slurry component was transferred to a grinder for grinding for about 6-8 hours; after the grinding was completed, it was added thereto. 1 g of fungicide 2-methyl-4-isothiazolin-3-one (DuPond), after stirring, the finished color paste is obtained. The prepared pigment paste was compared with the above comparative paste, and the test data was as follows: Table V-1 Sample name intensity data + Viscosity test data 0 Fresh preparation 24 hours after 48 hours and 1 week after the color paste 100% 86.4 ku 86.9 Ku 87.4 ku 92.0 ku The color paste of the invention is 122% 89.1 ku 89.3 ku 90.1 ku 93.3 ku adopts the DIN 6174 method; 'the method of GB 9269-88 is adopted. The prepared pigment paste was compared with the above comparative paste for stability test. The results are as follows: 159079.doc -26· 201219504 Table V-2 Sample name viscosity test data Freshly prepared 24 hours after 48 hours! 87.9 ku1 after week / 89.4^/ 87.5 ku2 88.9 ku2 89.7 ku1 / 90.6 ku1 / 90.4ku2 9L41aj2 Place the sample in an oven at 5 degrees, and test the viscosity of each sample according to GB 9269-88. 2 Place the sample in a refrigerator at 0 degrees, and test the viscosity of each sample according to GB 9269-88 method. .... . . . . . . . . . . contrast paste 86.4 ku 89.1 ku 95.3 ku1/ 93.2 ku2 time divided separately, the time of the period η ' . . . . . . . . . . . . . . . _ _ produced samples were tested, using HPLC-MS not The presence of any phenanthrene, anthracene ethoxylate, octylbenzene, and octylbenzene-based compounds was detected. 'Work: Industry fit.. Use. Sex:: : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Control the preparation process 'No, enter any legal organic matter. The pigment paste of the invention needs less color formula of the color strength ' _ content of the pro-formulation to be compared, and the capital is higher than the traditional product by about 20% ^ ^ ^ ^ ^ , Ρ ^ ^ α ^ ^ ^ ^ ^ ^ Good stability; compare the obtained pigment pastes for storage stability test, store under high temperature (machine) and low temperature conditions for two weeks, test, 159079.doc -27- 201219504 The obtained white colorant has almost no change in fluidity, and the viscosity is always retained at 90 ku±l ku (br〇〇kfield method), and its stability is much higher than that of similar products on the market. The pigment color paste obtained by the invention is sent to a third-party testing institution for testing, and high-performance liquid chromatography-tandem mass spectrometry does not detect the presence of nonylphenol, nonylphenol ethoxylate, octylphenol and octylphenol ethoxylate. . Compared with traditional products, the color paste obtained by the invention has the following advantages: (1) low odor and environmental friendliness, can meet the environmental protection requirements of current and future customers; (2) the product does not contain volatile organic substances, and does not contain Sulfhydryl, octylphenol and its ethoxylates meet the latest environmental regulations; (3) Excellent performance, optimized pigment content and higher tinting strength; (4) Good product stability, thus reducing color Precipitation tendency of pulp; (5) Good fluidity's high storage stability and good compatibility; (6) The preparation process is simple and easy to implement on an industrial scale. 159079.doc -28-

Claims (1)

201219504 ........ ........... ...............:...:. .......... ... ...... .... —t, the scope of application for patents: . . . - - &quot; . : ... .. . ... ... ..... .. ... . .... 1. An aqueous white color paste comprising: 5% to 8 °/ of a wet agent based on the mass of the color. , for example, 5%, 5.6%, 6.2% or 7.2% to 8%; white powder..... '........ Dispersant........:. Fungicide defoamer _去_离. 子水 54%, 56% 50% to 65%, for example 52% . . . 57.5% or 61% to 65%; ................. .............: .... 3 5% to 40%, for example 35%, 35.5%, 36% or .. -. . . . ..... .... ... ............... 37% to 40% ; / :...... ... ... II-;;.'.... 0.3% to 0.6%, for example, 0.5% to 0.6%; -.. .--. - . . . . . . . - 0.4% to 1% ' For example, 〇·5% or 0.8% to 1%; ... . . . . ................................................. 1% to 5%, for example 1 %, 2%, 2 8% or 4% to 5% 〇2 The aqueous white color paste of claim 1, wherein the wetting agent is selected from the group consisting of diethylene glycol dioxime ether, di 6 glycol monobutyl ether, three At least one of ethylene glycol monoethyl ether and triethylene glycol monobutyl ether, ... . . . . . . . . : . . . . . . . . An aqueous white color paste of the item 1 or 2, wherein the dispersing agent is selected from at least two of the following copolymers: a vinyl block copolymer 'acrylic shy yang, and the ring is broken Other poly-ash ash has a hydrophobic group of 4, as in the water-based white color of claim 3, where: ..... ..... ·. ... . The vinyl block copolymer is formed by polymerizing at least one of a styrene monomer and an isobutylene monomer with an ethylene monomer which is unsubstituted or passed through F, Cl, Br, I, -2. At least one substituent of -oh, -S03h, _C02H, methyl, ethyl, propyl, isopropyl, butyl, tbutyl butyl butyl 159079.doc 201219504 is substituted one or more times, the ethylene The base block copolymer has a weight average molecular weight of from 1,500 to 3,000, preferably from 2 to 2,500; the propylene-based block copolymer is formed by polymerizing at least one of a stupid ethylene monomer and an isobutylene monomer with a propylene monomer, The propylene monomer is unsubstituted, or via F, CM, Br, I, -N02, -OH, -S03H, -C02H, methyl, ethyl, propyl, isopropyl, butyl, butylene And replacing at least one substituent of the third butyl group one or more times, the acryl-based block copolymer having a weight average molecular weight of from 1,500 to 3,000, preferably from 2,000 to 2,500; The oxy block copolymer is formed by polymerizing an ethylene oxide monomer and a propylene oxide monomer, and has a weight average molecular weight of 1,500 to 3,000, preferably 2,000 to 2,500; and the other block copolymer having a hydrophobic group is derived from benzene At least one of the ethylene monomer and the isobutylene monomer is polymerized with at least one of (meth)acrylic acid or its C1_C8 alkyl vinegar, preferably C1, C2, C3, C4 alkyl vinegar, having a 1500 to 3000 ratio. A weight average molecular weight of from 2,000 to 2,500. 5. The aqueous white color paste of claim 3 or 4, wherein: the ethylene-based block copolymer comprises at least one of the block copolymers represented by A1B1, A1B1A1, B1A1B1, and A1B1A1B1, wherein Ai is selected from -r .-r.-l—* 159079.doc 201219504 r3 I -G- B1 is a block represented by -C-nt where R3, R4, R5 and R6 r5 r6 are independently H, F, C1, B r, I, N 0 2 , Ο H, -S〇3H, -c〇2H, decyl, ethyl, propyl, isopropyl, butyl, t-butyl or t-butyl, preferably, r3, r4, Hydrogen; .. 'I .. where ml is 5-15, m2 is 10-20, nl is 15-25; :;::: ; The propylene-based embedded polymer includes A2B2, at 2B2A2, ... ....... . . . . . . . . . . . . . . . . . . . . . . . . . ... B2 is a block represented by at least one of a block represented by ml and R7 R&amp; II -G-C- n2 m2, wherein R7, R8 and Ruler 9 are independently Η, F, Cl, Br, I, respectively , -N02, -ΌΗ, -SO3H, -C〇2H, Shenji, hexyl, propyl, isopropyl, butyl, second butyl...... ..... .... . . . . . or a third butyl group, preferably, R7, R8 and clothing 9 are all hydrogen, wherein ml is 5_, .... 15, m2 is 10-20, n2 For 15-25 ; .. . . . . . . . . . . . . . . . . . . . . . . Copolymers include A3B3, A3B3A3, B3A3B3, .. ' ... - .... ................................... . . . at least one of the block copolymers shown in A3B3A3B3, wherein A3 is a segment shown by •C—C—〇-|^3, and B 3 is a C-C represented by n3. a block of -0, wherein m3 is 20-40, n3 is 10-30; . . . : : ...... The other block copolymer having a hydrophobic group includes A4B4 , in the block copolymers shown by A4B4A4, B4A4B4, and A4B4A4B4, to 159079.doc 201219504 -c -c - one less, A4 is selected from And -CC—I Jm2 C—C is a block represented by the dispersion, wherein at least one of the segments, B4 is 0=〒 Ri2 is hydrogen, has 1 to 8, preferably 1 to 4 carbon atoms, For example, i, 2, 3, 4 carbon atoms. The base 'where ... is 孓^, and the claw 2 is 1〇2〇, which is 10-20. 6. The aqueous white color paste of claim 5, wherein: at least 50% by weight of the vinyl block copolymer, preferably at least 7 ounces by weight 0/❹, preferably at least 80% by weight, preferably at least 90% by weight Preferably, at least 95% by weight is a block copolymer represented by A1B1; at least 50% by weight, preferably at least 7% by weight, preferably at least 80% by weight, preferably at least 90% by weight of the propylene-based block copolymer %, preferably at least 95% by weight of the block copolymer shown in 262; at least 50 weight ❹ / 〇, preferably at least 7% by weight, preferably at least 80% by weight of the epoxy-based fragmented copolymer, It is preferably at least 90% by weight. /❶, preferably at least 95% by weight of the block copolymer of A3B3; at least 5% by weight, preferably at least 70% by weight, preferably at least 80% by weight of the other hydrophobic group-containing block copolymer %, preferably at least 9 〇 weight / 〇, preferably at least 95% by weight is a block copolymer represented by A4B4. 7. The aqueous white color paste according to any one of claims 3 to 6, wherein: the vinyl block copolymer has a terminal base and a ruler 2, and the heart and the ruler 2 are respectively 159079.doc 201219504 Alkene- or carboxy-carboxy tomb; 4 the propylene-based block copolymer has a terminal group HR2, and R1 &amp; R2 are each independently methyl, allyl or ethyl carboxyl; ...... ... ' ; ..... ' ' The cycloolefin-based block copolymer has terminal groups R1G and Rn, and Ri (^Rn is independently hydroxyethyl, hydroxypropyl or ethyl carboxyl group; ................ 8. As for the water color white color of the request center, the branching agent is B AS? Company Winter Lutens〇1 φ isomeric alcohol oxime ether 々义舞舞: Please ask for the item - the water-based white color of the item, the application for bA^sf company (four) coffee pain nasal alcohol ether eight butyl series 乂 ^ ^ ^ ^ ^ xl ^ ^ &gt; xp ^ ^ ^B cp$ ^ yl〇. ¥ Selling the name of this item, any water-based white color, the bactericidal office: at least one round selected from the following:: I ketone 1,2-benzene And isopipeline _3_ ketone, Table 4_ Dimercaptopurine and its trimethyl homologue. .. ...: ...'. .. '; . . . . . . . 11, as shown in the above table, the second TS r is phosphoric acid: tri-n-butyl acrylate and / / "kw β ' winter propylene glycol polyoxyl: propylene polyoxyethylene ether q 12. iiL ^ ^ ^ B, % ^ ^ , and the party of the water-based white color paste of Chengcheng 13. As prepared in the aforementioned request, the sergeant's method includes the following steps: a) according to the ratio, at the time of the mountain π Adding the wetting agent, dispersing agent, defoaming agent and at least a part of the decontaminated 7 ion-free water to the state, and stirring; S 159079.doc • 5: 201219504 b) l searching for the slurry obtained in step a) Titanium dioxide is added to the slurry element to fully mix and infiltrate; c) the slurry obtained in step b)t is uniformly dispersed to obtain semi-finished color polymerization; the agent rtr is added to the semi-finished color paste obtained in step c)t. ::: The balance of deionized water, to obtain the finished color paste. For the method of claim 13, the dispersion in the _ "#C" in the dispersion, ball milling and sanding is carried out by high-speed separation. 159079.doc 201219504 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 159079.doc • 2·