阅读说明：本技术 高研磨效率色浆及其制备方法和分散墨水 (High-grinding-efficiency color paste, preparation method thereof and dispersion ink ) 是由 柴凯 何文辉 张瑜平 于 2021-10-29 设计创作，主要内容包括：本发明提供一种高研磨效率色浆及其制备方法和分散墨水,分散墨水包括该高研磨效率色浆,高研磨效率色浆按总质量为1计,按质量百分比包括：分散染料色粉15％～20％、20％～30％分散剂、20％～30％促溶混合物、0.5％～2％润湿剂和余量的水；分散剂为超支化聚合物,超支化聚合物包括疏水主链和阴离子亲水基,阴离子亲水基设置在疏水主链的至少一个支链上；促溶混合物中的第一促溶剂、第二促溶剂和第三促溶剂可分别为多元醇、二醇醚、酰胺类化合物、环状烷基酯中至少一种；采用以上方案,超支化聚合物增加分散剂结构上可吸附基团数目,得到更小更均匀的染料颗粒,抗纳米粒子的团聚和生长,促溶混合物通过促进原料溶解来改变染料晶体,有助于研磨。(The invention provides a high-grinding-efficiency color paste, a preparation method thereof and dispersion ink, wherein the dispersion ink comprises the high-grinding-efficiency color paste, and the high-grinding-efficiency color paste comprises the following components in percentage by mass, based on the total mass of 1: 15-20% of disperse dye toner, 20-30% of dispersant, 20-30% of dissolution promoting mixture, 0.5-2% of wetting agent and the balance of water; the dispersant is a hyperbranched polymer, the hyperbranched polymer comprises a hydrophobic main chain and an anionic hydrophilic group, and the anionic hydrophilic group is arranged on at least one branched chain of the hydrophobic main chain; the first dissolving promoter, the second dissolving promoter and the third dissolving promoter in the dissolving promoter mixture can be respectively at least one of polyol, glycol ether, amide compounds and cyclic alkyl ester; by adopting the scheme, the hyperbranched polymer increases the number of adsorbable groups on the structure of the dispersant, so that smaller and more uniform dye particles are obtained, the agglomeration and the growth of nano particles are resisted, and the dissolution promoting mixture changes dye crystals by promoting the dissolution of raw materials and is beneficial to grinding.)

1. High grinding efficiency mill base, its characterized in that: the composite material comprises the following components in percentage by mass based on the total mass of 1: 15-20% of disperse dye toner, 20-30% of dispersant, 20-30% of dissolution promoting mixture, 0.5-2% of wetting agent and the balance of water;

the dispersant is a hyperbranched polymer comprising a hydrophobic backbone and an anionic hydrophilic group disposed on at least one branch of the hydrophobic backbone;

the dissolution promoting mixture comprises a first dissolution promoting agent, a second dissolution promoting agent and a third dissolution promoting agent, wherein the first dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compound and cyclic alkyl ester, the second dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compound and cyclic alkyl ester, and the third dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compound and cyclic alkyl ester.

2. The high grinding efficiency color paste of claim 1, wherein:

the hydrophobic main chain is formed by condensation polymerization of long-chain alkane with the carbon chain length of C20-C30, and/or the average molecular weight of the hyperbranched polymer is 20000-40000.

3. The high grinding efficiency color paste of claim 1, wherein:

the anionic hydrophilic group is at least one of hydroxyl, carboxyl and sulfonic group.

4. The high grinding efficiency color paste of claim 1, wherein:

the polyhydric alcohol includes at least one of ethylene glycol, 1, 5-pentanediol, polyvinyl alcohol, hexylene glycol, triethylene glycol, sorbitol, diethylene glycol, 1, 4-butanediol, polypropylene glycol, butanediol, mannitol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, glycerol, 1, 2-propanediol, polyethylene glycol, and 1, 3-propanediol.

5. The high grinding efficiency color paste of claim 1, wherein:

the glycol ether comprises at least one of ethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol n-butyl ether, diethylene glycol monomethyl ether, methoxy triethylene glycol, ethoxy triethylene glycol and 1-butoxyethoxy-2-propanol.

6. The high grinding efficiency color paste of claim 1, wherein:

the amide compound is at least one of polyvinylpyrrolidone, alpha-pyrrolidone and N, N-dimethylformamide; and/or the cyclic alkyl ester is at least one of valerolactone, butyrolactone, butenolide, caprolactone and heptalactone.

7. The high grinding efficiency color paste according to any one of claims 1 to 6, wherein:

the viscosity of the color paste is 8Pa^.s～15Pa^.s, surface tension of 40N/m to 50N/m.

8. The preparation method of the color paste with high grinding efficiency is characterized by comprising the following steps: the preparation method is used for preparing the high grinding efficiency color paste as defined in any one of claims 1 to 7, and comprises the following steps:

s1, mixing and pulping the disperse dye toner, the dissolution promoting mixture, the wetting agent and the water, adding the dispersing agent after the dissolution promoting mixture uniformly mixes the disperse dye toner, and grinding into slurry to obtain pre-dispersion color paste;

s2, grinding, centrifuging and filtering the pre-dispersed color paste to obtain color paste; the grinding medium during grinding is 0.28-0.32 mm of zirconium beads, the filling volume of the zirconium beads is 75-85%, and the grinding linear velocity is 13-14.2 m/s.

9. The method for preparing the color paste with high grinding efficiency according to claim 8, wherein the method comprises the following steps:

the preparation process of the hyperbranched polymer comprises the following specific steps: and carrying out polycondensation reaction on the long-chain alkane with the carbon chain length within the range of C20-C30, wherein in the polycondensation process, an organic end-capping agent with the carbon chain length of C2-C5 is used, and the organic end-capping agent comprises at least one of thioglycolic acid, mercaptoethanol and mercaptopropanol.

10. A dispersed ink characterized by: the dispersion ink comprises the high milling efficiency color paste according to any one of claims 1 to 7.

Technical Field

The invention relates to the field of ink, in particular to high-grinding-efficiency color paste, a preparation method thereof and dispersion ink.

Background

The disperse ink is an ink type with extremely large use amount in the textile digital printing industry, and is characterized by small molecule, simple structure and no ionizable water-soluble group, so that the disperse ink is used for dyeing in a disperse state in the printing and dyeing process. Compared with the commercial toner of the traditional disperse dye, the disperse ink overcomes the difficulties of high energy consumption, high pollution, high discharge and low benefit of the traditional disperse dye, and the printing finished product has good fastness, but the disperse ink of the finished product has poor stability due to the fact that the disperse toner is easy to settle in the storage process, and the technical problem at present is how to solve the problem.

When the number of hydrophobic functional groups in the structure of the existing disperse dye is large or the proportion of the structure of the hydrophobic functional groups is large, the grindability of the disperse dye is reduced, the dye is not dispersed stably, and the stability of the disperse ink paste is influenced. For example, the sodium lignosulfonate dispersant or the related modified dispersant used in the prior art is easy to have viscosity mutation when the content of the toner in the ink is high, so that a color paste with strong dispersion and high stability cannot be obtained, and an ink with good stability cannot be obtained.

In addition, in the production process of the color paste, the disperse dye toner needs to be sanded to nano-scale particles, and the quality of the grinding directly determines the quality of the color paste. The traditional method for improving the sanding efficiency of color paste comprises two methods: 1. zirconium beads are added into a sanding system, so that the sanding efficiency is improved, but the particle size distribution of color paste is widened, the cavity wall of a sanding machine is abraded by excessive zirconium beads, and the service life of the sanding machine is shortened; 2. through selecting for use the zirconium pearl sanding that the particle diameter is littleer, though can accelerate grinding efficiency, the zirconium pearl particle diameter is littleer, and its material price and energy consumption amount rise geometrically doubly, make the energy consumption cost and the material cost greatly increased of production.

Disclosure of Invention

The first purpose of the invention is to provide a high-grinding-efficiency color paste with stable dispersion and high grinding efficiency.

The second purpose of the invention is to provide a preparation method of the high-grinding-efficiency color paste.

The third purpose of the invention is to provide the dispersion ink containing the high-grinding-efficiency color paste.

In order to achieve the first object, the color paste with high grinding efficiency provided by the invention comprises, by mass, 1: 15-20% of disperse dye toner, 20-30% of dispersant, 20-30% of dissolution promoting mixture, 0.5-2% of wetting agent and the balance of water; the dispersant is a hyperbranched polymer, the hyperbranched polymer comprises a hydrophobic main chain and an anionic hydrophilic group, and the anionic hydrophilic group is arranged on at least one branched chain of the hydrophobic main chain; the dissolution promoting mixture comprises a first dissolution promoting agent, a second dissolution promoting agent and a third dissolution promoting agent, wherein the first dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compounds and cyclic alkyl ester, the second dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compounds and cyclic alkyl ester, and the third dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compounds and cyclic alkyl ester.

According to the scheme, when the dispersant contains the polymer with the hyperbranched structure, the hyperbranched polymer comprises a hydrophobic main chain and an anionic hydrophilic group, the anionic hydrophilic group is arranged on at least one branched chain of the hydrophobic main chain, the number of adsorbable groups on the structure of the dispersant is greatly increased by the hyperbranched polymer, the steric hindrance of the hyperbranched polymer is large, the dispersing effect on dye toner is improved, smaller and more uniform dye particles can be obtained, the dye particles are dispersed and stabilized, and the branched topological structure of the hyperbranched polymer also endows the dispersant with good adaptability to the dye toner, lower viscosity and the like, so that the dispersant has the adsorption performance, has the resistance to the agglomeration and growth of nano particles, is beneficial to grinding, prevents the problem of viscosity mutation when the ink is high in concentration, and improves the stability of the ink; and the dissolution promoting mixture formed by mixing at least three dissolution promoting agents is used, the principle of similar and compatible dissolution is utilized, the raw material dissolution is promoted to change the dye crystal, the solubility of the disperse dye in the subsequent pulping stage can be greatly improved, and the grinding efficiency is improved.

The further scheme is that the hydrophobic main chain is formed by condensation polymerization of long-chain alkane with the carbon chain length of C20-C30, and/or the average molecular weight of the hyperbranched polymer is 20000-40000.

Therefore, in the hydrophobic carbon chain, the longer the carbon chain is, the more easily the polar group in the solution is embedded, so that the hydrophobicity of the hyperbranched polymer is higher, the agglomeration is further avoided, and meanwhile, when the length of the carbon chain is controlled, the average molecular weight of the hyperbranched polymer needs to be controlled, and the molecular weight is too low to provide effective space shielding, so that the dispersion effect cannot be achieved; if the molecular weight is too high, it is difficult to control the degree of polymerization, which results in a large difference between batches and poor solubility of the final polymer, and the carbon chain length and average molecular weight in the above range can make the dispersing action of the dispersant better.

In a further scheme, the anionic hydrophilic group is at least one of hydroxyl, carboxyl and sulfonic acid group.

It can be seen that at least one of hydroxyl group, carboxyl group, and sulfonic group is disposed on the hydrophobic main chain as an anionic hydrophilic group, which can increase the surface tension of the final ink and ensure the dyeing effect.

Further, the polyhydric alcohol may include at least one of ethylene glycol, 1, 5-pentanediol, polyvinyl alcohol, hexylene glycol, triethylene glycol, sorbitol, diethylene glycol, 1, 4-butanediol, polypropylene glycol, butylene glycol, mannitol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, glycerol, 1, 2-propanediol, polyethylene glycol, and 1, 3-propanediol.

In a further scheme, the glycol ether comprises at least one of ethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol n-butyl ether, diethylene glycol monomethyl ether, methoxy triethylene glycol, ethoxy triethylene glycol and 1-butoxyethoxy-2-propanol.

In a further scheme, the amide compound is at least one of polyvinylpyrrolidone, alpha-pyrrolidone and N, N-dimethylformamide; and/or the cyclic alkyl ester is at least one of valerolactone, butyrolactone, butenolide, caprolactone and heptalactone.

The further proposal is that the viscosity of the color paste is 8Pa^.s～15Pa^.s, surface tension of 40N/m to 50N/m.

Therefore, the content of each component of the color paste is limited, and the viscosity and the surfactant of the color paste are controlled within the range by combining the performance of each component, so that the ink can be printed smoothly, and the dyeing effect is good.

In order to achieve the second purpose, the preparation method of the color paste with high grinding efficiency is characterized by comprising the following steps: the preparation method is used for preparing the high-grinding-efficiency color paste, and comprises the following steps:

s1, mixing and pulping the disperse dye toner, the dissolution promoting mixture, the wetting agent and water, adding the dispersing agent after the dissolution promoting mixture uniformly mixes the disperse dye toner, and grinding into slurry to obtain pre-dispersion color paste;

s2, grinding, centrifuging and filtering the pre-dispersed color paste to obtain color paste; the grinding medium during grinding is zirconium beads with the diameter of 0.28-0.32 mm, the filling volume of the zirconium beads is 75-85%, and the grinding linear velocity is 13-14.2 m/s.

According to the scheme, after all components of the color paste are uniformly mixed, the color paste with better solubility is ground by the zirconium beads with the diameter range and the filling volume, so that the grinding efficiency is effectively improved.

The further scheme is that the preparation of the hyperbranched polymer specifically comprises the following steps: the long-chain alkane with the carbon chain length within the range of C20-C30 is subjected to polycondensation reaction, and in the polycondensation process, an organic end-capping agent with the carbon chain length of C2-C5 is used, and the organic end-capping agent comprises at least one of thioglycolic acid, mercaptoethanol and mercaptopropanol.

Therefore, the organic end capping agent with the carbon chain length within the range has a good end capping effect, and the prepared dispersant has stable performance and small batch-to-batch difference.

To achieve the third objective, the present invention provides a dispersion ink comprising the high grinding efficiency color paste.

Detailed Description

The high-grinding color paste is applied to the preparation of ink, the ink comprises the high-grinding color paste, the high-grinding color paste comprises a dispersant with hyperbranched polymer and a dissolution promoting mixture, the adsorption is improved and the agglomeration of nano particles is avoided through the hyperbranched structure in the hyperbranched polymer, and the solubility of dye is better through the dissolution promoting mixture, so that the dispersion and the stability of the dye are provided.

The high grinding efficiency color paste comprises the following components in percentage by mass, based on the total mass of 1: 15 to 20 percent of disperse dye toner, 20 to 30 percent of dispersant, 20 to 30 percent of dissolution promoting mixture, 0.5 to 2 percent of wetting agent and the balance of water.

The disperse dye toner is commercially available, and as the cyan use toner, at least one of c.i.disperse Blue 35, c.i.disperse Blue 60, c.i.disperse Blue 148, c.i.disperse Blue 87, c.i.disperse Blue 19, c.i.disperse Blue 284, and c.i.disperse Blue 360 can be used; the magenta toner may use at least one of c.i.disperse Red 15, c.i.disperse Red 277, c.i.disperse Red 65, c.i.disperse Red 43, c.i.disperse Red 143, and c.i.disperse Red 153; the Yellow use toner may use at least one of c.i. disperse Yellow 23, c.i. disperse Yellow 64, c.i. disperse Yellow 86, c.i. disperse Yellow 54, c.i. disperse Yellow 114, c.i. disperse Yellow 3, c.i. disperse Yellow 7, and c.i. disperse Yellow 82.

The dispersing agent is a hyperbranched polymer, the hyperbranched polymer comprises a hydrophobic main chain and an anionic hydrophilic group, the anionic hydrophilic group is arranged on at least one branched chain of the hydrophobic main chain, further, the hyperbranched polymer can be a polyamide type hyperbranched polymer or a polyacrylic acid type hyperbranched polymer, further, the hydrophobic main chain is formed by condensation polymerization of long-chain alkane with the carbon chain length of C20-C30, in the condensation polymerization process, an organic end-capping agent with the carbon chain length of C2-C5 is used, and further, optimally, the organic end-capping agent comprises at least one of thioglycolic acid, mercaptoethanol and mercaptopropanol. The average molecular weight of the hyperbranched polymer is 20000-40000, the HLB value range is 12-25, and the pH value range is 3-9. The anionic hydrophilic group is at least one of hydroxyl, carboxyl and sulfonic acid group. As the dispersant, D4330 by BASF, MF (formaldehyde condensate of sodium methylnaphthalenesulfonate), disperse series in the air chemical industry, and the like can be used.

The dissolution promoting mixture comprises a first dissolution promoting agent, a second dissolution promoting agent and a third dissolution promoting agent, wherein the first dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compounds and cyclic alkyl ester, the second dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compounds and cyclic alkyl ester, and the third dissolution promoting agent can be at least one of polyalcohol, glycol ether, amide compounds and cyclic alkyl ester. The dissolution promoting mixture can also comprise a fourth dissolution promoting agent, and the fourth dissolution promoting agent can also be at least one of polyol, glycol ether, amide compounds and cyclic alkyl ester.

The polyhydric alcohol comprises at least one of ethylene glycol, 1, 5-pentanediol, polyvinyl alcohol, hexanediol, triethylene glycol, sorbitol, diethylene glycol, 1, 4-butanediol, polypropylene glycol, butanediol, mannitol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, glycerol, 1, 2-propanediol, polyethylene glycol, and 1, 3-propanediol; further, the polyhydric alcohol is at least one selected from the group consisting of ethylene glycol, triethylene glycol, sorbitol, diethylene glycol, glycerol, 1, 2-propanediol, polyethylene glycol, and 1, 3-propanediol.

The glycol ether comprises at least one of ethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol n-butyl ether, diethylene glycol monomethyl ether, methoxy triethylene glycol, ethoxy triethylene glycol and 1-butoxyethoxy-2-propanol; further, the glycol ether includes diethylene glycol monomethyl ether and/or diethylene glycol monobutyl ether.

The amide compound is at least one of polyvinylpyrrolidone, alpha-pyrrolidone and N, N-dimethylformamide.

The cyclic alkyl ester is at least one of valerolactone, butyrolactone, butenolide, caprolactone and heptalactone.

When the first, second and third desolvation agents are all polyhydric alcohols, the first, second and third desolvation agents may be at least one of ethylene glycol, 1, 5-pentanediol, polyvinyl alcohol, hexylene glycol, triethylene glycol, sorbitol, diethylene glycol, 1, 4-butanediol, polypropylene glycol, butylene glycol, mannitol, neopentylglycol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, glycerol, 1, 2-propanediol, polyethylene glycol and 1, 3-propanediol; further, the polyhydric alcohol is selected from any three of ethylene glycol, triethylene glycol, sorbitol, diethylene glycol, glycerol, 1, 2-propanediol, polyethylene glycol, and 1, 3-propanediol, but the first cosolvent, the second cosolvent, and the third cosolvent may not be the same substance. When the first cosolvent, the second cosolvent and the third cosolvent are all glycol ethers, amides or cyclic alkyl esters, the same is true when the first cosolvent, the second cosolvent and the third cosolvent are all polyols.

The wetting agent can act as a surface tension modifier to achieve good printing by reducing the surface tension or interfacial tension of the ink. The wetting agent is preferably BYK series and/or Surfynol series wetting agent of air chemical industry, such as at least one of Surfynol420, Surfynol465, Surfynol485, Surfynol604, BYK510, BYK104E, and BYK 348.

The preparation method of the color paste with high grinding efficiency comprises the following steps:

s1, mixing and pulping the disperse dye toner, the dissolution promoting mixture, the wetting agent and water, adding the dispersing agent after the dissolution promoting mixture uniformly mixes the disperse dye toner, and grinding into slurry to obtain pre-dispersion color paste;

s2, grinding, centrifuging and filtering the pre-dispersed color paste to obtain the color paste with the viscosity of 8Pa^.s～15Pa^.s, surface tension is 40N/m-50N/m; the grinding medium during grinding is zirconium beads with the diameter of 0.28-0.32 mm, the filling volume of the zirconium beads is 75-85%, and the grinding linear velocity is 13-14.2 m/s. In this preparation, the experimental procedure, in which no specific conditions are specified, is carried out according to the conventional procedures and conditions for preparing color pastes.

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

The following shows the specific names and proportions of the components of the high grinding efficiency mill base.

The 3 dispersed pigment toners shown in table 1.

TABLE 1

Table 2 shows the ingredients and their proportions in the dissolution promoting mixture.

TABLE 2

Two wetting agents are shown in table 3.

TABLE 3

For short	W-1	W-2
			Name of Compound	Surfynol 604	BYK 510

The ingredients of the formulation shown in Table 4 were added to ion exchange water, respectively, to prepare high grinding mill base samples, to obtain mill bases of examples 1-6 and mill bases of comparative examples 1-4. When preparing a high-grinding color paste sample, firstly, mixing and grinding the disperse dye toner, the dissolution promoting mixture, the wetting agent and the deionized water, and then adding the dispersing agent and grinding into a paste state to obtain the pre-dispersing color paste. Grinding and dispersing the mixture for 10 to 15 hours in a relaxation-resistant 25L sand mill by using sand milling zirconium beads with the diameter of 0.28 to 0.32mm, centrifuging at the rotating speed of 8000 to 20000r/min, and filtering on a 1.2mm GF membrane-1.0 mm PP membrane-0.8 mm PVDF membrane by adopting a series filtration method to obtain the color paste with high grinding efficiency.

TABLE 4

Firstly, stability tests are carried out on the high grinding efficiency color paste obtained in the above embodiments at the temperature of 65 ℃, the change of the medium particle size and the filtration condition of the color paste are observed, and the results are shown in table 5:

TABLE 5

As can be seen from the above, the color pastes of the embodiments 1 to 3 of the present invention have good stability. In the first comparative example, sulfonated lignin Ultrazin NA is used as a dispersant, generally, the system of the dispersant usually takes 25-30 h for grinding, is difficult to uniformly disperse within 10-15 h, has overlarge toner particle size and fails in filtration, and more seriously, when the content of toner is high, the sulfonated lignin Ultrazin NA is used as the dispersant, so that the viscosity mutation occurs, the whole sanding system is in a jelly shape, and the sanding fails. In the traditional process, less cosolvent is added for the toner during sanding, and as shown in example 4, example 5, comparative example two and comparative example three, one or two dissolution promoters are respectively used for preparing the color paste, and as can be seen from the results in table 5, the particle size distribution of the substance is larger, the solubility of the dye is lower, and the color paste filtration fails; in example 6, the dispersion of the final color paste is unstable due to the excessive toner content, so the ratio of the components in the color paste needs to be adjusted; the color paste in comparative example 4 does not contain a dissolution accelerator, the solubility of the dye is poor, and the color paste fails to filter.

Secondly, the high grinding efficiency color paste obtained in the above examples is prepared into dispersion ink, and the performance of the ink is tested, and the results are shown in Table 6:

TABLE 6

As can be seen from Table 6, the color pastes of examples 1 to 3 of the present invention have good compatibility with ink, and the dispersed ink prepared by the present invention has good stability, and has high light fastness and rubbing fastness.

Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.