WO2019128157A1 - 一种印花糊料用液体防腐剂及其制备方法和应用 - Google Patents

一种印花糊料用液体防腐剂及其制备方法和应用 Download PDF

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WO2019128157A1
WO2019128157A1 PCT/CN2018/092495 CN2018092495W WO2019128157A1 WO 2019128157 A1 WO2019128157 A1 WO 2019128157A1 CN 2018092495 W CN2018092495 W CN 2018092495W WO 2019128157 A1 WO2019128157 A1 WO 2019128157A1
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Prior art keywords
preservative
printing paste
liquid preservative
liquid
auxiliary agent
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PCT/CN2018/092495
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English (en)
French (fr)
Inventor
刘蕴慧
张健
张宗亮
张强
郇路恒
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青岛明月海藻集团有限公司
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Publication of WO2019128157A1 publication Critical patent/WO2019128157A1/zh

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6138—Polymerisation products of glycols, e.g. Carbowax, Pluronics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6422—Compounds containing nitro or nitroso groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65118—Compounds containing hydroxyl groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65125—Compounds containing ester groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/6515—Hydrocarbons
    • D06P1/65162—Hydrocarbons without halogen

Definitions

  • the invention belongs to the technical field of auxiliaries for printing pastes, in particular to a liquid preservative for printing pastes, a preparation method and application thereof.
  • the printing paste refers to a polymer compound which can be thickened in the printing paste.
  • the printing paste is generally dissolved in water or a hydrophilic polymer thick colloidal solution which is sufficiently swollen in water before being added to the printing paste, or an oil/water type or water/oil type emulsion paste.
  • a part of the dye is dissolved in water, and another part of the dye is dissolved, adsorbed or dispersed in the original paste.
  • the printing paste is the main component of the printing paste, which determines the printing running performance, the surface color of the dye, the smoothness of the pattern outline, and the like.
  • Commonly used printing pastes are sodium alginate, gelatin, gum arabic, and the like.
  • the thickening effect of the printing paste is mainly reflected in the viscosity.
  • the factors affecting the viscosity of the solution include temperature, shear rate, microorganisms, etc., and microorganisms are a controllable factor with great influence.
  • the addition of preservatives can effectively reduce the effect of microorganisms on the printing viscosity.
  • the preservative used in printing paste is mainly solid preservative.
  • This kind of preservative is currently added in the printing paste in two ways: one is added in the process of milling, the summer milling temperature is higher, the pole It is easy to cause the decomposition of some preservatives, thus affecting the anti-corrosion effect; the second is to add in the process of mixing, the difference of particle size, density and other indicators of preservatives and other additives to the uniformity of the printing paste and the anti-corrosion effect Have a certain impact.
  • the invention provides a liquid preservative for printing paste, a preparation method and application thereof, and solves the problems that the prior art preservative has large dust, high temperature easy decomposition and poor mixing uniformity, which affects the anticorrosion effect.
  • a liquid preservative for printing pastes of the present invention is mainly achieved by the following technical solutions: the liquid preservatives include solid preservatives, auxiliaries and water, the solid preservatives, auxiliaries and water
  • the weight ratio is 4-5: 3-4: 1-2;
  • the auxiliary agent is a mixture of polyethylene glycol, propylene glycol, glycerin, isohexadecane and polyether modified silicone, and polyethylene glycol is 30-40% of the total weight of the auxiliary agent, propylene glycol is 10-20% of the total weight of the auxiliary agent, glycerol is 20-30% of the total weight of the auxiliary agent, and isohexadecane is 10-20% of the total weight of the auxiliary agent.
  • the polyether modified silicone is 3-5% of the total amount of the auxiliary agent.
  • the invention relates to a composite liquid preservative, wherein the components of the liquid preservative have synergistic effect, the liquid preservative has good uniformity, has appropriate viscosity, and fully exerts the effective antiseptic effect of the original solid preservative.
  • it is used in the production process of printing paste, greatly reducing the dust in the printing paste production process, the mixing effect is good, the mixing is uniform, the appearance of the printing paste is improved, the anti-corrosion effect is good, and the dosage is small.
  • the production cost is reduced; and, after application, the printing paste has better dispersibility in water, reduces the clumping phenomenon of the printing paste during dissolution, reduces the printing enthalpy, and increases the production efficiency.
  • the liquid preservative has a viscosity of 20-40 mPa ⁇ s and a density of 1.065-1.080 g/cm 3 .
  • the liquid preservative of the invention has small viscosity and can effectively reduce the influence of microorganisms on the printing viscosity, the density is moderate, and the properties are uniform and stable.
  • the solid preservative is either or both of sodium butyl benzoate and 2-bromo-2-nitro-1,3-propanediol. These solid preservatives are frequently used in printing pastes, have good antiseptic effect, and can be better integrated with the printing paste, and have no effect on the printing effect.
  • the present invention is not limited to these two solid preservatives, but may be other solid preservatives.
  • the polyethylene glycol is either or both of polyethylene glycol 200 and polyethylene glycol 400.
  • Polyethylene glycol has excellent lubricity, moisture retention and dispersibility.
  • Polyethylene glycol 200 and polyethylene glycol 400 have moderate molecular weight, suitable viscosity, non-toxic and non-irritating properties, and have certain moisture absorption properties in the liquid preservative.
  • the liquid preservative has a suitable viscosity to facilitate the use of a liquid preservative.
  • the invention relates to a method for preparing a liquid preservative for printing paste, which is mainly realized by the following technical solutions: comprising the following steps: 1) weighing polyethylene glycol, propylene glycol, glycerin, and different sixteen respectively The alkane and the polyether modified silicone are uniformly mixed to obtain an auxiliary agent, and are used as a spare; 2) water is taken, a solid preservative and the auxiliary agent obtained in the step 1) are added, stirred, and completely miscible, thereby obtaining a liquid preservative.
  • the liquid preservative of the invention has simple preparation method and convenient operation, and is realized under normal conditions, has no special requirements on equipment, has high production efficiency, low cost and is easy to realize industrialization.
  • the obtained liquid preservative has uniform texture and good fluidity, and can be used in the production process of printing paste, the mixing thereof is uniform, the dust and particle agglomeration phenomenon is greatly reduced, the high temperature resistance, the acid and alkali resistance, the property are stable, and the printing is performed. There is no side effect in the production process of the paste, no effect on the printing effect, and the anti-corrosion effect is good.
  • both step 1) and step 2) are carried out at room temperature.
  • the liquid preservative of the invention is prepared at room temperature, can be produced at any time, has stable performance and is convenient for storage.
  • the use of a liquid preservative for a printing paste of the present invention is mainly achieved by the following technical solution: the liquid preservative is used in a sodium alginate printing paste. Since sodium alginate is used for printing paste, it is usually 30-mesh sodium alginate powder. The content of fine powder of less than 120 mesh in this sodium alginate powder is more than 10%. The presence of these fine powders will cause printing paste. The dust is flying during the production process, which pollutes the environment, affects the health of the employees, reduces the product yield and increases the cost.
  • the liquid preservative of the invention is used in the mixing stage of sodium alginate, which reduces the generation of dust and reduces the dust. The impact on the environment and the health of employees increases the uniformity of the materials and improves the appearance of the printed paste.
  • the method comprises the following steps: a) taking a liquid preservative during the mixing process of the printing paste production, adding the sodium alginate powder by spraying, and mixing uniformly; b) adding the thickener sequentially , dyeing agent and water softener, mixing evenly, packaging, that is, printing paste.
  • the liquid preservative of the invention is added to the sodium alginate powder by spraying, has good fluidity and is convenient to be added, and the liquid preservative after atomization is gently adsorbed on the surface of the sodium alginate powder, thereby further reducing dust generation. Increased uniformity of the mix.
  • the weight ratio of the liquid preservative to the sodium alginate powder is 2-3:100.
  • the use of the liquid preservative greatly reduces the amount of pure solid preservative, reduces the production cost, avoids the influence of temperature on the anti-corrosion effect, ensures better anti-corrosion effect, improves the quality of the printing paste, and improves the economy. benefit.
  • the activator is added in an amount of 0-10% of the total weight of the printing paste
  • the softener is added in an amount of 0-6% of the total weight of the printing paste.
  • the dyeing agent is anhydrous sodium sulfate and/or sodium chloride
  • the water softening agent is sodium hexametaphosphate and/or disodium edetate.
  • the liquid preservative of the invention can make the printing paste have better printing effect and improve the quality of the printing paste under the combined action of the dyeing agent and the water softener; the dyeing agent and the soft water agent are cheap and easy to use, and the use thereof Convenient, reducing the production cost of printing paste.
  • the liquid preservative of the present invention is a composite liquid preservative formed by adding an auxiliary agent and water to a solid preservative, and the solid antiseptic in the liquid preservative
  • the agent has good solubility in water under the action of the auxiliary agent, and the dispersion is uniform.
  • the components are synergistic, the compatibility is good, and the mutual complementation is achieved.
  • the obtained liquid preservative is uniform and uniform, has appropriate viscosity, and can withstand high temperature and resistance.
  • a liquid preservative for printing paste comprising a solid preservative, an auxiliary agent and water, the weight ratio of the solid preservative, auxiliary agent and water is 4-5: 3-4: 1-2
  • the auxiliary agent is a mixture of polyethylene glycol, propylene glycol, glycerin, isohexadecane and polyether modified silicone, and the polyethylene glycol is 30-40% of the total weight of the auxiliary agent, and the propylene glycol is an auxiliary agent.
  • glycerol is 20-30% of the total weight of the auxiliary agent
  • isohexadecane is 10-20% of the total weight of the auxiliary agent
  • the polyether modified silicone is the total amount of the auxiliary agent 3 -5%.
  • the liquid preservative has a viscosity of 20 to 40 mPa ⁇ s and a density of 1.065 to 1.080 g/cm 3 .
  • the solid preservative is any one or two of sodium butyl parahydroxybenzoate and 2-bromo-2-nitro-1,3-propanediol.
  • the polyethylene glycol is any one or two of polyethylene glycol 200 and polyethylene glycol 400.
  • a preparation method of liquid preservative for printing paste comprises the following steps: 1) weighing polyethylene glycol, propylene glycol, glycerin, isohexadecane and polyether modified silicone separately, and mixing uniformly 2, taking water, adding a solid preservative and the auxiliary agent obtained in step 1), stirring, making it completely miscible, that is, a liquid preservative.
  • both the step 1) and the step 2) are carried out at room temperature.
  • the method comprises the following steps: a) taking a liquid preservative during the mixing process of the printing paste production, adding the sodium alginate powder by spraying, and mixing uniformly; b) sequentially adding a thickener, a dyeing agent and Softener, evenly mixed, packaged, that is, printed paste.
  • the weight ratio of the liquid preservative to the sodium alginate powder is 2-3:100.
  • the activator is added in an amount of 0-10% of the total weight of the printing paste
  • the softener is added in an amount of 0-6% of the total weight of the printing paste.
  • the agent is anhydrous sodium sulfate and/or sodium chloride
  • the water softener is sodium hexametaphosphate and/or disodium edetate.
  • the invention relates to a liquid preservative for printing paste, the preparation method thereof comprises the following steps:
  • solid preservative is sodium butyl paraben and the polyethylene glycol is polyethylene glycol 200;
  • the obtained product has a good appearance, the 120-mesh dust passing rate is 2%, and the temperature is lowered at 30 ° C for 7 days, and the viscosity drop rate is 6%.
  • the invention relates to a liquid preservative for printing paste, the preparation method thereof comprises the following steps:
  • the solid preservative is a mixture of sodium butyl parahydroxybenzoate and 2-bromo-2-nitro-1,3-propanediol
  • the polyethylene glycol is polyethylene glycol 400
  • the invention relates to a liquid preservative for printing paste, the preparation method thereof comprises the following steps:
  • the solid preservative is a mixture of sodium butyl parahydroxybenzoate and 2-bromo-2-nitro-1,3-propanediol
  • the polyethylene glycol is polyethylene glycol 400
  • Example 1 and Example 3 The liquid preservative obtained in Example 1 and Example 3 and the commercially available liquid preservative poly-2-methyl-4-isothiazolin-3-one compound were respectively subjected to performance test experiments including density, viscosity and stability. Among them, the stability was measured by placing the liquid preservative in an incubator at 30 ° C for 7 days, and then measuring the viscosity and calculating the viscosity drop rate. The experimental results are shown in Table 1.
  • the liquid preservative of the present invention has a density of viscosity, good fluidity and convenient use; and the liquid preservative of the present invention has a viscosity reduction rate of less than 5 after being placed in an incubator at 30 ° C for 7 days. %, the density change is small, which is significantly smaller than the viscosity and density change of the existing commercially available liquid preservative poly-2-methyl-4-isothiazolin-3-one compound; therefore, the liquid preservative of the present invention has Very good quality stability.
  • Example 1 and Example 3 The liquid preservative obtained in Example 1 and Example 3 and the commercially available liquid preservative poly-2-methyl-4-isothiazolin-3-one compound were respectively used in the mixing stage of sodium alginate production printing paste.
  • Medium take 100g sodium alginate powder, spray the above different liquid preservatives into the sodium alginate powder according to the weight added amount of 2.5%, mix evenly, and then add thickener, dyeing agent and soft water in turn.
  • the agent is uniformly mixed and packaged, that is, the printing paste is obtained; the amount of dust in the air in the mixing stage, the uniformity of material mixing and the corrosion resistance of the obtained printing paste are measured, and the printing comparison experiment is performed, and the experimental results are shown in Table 2. .
  • the liquid preservative of the present invention is used in the mixing stage of sodium alginate production printing paste, in the production process of sodium alginate printing paste, the amount of dust is less than 3%, the liquid preservative It is convenient to spray, the material after mixing is uniform, the dust is less, the corrosion resistance is good, and the printing effect prepared by the printing paste is good; and the existing commercially available liquid preservative poly-2-methyl-4-isothiazole is used.
  • the amount of dust is more than 6%, the material after the mixing is evenly poor, the dust is less, and the corrosion resistance is poor, and the printing effect prepared by the printing paste is generally
  • the liquid preservative of the invention has good anti-corrosion performance, greatly reduces the amount of dust in the mixing stage of the sodium alginate printing paste, and reduces the agglomeration of the powder particles during the mixing process, and has no effect on the printing effect.
  • the liquid preservative of the present invention is a composite liquid preservative formed by adding an auxiliary agent and water to a solid preservative, and the solid antiseptic in the liquid preservative
  • the agent has good solubility in water under the action of the auxiliary agent, and the dispersion is uniform.
  • the components are synergistic, the compatibility is good, and the mutual complementation is achieved.
  • the obtained liquid preservative is uniform and uniform, has appropriate viscosity, and can withstand high temperature and resistance.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Coloring (AREA)

Abstract

本发明公开了一种印花糊料用液体防腐剂及其制备方法和应用。本发明的液体防腐剂包括固体防腐剂、助剂和水，固体防腐剂、助剂和水的重量比为 4-5：3-4：1-2；助剂为聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅的混合物，聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅的重量百分含量分别为 30-40％、10-20％、20-30％、10-20％和 3-5％；本发明还给出上述液体防腐剂的制备方法，在水中添加固体防腐剂和助剂混合均匀而得到，上述液体防腐剂用于海藻酸钠印花糊料中。本发明的液体防腐剂各组分具有很有的协同作用，成分均匀一致，分散性好，降低了混料时的粉尘和团聚现象，用量少，防腐效果好。

Description

一种印花糊料用液体防腐剂及其制备方法和应用 技术领域
本发明属于印花糊料用助剂的技术领域，特别是指一种印花糊料用液体防腐剂及其制备方法和应用。
背景技术
印花糊料是指加在印花色浆中能起到增稠作用的高分子化合物。印花糊料在加到印花色浆之前，一般均溶于水或是在水中充分溶胀而分散的亲水性高分子稠厚胶体溶液，或者是油/水型或水/油型乳化糊。调制成印花色浆时，一部分染料溶解在水中，另一部分染料则溶解、吸附或分散在印花原糊中。印花糊料是印花色浆的主要组分，它决定着印花运转性能，染料的表面给色量、花纹轮廓的光洁度等。常用的印花糊料有海藻酸钠、龙胶、阿拉伯树胶等。
印花糊料的增稠作用主要体现在粘度方面，影响溶液粘度的因素包括温度、剪切速率、微生物等，其中微生物为一个影响较大的可控因素。防腐剂的加入可以有效降低微生物对印花粘度的影响。目前，印花糊料使用的防腐剂主要为固体防腐剂，这种防腐剂当前在印花糊料中的加入方式有两种：一是在磨粉的过程中加入，夏季磨粉温度较高，极易造成部分防腐剂的分解，从而影响防腐效果；二是在混料的过程中加入，防腐剂的粒度、密度等指标与其它助剂的差异对印花糊料的混料均一性以及防腐效果都有一定的影响。
发明内容
本发明提供一种印花糊料用液体防腐剂及其制备方法和应用，解决了现有技术中防腐剂使用过程中粉尘大、高温易分解和混合均匀性差而影响其防腐效果的问题。
本发明的一种印花糊料用液体防腐剂，其主要是通过以下技术方案加以实现的：所述液体防腐剂包括固体防腐剂、助剂和水，所述固体防腐剂、助剂和水的重量比为4-5：3-4：1-2；所述助剂为聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅的混合物，聚乙二醇为助剂总重量的30-40％，丙二醇为助 剂总重量的10-20％，丙三醇为助剂总重量的20-30％，异十六烷为助剂总重量的10-20％，聚醚改性有机硅为助剂总量的3-5％。
本发明是一种复合液体防腐剂，这种液体防腐剂的各组分协同增效作用明显，所得液体防腐剂均匀性好，具有适当的粘度，充分发挥了原有固体防腐剂的高效防腐效果；同时，其用于印花糊料的生产过程中，大大降低了印花糊料生产过程中的粉尘，混合效果好，混料均匀，改善了印花糊料的外观，且防腐效果好，用量少，降低了生产成本；并且，应用后印花糊料在水中的分散性更好，降低了印花糊料在溶解时的抱团现象，减少了印花瑕疵，增加了生产效率。
作为一种优选的实施方案，所述液体防腐剂的粘度为20-40mPa·s，密度为1.065-1.080g/cm 3。本发明的液体防腐剂的粘度小，可以有效降低微生物对印花粘度的影响，密度适中，性质均一稳定。
作为一种优选的实施方案，所述固体防腐剂为对羟基苯甲酸丁酯钠、2-溴-2-硝基-1,3-丙二醇中的任意一种或两种。这些固体防腐剂在印花糊料中使用频率高，其防腐效果好，可以更好地与印花糊料融为一体，对印花效果没有影响。当然，本发明中也不仅限于这两种固体防腐剂，还可以是其它的固体防腐剂。
作为一种优选的实施方案，所述聚乙二醇为聚乙二醇200、聚乙二醇400中的任意一种或两种。聚乙二醇具有优良的润滑性、保湿性和分散性，聚乙二醇200和聚乙二醇400分子量适中，粘度适宜，无毒无刺激性，在该液体防腐剂中具有一定的吸湿性能，使液体防腐剂具有适宜粘度，方便液体防腐剂的使用。
本发明的一种印花糊料用液体防腐剂的制备方法，其主要是通过以下技术方案加以实现的：包括以下步骤：1)分别称取聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅，混合均匀，得助剂，备用；2)取水，添加固体防腐剂和步骤1)所得的助剂，搅拌，使其完全混溶，即得液体防腐剂。
本发明的液体防腐剂的制备方法简单，操作方便，均在常规条件下实现，对设备没有特殊要求，生产效率高，成本低，易于实现产业化。所得液体防腐剂质地均匀一致，流动性好，可以用于印花糊料的生产过程中，其混料均匀，大大降低了粉尘和颗粒团聚现象，能够耐高温，耐酸碱，性质稳定，在印花糊料的生产过程中没有副作用，对印花效果无影响，防腐效果好。
作为一种优选的实施方案，所述步骤1)和所述步骤2)均是在室温下进行。本发明的液体防腐剂是在室温下制备而成的，随时可以生产，性能稳定，方便储存。
本发明的一种印花糊料用液体防腐剂的应用，其主要是通过以下技术方案加以实现的：所述液体防腐剂用于海藻酸钠印花糊料中。由于海藻酸钠用于印花糊料时，通常是采用30目的海藻酸钠粉末，这种海藻酸钠粉末中小于120目的细粉的含量达10％以上，这些细粉的存在会造成印花糊料生产过程中粉尘飞扬，既污染环境，影响员工身体健康，又会降低产品收率，增加成本；本发明的液体防腐剂用于海藻酸钠的混料阶段，减少了粉尘的产生，降低了粉尘对环境和员工身体健康的影响，增加了物料的均一性，改善了印花糊料的外观。
作为一种优选的实施方案，包括以下步骤：a)在印花糊料生产的混料过程中，取液体防腐剂，以喷雾方式加入海藻酸钠粉末中，混合均匀；b)依次加入增稠剂、促染剂和软水剂，混合均匀，包装，即得印花糊料。本发明的液体防腐剂以喷雾的方式添加到海藻酸钠粉末中，流动性好，添加方便，雾化后的液体防腐剂在海藻酸钠粉末表面轻轻被吸附，进一步减少了粉尘的产生，增加了混料的均匀性。
作为一种优选的实施方案，所述液体防腐剂与海藻酸钠粉末的重量比为2-3：100。这种液体防腐剂的使用大大降低了纯固体防腐剂的用量，降低了生产成本，避免了温度对防腐效果的影响，保证了较好的防腐效果，提高了印花糊料的质量，提高了经济效益。
作为一种优选的实施方案，所述促染剂的添加量为所述印花糊料总重量的0-10％，所述软水剂的添加量为所述印花糊料总重量的0-6％，所述促染剂为无水硫酸钠和/或氯化钠，所述软水剂为六偏磷酸钠和/或乙二胺四乙酸二钠。本发明的液体防腐剂在促染剂和软水剂的配合作用下，可以使印花糊料具有更好的印花效果，提高印花糊料的品质；这些促染剂和软水剂价廉易得，使用方便，降低了印花糊料的生产成本。
与现有技术相比，本发明的有益效果是：本发明的液体防腐剂是在固体防腐剂中添加助剂和水而形成的一种复合液体防腐剂，这种液体防腐剂中的固体防腐剂在助剂的作用下在水中的溶解性好，分散均匀，各组分之间相互协同， 相容性好，相辅相成，所得液体防腐剂的均匀一致，具有适当的粘度，能够耐高温，耐酸碱，性能稳定，方便储存，充分发挥了原有固体防腐剂的高效防腐效果；其制备方法简单，操作方便，易于实现产业化，可以应用于印花糊料的生产过程中，大大降低印花糊料生产过程中的粉尘和团聚现象，混合效果好，混料均匀，改善了印花糊料的外观，在印花糊料的生产过程中没有副作用，对印花效果无影响，防腐效果好，用量少，降低了生产成本，提高了生产效率。
具体实施方式
下面将结合本发明的具体实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
一种印花糊料用液体防腐剂，所述液体防腐剂包括固体防腐剂、助剂和水，所述固体防腐剂、助剂和水的重量比为4-5：3-4：1-2；所述助剂为聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅的混合物，聚乙二醇为助剂总重量的30-40％，丙二醇为助剂总重量的10-20％，丙三醇为助剂总重量的20-30％，异十六烷为助剂总重量的10-20％，聚醚改性有机硅为助剂总量的3-5％。
具体地，所述液体防腐剂的粘度为20-40mPa·s，密度为1.065-1.080g/cm 3。
优选地，所述固体防腐剂为对羟基苯甲酸丁酯钠、2-溴-2-硝基-1,3-丙二醇中的任意一种或两种。
具体地，所述聚乙二醇为聚乙二醇200、聚乙二醇400中的任意一种或两种。
一种印花糊料用液体防腐剂的制备方法，包括以下步骤：1)分别称取聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅，混合均匀，得助剂，备用；2)取水，添加固体防腐剂和步骤1)所得的助剂，搅拌，使其完全混溶，即得液体防腐剂。
具体地，所述步骤1)和所述步骤2)均是在室温下进行。
一种印花糊料用液体防腐剂的应用，所述液体防腐剂用于海藻酸钠印花糊料中。
优选地，包括以下步骤：a)在印花糊料生产的混料过程中，取液体防腐剂，以喷雾方式加入海藻酸钠粉末中，混合均匀；b)依次加入增稠剂、促染剂和软水剂，混合均匀，包装，即得印花糊料。
具体地，所述液体防腐剂与海藻酸钠粉末的重量比为2-3：100。
进一步地，所述促染剂的添加量为所述印花糊料总重量的0-10％，所述软水剂的添加量为所述印花糊料总重量的0-6％，所述促染剂为无水硫酸钠和/或氯化钠，所述软水剂为六偏磷酸钠和/或乙二胺四乙酸二钠。
实施例一
本发明的一种印花糊料用液体防腐剂，其制备方法包括以下步骤：
1)按照重量比为3.5：2：3：1：0.5的比例分别称取聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅，将其混合均匀，得助剂；
其中，固体防腐剂为对羟基苯甲酸丁酯钠，聚乙二醇为聚乙二醇200；
2)按照重量比为5：4：1的比例分别称取固体防腐剂、上述助剂和水，在水中，添加固体防腐剂和上述助剂，混匀，至完全溶融状态，得液体防腐剂。
具体使用时，所得产品外观较好，120目粉尘通过率为2％，在30℃恒温放置7天，粘度下降率为6％。
实施例二
本发明的一种印花糊料用液体防腐剂，其制备方法包括以下步骤：
1)按照重量比为3.7：1：3：2：0.3的比例分别称取聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅，将其混合均匀，得助剂；
其中，固体防腐剂为对羟基苯甲酸丁酯钠和2-溴-2-硝基-1,3-丙二醇的混合物，聚乙二醇为聚乙二醇400；
2)按照重量比为4：3：2的比例分别称取固体防腐剂、上述助剂和水，在水中，添加固体防腐剂和上述助剂，混匀，至完全溶融状态，得液体防腐剂。
实施例三
本发明的一种印花糊料用液体防腐剂，其制备方法包括以下步骤：
1)按照重量比为3.2：1.2：2：1.5：0.4的比例分别称取聚乙二醇、丙二醇、 丙三醇、异十六烷和聚醚改性有机硅，将其混合均匀，得助剂；
其中，固体防腐剂为对羟基苯甲酸丁酯钠和2-溴-2-硝基-1,3-丙二醇的混合物，聚乙二醇为聚乙二醇400；
2)按照重量比为4.5：3.5：1.5的比例分别称取固体防腐剂、上述助剂和水，在水中，添加固体防腐剂和上述助剂，混匀，至完全溶融状态，得液体防腐剂。
实验1
将实施例一和实施例三所得的液体防腐剂和市售的液体防腐剂聚2-甲基-4-异噻唑啉-3-酮化合物分别进行性能测试实验，包括密度、粘度和稳定性，其中，稳定性的测定是将液体防腐剂置于30℃的恒温箱中放置7天，然后，测定其粘度，并计算粘度下降率，实验结果如表1所示。
表1 不同液体防腐剂的性能指标测定结果
Figure PCTCN2018092495-appb-000001
由表1可以看出，本发明的液体防腐剂的密度为，粘度为；其流动性好，方便使用；本发明的液体防腐剂在30℃的恒温箱中放置7天后，粘度下降率小于5％，密度变化很小，这明显小于现有的市售液体防腐剂聚2-甲基-4-异噻唑啉-3-酮化合物的粘度和密度变化情况；因此，本发明的液体防腐剂具有很好的质量稳定性。
实验2
将实施例一和实施例三所得的液体防腐剂和市售的液体防腐剂聚2-甲基-4-异噻唑啉-3-酮化合物分别用于海藻酸钠生产印花糊料的混料阶段中，取100g海藻酸钠粉末，采用喷雾的方式将上述不同液体防腐剂按照2.5％的重量添加量分别加入海藻酸钠粉末中，混合均匀，然后，依次加入增稠剂、促染剂和软水剂，混合均匀，包装，即得印花糊料；测定该混料阶段空气中的粉尘量，物料混合均匀性和所得印花糊料的防腐性，并进行印花比较实验，实验结果如表2所示。
表2 不同液体防腐剂用于海藻酸钠印花糊料混料阶段中性能指标测定结果
样品名称 粉尘量(％) 混料均匀性 粘度下降率(％) 印花效果
实施例一 2.58 好 6.2％ 不影响
实施例二 2.67 好 6.9％ 不影响
实施例三 2.84 好 7.1％ 不影响
对照样 7.36 差 13.8％ 印花均匀性略差
由表2可以看出，本发明的液体防腐剂用于海藻酸钠生产印花糊料的混料阶段时，在海藻酸钠印花糊料的生产过程中，粉尘量小于3％，该液体防腐剂方便喷雾，混料后的物料均匀一致，粉尘少，防腐性好，由此印花糊料制备的印花效果好；而使用现有的市售的液体防腐剂聚2-甲基-4-异噻唑啉-3-酮化合物在海藻酸钠印花糊料的混料阶段中，粉尘量大于6％，混料后的物料均匀较差，粉尘少，防腐性差，由此印花糊料制备的印花效果一般；此外，本发明的液体防腐剂防腐性能好，大大降低了海藻酸钠生产印花糊料的混料阶段的粉尘量，降低了混料过程中粉末颗粒的团聚现象，对印花效果无影响。
与现有技术相比，本发明的有益效果是：本发明的液体防腐剂是在固体防腐剂中添加助剂和水而形成的一种复合液体防腐剂，这种液体防腐剂中的固体防腐剂在助剂的作用下在水中的溶解性好，分散均匀，各组分之间相互协同，相容性好，相辅相成，所得液体防腐剂的均匀一致，具有适当的粘度，能够耐高温，耐酸碱，性能稳定，方便储存，充分发挥了原有固体防腐剂的高效防腐效果；其制备方法简单，操作方便，易于实现产业化，可以应用于印花糊料的生产过程中，大大降低印花糊料生产过程中的粉尘和团聚现象，混合效果好，混料均匀，改善了印花糊料的外观，在印花糊料的生产过程中没有副作用，对印花效果无影响，防腐效果好，用量少，降低了生产成本，提高了生产效率。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种印花糊料用液体防腐剂，其特征在于：所述液体防腐剂包括固体防腐剂、助剂和水，所述固体防腐剂、助剂和水的重量比为4-5：3-4：1-2；
    所述助剂为聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅的混合物，聚乙二醇为助剂总重量的30-40％，丙二醇为助剂总重量的10-20％，丙三醇为助剂总重量的20-30％，异十六烷为助剂总重量的10-20％，聚醚改性有机硅为助剂总量的3-5％。
  2. 根据权利要求1所述的印花糊料用液体防腐剂，其特征在于：
    所述液体防腐剂的粘度为20-40mPa .s，密度为1.065-1.080g/cm 3。
  3. 根据权利要求1所述的印花糊料用液体防腐剂，其特征在于：
    所述固体防腐剂为对羟基苯甲酸丁酯钠、2-溴-2-硝基-1,3-丙二醇中的任意一种或两种。
  4. 根据权利要求1所述的印花糊料用液体防腐剂，其特征在于：
    所述聚乙二醇为聚乙二醇200、聚乙二醇400中的任意一种或两种。
  5. 根据权利要求1-4中任意一项所述的印花糊料用液体防腐剂的制备方法，其特征在于，包括以下步骤：
    1)分别称取聚乙二醇、丙二醇、丙三醇、异十六烷和聚醚改性有机硅，混合均匀，得助剂，备用；
    2)取水，添加固体防腐剂和步骤1)所得的助剂，搅拌，使其完全混溶，即得液体防腐剂。
  6. 根据权利要求5所述的印花糊料用液体防腐剂的制备方法，其特征在于：
    所述步骤1)和所述步骤2)均是在室温下进行。
  7. 根据权利要求1-4中任意一项所述的印花糊料用液体防腐剂的应用，其特征在于：
    所述液体防腐剂用于海藻酸钠印花糊料中。
  8. 根据权利要求7所述的印花糊料用液体防腐剂的应用，其特征在于，包括以下步骤：
    a)在印花糊料生产的混料过程中，取液体防腐剂，以喷雾方式加入海藻酸钠粉末中，混合均匀；
    b)依次加入促染剂和软水剂，混合均匀，包装，即得印花糊料。
  9. 根据权利要求8所述的印花糊料用液体防腐剂的应用，其特征在于：
    所述液体防腐剂与海藻酸钠粉末的重量比为2-3：100。
  10. 根据权利要求8所述的印花糊料用液体防腐剂的应用，其特征在于：
    所述促染剂的添加量为所述印花糊料总重量的0-10％，所述软水剂的添加量为所述印花糊料总重量的0-6％，所述促染剂为无水硫酸钠和/或氯化钠，所述软水剂为六偏磷酸钠和/或乙二胺四乙酸二钠。
PCT/CN2018/092495 2017-12-26 2018-06-22 一种印花糊料用液体防腐剂及其制备方法和应用 WO2019128157A1 (zh)

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