WO2021213403A1 - 一种在硅橡胶上可涂绘不易脱落可清理的颜料及其制作方法 - Google Patents

一种在硅橡胶上可涂绘不易脱落可清理的颜料及其制作方法 Download PDF

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WO2021213403A1
WO2021213403A1 PCT/CN2021/088486 CN2021088486W WO2021213403A1 WO 2021213403 A1 WO2021213403 A1 WO 2021213403A1 CN 2021088486 W CN2021088486 W CN 2021088486W WO 2021213403 A1 WO2021213403 A1 WO 2021213403A1
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silicone rubber
pigment
polyoxyethylene ether
paint
sulfonate
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PCT/CN2021/088486
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English (en)
French (fr)
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虎盈
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北京督想教育科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0079—Azoic dyestuff preparations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/007—Metal oxide
    • C09D17/008—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/06—Artists' paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the embodiments of the present application relate to the technical field of pigments, and in particular to a pigment that can be painted on a silicone rubber that is not easy to fall off and can be cleaned and a manufacturing method thereof.
  • Silicone rubber refers to a rubber whose main chain consists of alternating silicon and oxygen atoms, and two organic groups are usually attached to the silicon atoms. Silicone rubber is divided into high temperature silicone rubber and room temperature silicone rubber. High temperature silicone rubber is mainly used to manufacture various silicone rubber products, while room temperature silicone rubber is mainly used as an adhesive, potting material or mold. Due to the low surface energy of silicone rubber, it is difficult for the prepared coating to spread on its surface, and the adhesion effect is poor.
  • the embodiments of the present application provide a paint that can be painted on silicone rubber, is not easy to fall off, and a cleaning method thereof, so as to solve the difficulty of coloring on silicone rubber by existing general-purpose pigments, poor painting performance, poor flexibility, and easy fall off. Problems that cannot be effectively cleaned up.
  • the embodiments of the present application provide a paint that can be painted on the silicone rubber, which is not easy to fall off and can be cleaned.
  • the content by weight includes: 54.75-55.75% of water and 0.75-1% of propylene glycol.
  • Titanium dioxide 15-16%, acrylic resin 16-16.75%, polymethacrylate 9.75-10%, polyether sulfonate 0.25-0.4%, branched chain alkylbenzene sulfonate 0.1-0.25%, fatty alcohol poly Oxyethylene ether 0.25-0.5%, fatty alcohol polyoxyethylene ether carboxylate 0.075-0.125%, nonylphenol polyoxyethylene ether 0.025-0.075%, secondary alkyl sulfonate 0.05-0.1%, polyethylene glycol 0.05 -0.1%, triethanolamine 0.125-0.25%.
  • the content by weight percentage includes: 55.25% of water, 1% of propylene glycol, 15.5% of titanium dioxide, 16.75% of acrylic resin, 9.88% of polymethacrylate, 0.4% of polyether sulfonate, branched alkyl benzene sulfonate Sodium sulfate 0.25%, fatty alcohol polyoxyethylene ether 0.4%, fatty alcohol polyoxyethylene ether carboxylate 0.12%, nonylphenol polyoxyethylene ether 0.05%, secondary alkyl sulfonate 0.1%, polyethylene glycol 0.1 %, 0.2% triethanolamine.
  • the pigment also includes a colorant with a weight percentage of 0.5-1.0%.
  • the colorant includes pigment red P.R.112, pigment yellow P.Y.151, pigment orange P.O.34, pigment green P.G.7 or pigment blue P.B.15:0.
  • the embodiments of the present application provide the above-mentioned manufacturing method of a paint that can be painted on a silicone rubber that is not easy to fall off and can be cleaned, including the following steps:
  • the method further includes the step of adding 0.5-1.0% by weight of colorant between step S1 and step S2.
  • the fineness of the color material can reach 10-15 microns by grinding.
  • the examples of this application are based on water, propylene glycol, titanium dioxide, acrylic resin, polymethacrylate, polyether sulfonate, sodium branched alkylbenzene sulfonate, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether carboxylic acid Salt, nonylphenol polyoxyethylene ether, sodium secondary alkyl sulfonate, polyethylene glycol, triethanolamine as raw materials. in:
  • Water and propylene glycol are solvents, which are used to adjust the volatilization rate of the pigment, maintain the humidity, and control the proper setting time of the pigment.
  • Titanium dioxide is a filler. Titanium dioxide is insoluble in water and has stable physical and chemical properties. It is used to enhance the leveling and decoloring power of pigments, improve the hiding power of pigments, and enhance the glossiness.
  • Acrylic resin is a film-forming material, and its functions include: 1. It has film-forming properties, and its addition makes the pigment dry and condense into a film (different from water powder and other pigments); 2. Enhance the light resistance and aging resistance of the pigment; 3. The proper ratio will enhance the washing resistance (hands are not easy to rub down).
  • Polymethacrylate is a softener and adhesive. Its function is to work with acrylic resin to enhance the flexibility of the pigment, so that the overall adhesiveness and toughness of the pigment after solidification are enhanced, and it is not easy to break, and it can still maintain the integrity on the soft silicone material. Pigment properties.
  • Polyether sulfonate, sodium branched alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether carboxylate are combined into surfactants, and their functions include: 1. Wetting effect: reduce the surface of the medium Tension and the interfacial tension between the medium and the pigment; 2. Stabilization: Improve the dispersion stability of the glued particles and the pigment in the pigment, and keep the pigment composition stable.
  • Polyoxyethylene nonylphenol ether and sodium secondary alkyl sulfonate are combined as emulsifiers, which are used to stabilize the pigment liquid, which is similar to the stabilizing effect of surfactants.
  • Polyethylene glycol is a wetting and dispersing agent for wetting pigments and adjusting pigment consistency.
  • Triethanolamine is a pH adjuster, used to properly increase the alkalinity of the pigment, and is easy to store the pigment.
  • the above components interact with each other, and the obtained pigment can be painted on the silicone rubber.
  • the pigment is flexible after solidification and is not easy to fall off. It can be competent for the flexible characteristics of silicone rubber. After the pigment is cleaned, the silicone rubber is not dyed and can be reused, saving silicon. The cost of purchasing a large amount of silicone rubber substrates for rubber painting.
  • the pigments in the examples of this application fill the gaps in silicone rubber pigments and have broad market prospects.
  • the pigments of Examples 1-5 of the same weight were respectively coated on the surface of the silicone rubber, and placed in a constant temperature (37°C) water bath for 20 minutes to fully cure the pigments, and the quality of the pigment layer after solid drying was observed.
  • Example 2 Complete and no bubbles Curl without cracks 1 good
  • Example 3 Complete and no bubbles Curl without cracks 1 good
  • Example 4 Complete and no bubbles Curl without cracks 1 good
  • Example 5 Complete and no bubbles Curl without cracks 1 good
  • the results show that the pigments of the examples of the present application can be well coated on the silicone rubber, and the obtained pigment layer is intact without bubbles, has good flexibility, and has an adhesion level of 1 and can be better attached to the silicone rubber without falling off. At the same time, the pigment layer has excellent exfoliation and good cleanability.
  • Acrylic paint (Shanghai Industrial Marley Painting Materials Co., Ltd./Model: Acrylic Paint Permanent Red);
  • Comparative Example 1 The only difference from Example 1 is that the acrylic resin is replaced with the same amount of alkyd resin;
  • Comparative Example 2 The only difference from Example 1 is that the acrylic resin is replaced with the same amount of amino resin;
  • Comparative Example 3 The only difference from Example 1 is that no acrylic resin is added;
  • Comparative Example 4 The only difference from Example 1 is that 1/2 times the amount of acrylic resin is added;
  • Comparative Example 5 The only difference from Example 1 is that 1.5 times the amount of acrylic resin is added;
  • Comparative Example 6 The only difference from Example 1 is the addition of 2 times the amount of acrylic resin.
  • Example 1 An average of 220 times of rubbing and abrasion occurred, and the experimental results were excellent.
  • Example 2 Abrasion occurred during 205 times of rubbing on average, and the experimental results were excellent.
  • Example 3 An average of 212 times of rubbing showed abrasion, and the experimental results were excellent.
  • Example 4 An average of 216 times of rubbing showed abrasion, and the experimental results were excellent.
  • Example 5 An average of 211 times of rubbing and abrasion occurred, and the experimental results were excellent. Comparative example 3 Abrasion occurred after 20 times of rubbing on average, and the experimental results were poor. Comparative example 4 An average of 50 times of rubbing was worn out, and the experimental results were poor.
  • the pigments of the examples of this application showed good performance in all aspects during the test.
  • the pigments have good ductility on the surface of the silicone rubber, no bubbles, and no obvious texture; after the silicone rubber is extruded, the pigments have no morphological changes and have good adhesion; It can be cleaned up once with tape, and there is no color residue on the surface of the silicone rubber; it has abrasion resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
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Abstract

一种在硅橡胶上可涂绘不易脱落可清理的颜料，颜料的原料包括水、丙二醇、二氧化钛、丙烯酸树脂、聚甲基丙烯酸酯、聚醚磺酸盐、支链烷基苯磺酸钠、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯醚羧酸盐、壬基酚聚氧乙烯醚、仲烷基磺酸钠、聚乙二醇和三乙醇胺。颜料的制作方法包括步骤为：在配料桶中依次加入丙烯酸树脂、聚乙二醇，高速分散机搅拌；再加入二氧化钛和水，高速分散；加入其它原料搅拌、静置。

Description

一种在硅橡胶上可涂绘不易脱落可清理的颜料及其制作方法
本申请要求于2020年04月21日提交中国专利局、申请号为CN2020103181536、申请名称为“一种在硅橡胶上可涂绘不易脱落可清理的颜料及其制作方法”的中国专利的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请实施例涉及颜料技术领域，具体涉及一种在硅橡胶上可涂绘不易脱落可清理的颜料及其制作方法。
背景技术
硅橡胶是指主链由硅和氧原子交替构成，硅原子上通常连有两个有机基团的橡胶。硅橡胶分为高温硅橡胶和室温硅橡胶，高温硅橡胶主要用于制造各种硅橡胶制品，而室温硅橡胶则主要是作为粘接剂、灌封材料或模具使用。由于硅橡胶表面能较低，制备涂层很难在其表面铺展，附着效果较差。
目前市面上存在涂装于硅橡胶上的保护油墨，但尚且不存在能涂绘于硅橡胶的颜料。通用颜料在硅橡胶上涂绘通常存在以下问题：与硅橡胶无法完美契合，着色困难；柔韧性差，不能适应硅橡胶的柔性，硅橡胶形变后凝固颜料层不能随之形变而脱落；颜料在固化过程中，融入硅橡胶体，清除颜料时有残留印迹，颜料无法有效清理而使硅橡胶不能重复使用。
有鉴于此，特提出本申请。
申请内容
为此，本申请实施例提供一种在硅橡胶上可涂绘不易脱落可清理的颜料及其制作方法，以解决现有通用颜料在硅橡胶上着色困难涂绘性能差、柔韧性差易脱落以及不能有效清理的问题。
为了实现上述目的，本申请实施例提供如下技术方案：
根据本申请实施例的第一方面，本申请实施例提供一种在硅橡胶上可涂绘不易脱落可清理的颜料，按重量百分含量计包括：水54.75-55.75％、丙二醇0.75-1％、二氧化钛15-16％、丙烯酸树脂16-16.75％、聚甲基丙烯酸酯9.75-10％、聚醚磺酸盐0.25-0.4％、支链烷基苯磺酸钠0.1-0.25％、脂肪醇聚氧乙烯醚0.25-0.5％、脂肪醇聚氧乙烯醚羧酸盐0.075-0.125％、壬基酚聚氧乙烯醚0.025-0.075％、仲烷基磺酸钠0.05-0.1％、聚乙二醇0.05-0.1％、三乙醇胺0.125-0.25％。
进一步地，按重量百分含量计包括：水55.25％、丙二醇1％、二氧化钛15.5％、丙烯酸树脂16.75％、聚甲基丙烯酸酯9.88％、聚醚磺酸盐0.4％、支链烷基苯磺酸钠0.25％、脂肪醇聚氧乙烯醚0.4％、脂肪醇聚氧乙烯醚羧酸盐0.12％、壬基酚聚氧乙烯醚0.05％、仲烷基磺酸钠0.1％、聚乙二醇0.1％、三乙醇胺0.2％。
进一步地，所述颜料还包括重量百分含量为0.5-1.0％的色料。
进一步地，所述色料包括颜料红P.R.112、颜料黄P.Y.151、颜料橙P.O.34、颜料绿P.G.7或颜料蓝P.B.15:0。
根据本申请实施例的第二方面，本申请实施例提供一种上述的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法，包括以下步骤：
S1、在配料桶依次加入丙烯酸树脂、聚乙二醇，开启高速分散机，转速控制在1000-1500r/min，搅拌时间为5-8分钟；
S2、然后加入二氧化钛、水，高速分散20-30分钟；
S3、接着加入丙二醇、三乙醇胺、仲烷基磺酸钠、聚甲基丙烯酸酯、聚醚磺酸盐、支链烷基苯磺酸钠、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯醚羧酸盐、壬基酚聚氧乙烯醚，搅拌10-15分钟，静置20-30分钟。
进一步地，所述方法在步骤S1和步骤S2之间，还包括加入重量百 分含量为0.5-1.0％的色料的步骤。
进一步地，采用研磨的方式使所述色料的细度达到10-15微米。
进一步地，加入色料后，搅拌20-25分钟。
本申请实施例具有如下优点：
本申请实施例以水、丙二醇、二氧化钛、丙烯酸树脂、聚甲基丙烯酸酯、聚醚磺酸盐、支链烷基苯磺酸钠、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯醚羧酸盐、壬基酚聚氧乙烯醚、仲烷基磺酸钠、聚乙二醇、三乙醇胺为原料。其中：
水和丙二醇为溶剂，用于调节颜料挥发速度，保持湿度，控制颜料凝固时间适当。
二氧化钛为填料，二氧化钛不溶于水，物理化学性质稳定，用于增强颜料流平性与消色力，提高颜料遮盖力，提升光泽度光泽度。
丙烯酸树脂为成膜物，其作用包括：1.本身具有成膜性，其加入使得颜料干后凝结成膜(不同于水粉等颜料)；2.增强颜料的耐光性和抗老化性；3.适当比例将增强抗洗涤性(手不易揉搓下来)。
聚甲基丙烯酸酯为柔性剂与胶黏剂，其作用是与丙烯酸树脂共同作用增强颜料柔性，使得颜料凝固后整体胶黏性与韧性增强，不易碎裂，在软硅胶材质上仍然可保持整体颜料性质。
聚醚磺酸盐、支链烷基苯磺酸钠、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯醚羧酸盐合为表面活性剂，其作用包括：1.湿润作用：降低介质的表面张力和介质与颜料间的界面张力；2.稳定作用：增进涂胶粒子和颜料在颜料中的分散稳定性，保持颜料组份稳定。
壬基酚聚氧乙烯醚、仲烷基磺酸钠合为乳化剂，其用于稳定颜料液，与表面活性剂稳定作用类似。
聚乙二醇为湿润分散剂，用于湿润颜料，调节颜料稠度。
三乙醇胺为PH调节剂，用于适当提升颜料碱性，易于颜料保存。
以上各组分相互作用，制得的颜料可在硅橡胶上涂绘，颜料凝固后具有柔性，不易脱落，能够胜任硅橡胶柔性特点，颜料清理后硅橡胶不 染色，可重复使用，节约了硅橡胶绘画时所需大量购买硅橡胶底材的费用，本申请实施例的颜料填补了用于硅橡胶颜料的空白，具有广阔的市场前景。
具体实施方式
以下由特定的具体实施例说明本申请的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本申请的其他优点及功效，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
实施例1
本实施例的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法包括以下步骤：
S1、在配料桶依次加入16.75％的丙烯酸树脂、0.1％的聚乙二醇，开启高速分散机，转速控制在1200r/min，搅拌时间为6分钟；
S2、然后加入15.5％的二氧化钛、55.25％的水，高速分散25分钟；
S3、接着加入1％的丙二醇、0.2％的三乙醇胺、0.1％的仲烷基磺酸钠、9.88％的聚甲基丙烯酸酯、0.4％的聚醚磺酸盐、0.25％的支链烷基苯磺酸钠、0.4％的脂肪醇聚氧乙烯醚、0.12％的脂肪醇聚氧乙烯醚羧酸盐、0.05％的壬基酚聚氧乙烯醚，搅拌10分钟，静置25分钟。
实施例2
本实施例的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法包括以下步骤：
S1、在配料桶依次加入16.05％的丙烯酸树脂、0.095％的聚乙二醇，开启高速分散机，转速控制在1000r/min，搅拌时间为8分钟；
S2、采用研磨的方式使颜料红P.R.112的细度达到10～15微米，加入0.6％的颜料红P.R.112，搅拌25分钟；
S3、然后加入15.6％的二氧化钛、55.5％的水，高速分散20分钟；
S4、接着加入0.8％的丙二醇、0.125％的三乙醇胺、0.077％的仲烷基磺酸钠、9.95％的聚甲基丙烯酸酯、0.38％的聚醚磺酸盐、0.25％的支链烷基苯磺酸钠、0.4％的脂肪醇聚氧乙烯醚、0.125％的脂肪醇聚氧乙烯醚羧酸盐、0.048％的壬基酚聚氧乙烯醚，搅拌12分钟，静置20分钟。
实施例3
本实施例的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法包括以下步骤：
S1、在配料桶依次加入16.5％的丙烯酸树脂、0.05％的聚乙二醇，开启高速分散机，转速控制在1500r/min，搅拌时间为6分钟；
S2、采用研磨的方式使颜料黄P.Y.151的细度达到10～15微米，加入1.0％的颜料黄P.Y.151，搅拌20分钟；
S3、然后加入15.5％的二氧化钛、55.2％的水，高速分散20～30分钟；
S5、接着加入0.75％的丙二醇、0.2％的三乙醇胺、0.05％的仲烷基磺酸钠、9.87％的聚甲基丙烯酸酯、0.25％的聚醚磺酸盐、0.2％的支链烷基苯磺酸钠、0.3％的脂肪醇聚氧乙烯醚、0.075％的脂肪醇聚氧乙烯醚羧酸盐、0.055％的壬基酚聚氧乙烯醚，搅拌15分钟，静置20分钟。
实施例4
本实施例的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法包括以下步骤：
S1、在配料桶依次加入16.75％的丙烯酸树脂、0.08％的聚乙二醇，开启高速分散机，转速控制在1200r/min，搅拌时间为8分钟；
S2、采用研磨的方式使颜料红P.R.112的细度达到10～15微米，加入0.5％的颜料红P.R.112，搅拌20分钟；
S3、然后加入15.8％的二氧化钛、54.75％的水，高速分散20～30分钟；
S4、接着加入0.9％的丙二醇、0.18％的三乙醇胺、0.08％的仲烷基磺酸钠、9.85％的聚甲基丙烯酸酯、0.4％的聚醚磺酸盐、0.1％的支链烷基苯 磺酸钠、0.5％的脂肪醇聚氧乙烯醚、0.08％的脂肪醇聚氧乙烯醚羧酸盐、0.03％的壬基酚聚氧乙烯醚，搅拌12分钟，静置30分钟。
实施例5
本实施例的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法包括以下步骤：
S1、在配料桶依次加入16.3％的丙烯酸树脂、0.1％的聚乙二醇，开启高速分散机，转速控制在1500r/min，搅拌时间为5分钟；
S2、采用研磨的方式使颜料黄P.Y.151的细度达到10～15微米，加入0.9％的颜料黄P.Y.151，搅拌22分钟；
S3、然后加入15.7％的二氧化钛、55.1％的水，高速分散20～30分钟；
S4、接着加入1％的丙二醇、0.25％的三乙醇胺、0.08％的仲烷基磺酸钠、9.75％的聚甲基丙烯酸酯、0.28％的聚醚磺酸盐、0.15％的支链烷基苯磺酸钠、0.25％的脂肪醇聚氧乙烯醚、0.08％的脂肪醇聚氧乙烯醚羧酸盐、0.06％的壬基酚聚氧乙烯醚，搅拌15分钟，静置25分钟。
测试例1
分别将相同重量的实施例1-5的颜料涂覆于硅橡胶表面，置于恒温(37℃)水浴箱中维持20分钟，使颜料充分固化，观察实干后的颜料层质量。
按GB/T 1731-1993《漆膜柔韧性测定法》测定颜料的柔韧性能，然后用50倍体式显微镜观察颜料是否有裂纹。
参照GB 9286-1998的划格法对颜料的附着力进行测定，同时参照民间刀削拨法，用工艺刀片划一扇形切面，用10N力于刀尖挑拨，按剥落颜料面积分好、中、差3种。
测试结果见表1。
表1
样品 颜料层质量 柔韧性 附着力 剥落性
实施例1 完整无气泡 卷曲无裂纹 1 好
实施例2 完整无气泡 卷曲无裂纹 1 好
实施例3 完整无气泡 卷曲无裂纹 1 好
实施例4 完整无气泡 卷曲无裂纹 1 好
实施例5 完整无气泡 卷曲无裂纹 1 好
结果表明：本申请实施例的颜料能够很好的涂覆在硅橡胶上，得到的颜料层完整无气泡，柔韧性良好，附着力达到1级，能够较好的附着于硅橡胶上不脱落，同时颜料层剥落性优异，具有较好的可清理性。
测试例2
一、实验材料
实施例1-5的颜料；
水彩颜料(上海实业马利画材有限公司/型号：324朱红色)；
水粉颜料(上海实业马利画材有限公司/型号：324朱红色)；
国画颜料(上海实业马利画材有限公司/型号：302大红色)；
油画颜料(上海实业马利画材有限公司/型号：324朱红色)；
纺织颜料(上海实业马利画材有限公司/型号：324朱红色)；
丙烯颜料(上海实业马利画材有限公司/型号：丙烯颜料永固红)；
玻璃颜料(上海实业马利画材有限公司/型号：306红色)；
陶瓷颜料(上海实业马利画材有限公司/型号：302大红)；
彩墨(北京一得阁墨业有限责任公司/型号：彩墨红色)；
对比例1：与实施例1的区别仅在于，用等量的醇酸树脂替换丙烯酸树脂；
对比例2：与实施例1的区别仅在于，用等量的氨基树脂替换丙烯酸树脂；
对比例3：与实施例1的区别仅在于，不添加丙烯酸树脂；
对比例4：与实施例1的区别仅在于，添加1/2倍量的丙烯酸树脂；
对比例5：与实施例1的区别仅在于，添加1.5倍量的丙烯酸树脂；
对比例6：与实施例1的区别仅在于，添加2倍量的丙烯酸树脂。
二、研究方法
2.1着色性检测
用统一的排笔在硅橡胶表面分别涂绘相同量的上述各颜料，待颜料实干后检测颜料在硅橡胶表面的涂绘情况。结果见表2。
表2
Figure PCTCN2021088486-appb-000001
Figure PCTCN2021088486-appb-000002
结果表明：本申请实施例的颜料、水粉颜料、国画颜料、油画颜料、丙烯颜料、玻璃颜料、陶瓷颜料、对比例3、对比例4、对比例5、对比例6在硅橡胶上具有良好的着色性。
2.2附着性检测
目的：检验颜料在硅橡胶表面的附着情况，在硅橡胶变形情况下颜料是否容易脱落、掉色。因水彩颜料、纺织颜料、彩墨、对比例1、对比例2的着色性较差，不再纳入检测。
具体操作：用手挤压硅橡胶，使其变形，查看在硅橡胶变形的情况下，附着其上的颜料的形态变化。结果见表3。
表3
Figure PCTCN2021088486-appb-000003
Figure PCTCN2021088486-appb-000004
结果表明：本申请实施例的颜料、水粉颜料、国画颜料、油画颜料、对比例3、对比例4在硅橡胶上具有较好的附着性。
2.3可清理性检测
即检验在外力作用下，颜料是否容易被清理掉。因丙烯颜料、玻璃颜料、陶瓷颜料、对比例5、对比例6的附着性较差，不再纳入检验。
具体操作：用同一种胶带覆盖在颜料表面，再扯下胶带，查看颜料被清理情况。结果见表4。
表4
Figure PCTCN2021088486-appb-000005
Figure PCTCN2021088486-appb-000006
结果表明：本申请实施例的颜料、对比例3、对比例4具有可清理性。
2.4耐磨损性检测
即检验在外力作用下，检测颜料是否容易被磨损掉。因水粉颜料、国画颜料、油画颜料的可清理性较差，不再纳入检验。
具体操作：用食指和拇指在颜料表面用相同的力度揉搓，查看在多少次数情况下颜料磨损状态。结果见表5。
表5
样品 结果
实施例1 平均揉搓220次出现磨损，实验结果优。
实施例2 平均揉搓205次出现磨损，实验结果优。
实施例3 平均揉搓212次出现磨损，实验结果优。
实施例4 平均揉搓216次出现磨损，实验结果优。
实施例5 平均揉搓211次出现磨损，实验结果优。
对比例3 平均揉搓20次出现磨损，实验结果差。
对比例4 平均揉搓50次出现磨损，实验结果差。
结果表明：本申请实施例的颜料具有耐磨损性。
三、结论
本申请实施例的颜料在检验中各方面性能均呈现良好状态，颜料在硅橡胶表面延展性良好，无气泡，无明显纹理；对硅橡胶挤压后，颜料未发生形态改变，附着性良好；用胶带清理一次即可清理干净，且在硅橡胶表面无任何颜色残留；具有耐磨损性。
虽然，上文中已经用一般性说明及具体实施例对本申请作了详尽的描述，但在本申请基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本申请精神的基础上所做的这些修改或改进，均属于本申请要求保护的范围。

Claims (8)

  1. 一种在硅橡胶上可涂绘不易脱落可清理的颜料，其特征在于，按重量百分含量计包括：水54.75-55.75％、丙二醇0.75-1％、二氧化钛15-16％、丙烯酸树脂16-16.75％、聚甲基丙烯酸酯9.75-10％、聚醚磺酸盐0.25-0.4％、支链烷基苯磺酸钠0.1-0.25％、脂肪醇聚氧乙烯醚0.25-0.5％、脂肪醇聚氧乙烯醚羧酸盐0.075-0.125％、壬基酚聚氧乙烯醚0.025-0.075％、仲烷基磺酸钠0.05-0.1％、聚乙二醇0.05-0.1％、三乙醇胺0.125-0.25％。
  2. 根据权利要求1所述的在硅橡胶上可涂绘不易脱落可清理的颜料，其特征在于，按重量百分含量计包括：水55.25％、丙二醇1％、二氧化钛15.5％、丙烯酸树脂16.75％、聚甲基丙烯酸酯9.88％、聚醚磺酸盐0.4％、支链烷基苯磺酸钠0.25％、脂肪醇聚氧乙烯醚0.4％、脂肪醇聚氧乙烯醚羧酸盐0.12％、壬基酚聚氧乙烯醚0.05％、仲烷基磺酸钠0.1％、聚乙二醇0.1％、三乙醇胺0.2％。
  3. 根据权利要求1所述的在硅橡胶上可涂绘不易脱落可清理的颜料，其特征在于，所述颜料还包括重量百分含量为0.5-1.0％的色料。
  4. 根据权利要求3所述的在硅橡胶上可涂绘不易脱落可清理的颜料，其特征在于，所述色料包括颜料红P.R.112、颜料黄P.Y.151、颜料橙P.O.34、颜料绿P.G.7或颜料蓝P.B.15:0。
  5. 一种权利要求1所述的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法，其特征在于，包括以下步骤：
    S1、在配料桶依次加入丙烯酸树脂、聚乙二醇，开启高速分散机，转速控制在1000-1500r/min，搅拌时间为5-8分钟；
    S2、然后加入二氧化钛、水，高速分散20-30分钟；
    S3、接着加入丙二醇、三乙醇胺、仲烷基磺酸钠、聚甲基丙烯酸酯、聚醚磺酸盐、支链烷基苯磺酸钠、脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯醚羧酸盐、壬基酚聚氧乙烯醚，搅拌10-15分钟，静置20-30分钟。
  6. 根据权利要求5所述的在硅橡胶上可涂绘不易脱落可清理的颜料 的制作方法，其特征在于，在步骤S1和步骤S2之间，还包括加入重量百分含量为0.5-1.0％的色料的步骤。
  7. 根据权利要求6所述的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法，其特征在于，采用研磨的方式使所述色料的细度达到10-15微米。
  8. 根据权利要求6所述的在硅橡胶上可涂绘不易脱落可清理的颜料的制作方法，其特征在于，加入色料后，搅拌20-25分钟。
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