Washable propylene ink and preparation method thereof

Abstract

The invention discloses water-washable propylene ink and a preparation method thereof. The water-washable propylene ink is mainly prepared from sulfonic acrylic acid-polyurethane composite emulsion, emulsion-coated pigment paste, a thickening agent, a defoaming agent, a dispersing agent, a builder, a sterilizing agent, water and the like. By optimizing the formula and adding the sulfonic acrylic acid-polyurethane composite emulsion, a washable film layer is formed, and it is guaranteed that patterns do not fall off or fade in the washing process. And meanwhile, a mode of coating the pigment slurry with milk is adopted, so that the pigment is more stable, and the washability of the ink and the durability of patterns are enhanced. According to the invention, the decontamination rate under various washing conditions exceeds 98%, which is significantly superior to that of commercially available propylene ink, and the propylene ink has good repeatability and stability. The ink not only meets the environmental protection requirement, but also can prolong the service life of textiles, and is suitable for household and industrial washing.

Description

Technical Field

[0001] The invention belongs to the field of acrylic ink, and in particular relates to washable acrylic ink and a preparation method thereof. Background Art

[0002] Acrylic ink is widely used in art painting, teaching, craft production and other fields due to its bright colors, strong covering power, quick drying and good adhesion. However, the main problem of traditional acrylic ink is that it is difficult to wash with water, especially after contaminating the skin, clothing or porous materials, it needs to be removed with organic solvents or strong detergents, which is not only inconvenient to operate, but also may cause skin irritation, affecting the safety of children.

[0003] The existing methods for making washable acrylic ink mainly include: 1. Selecting conventional pigments and adding detergents to achieve washable effects. The advantage is that the cost is relatively low, but the disadvantage is that it is not clean after washing with water and there is obvious residue; 2. Selecting water-soluble polymers (such as PVP) as film-forming materials: Although the washability is improved, the writing performance of the ink is not ideal, the decapping time is short, and the washability is also average. There will be color residue after washing with water. 3. Adding hydrophilic surfactants: It can improve the washability, but it is easy to cause the rheological instability of the ink, affect the painting performance, and may cause precipitation or stratification. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a water-washable acrylic ink, which significantly improves its water-washing performance while maintaining adhesion and color stability, so that the ink can be removed by conventional water washing after contaminating the skin or clothing.

[0005] In order to achieve the above purpose, the technical solution adopted by the present invention is: A water-washable acrylic ink comprises the following components by weight: 15-25 parts of sulfonic acrylic acid-polyurethane composite emulsion; 25-45 parts of latex pigment slurry; 0.3-2.0 parts of thickener; 0.1-0.3 parts of defoamer; 0.5-2.0 parts of dispersant; 8-15 parts of builder; 0.2-2 parts of bactericide; and 35-50 parts of distilled water.

[0006] The functions and effects of each additive in the above formula are as follows: Sulfonic acid acrylic acid-polyurethane composite emulsion: This is one of the core points of the present invention. The sulfonic acid acrylic acid-polyurethane composite emulsion selected in the present invention is an emulsion customized together with a professional emulsion synthesis manufacturer. In the present invention, it can be used as an ink film-forming substance. At the same time, because of the cross-linking density customized according to the washability requirements, it can achieve both film-forming and hydrophilicity. Finally, in the ink formula, it can provide both ink adhesion and hydrophilicity, maintain the adhesion of the ink on a variety of coated objects, and achieve a good water washing effect; emulsion-coated pigment slurry: It is also one of the core points of the present invention; organic silicon modified emulsion is used to coat the pigment. The pigment pigment after emulsion coating does not have good color development and is not easily deeply adsorbed by paper fibers or other coated surfaces, so that it can be easily washed clean with clean water; the pigment particle size is controlled at 200-300 nm; Thickener (hydroxyethyl cellulose commonly used in this field can be selected): adjust rheology and improve the use experience of ink; defoamer (organic silicon commonly used in this field can be selected): prevent the generation of bubbles and improve the uniformity of ink; dispersant (polymer hyperdispersant commonly used in this field can be selected): improve the dispersion stability of pigment and prevent sedimentation; keep the viscosity of ink within an appropriate range; builder (using safe and environmentally friendly food additives - sodium citrate): enhance water washability and improve stain removal effect; bactericide (phenoxyethanol commonly used in this field can be selected): prevent microbial contamination and extend the storage period.

[0007] The present invention also provides a method for preparing a water-washable acrylic ink, comprising the following steps: Step 1), grinding the organosilicon modified pigment slurry to 200-300 nm; Step 2), prepare thickener solution, add emulsion, pigment slurry, detergent and fungicide, stir evenly, adjust pH to 7-8, filter and remove impurities to obtain the finished product. Beneficial effects of the present invention:

[0008] 1. The present invention uses a sulfonic acid acrylic-polyurethane composite emulsion, which contains sulfonic acid groups, which can enhance water solubility, so that the ink film layer swells when washed with water, making it easy to remove. The emulsion has both the weather resistance of acrylic resin and the flexibility of polyurethane, ensuring that the coating has good adhesion and mechanical strength on substrates such as glass, ceramics, and cloth.

[0009] 2. The present invention adopts organic silicon modified emulsion pigment slurry, and the pigment is coated by nano-scale organic silicon emulsion, which can effectively prevent the pigment from penetrating into the deep layer of the fabric and improve the washing effect. The pigment particle size is controlled at 200-300 nm to ensure dispersion stability and improve color uniformity and brightness.

[0010] 3. The present invention optimizes the rheological properties of the ink by adding hydroxyethyl cellulose and a high molecular weight hyperdispersant, so that the ink has good anti-settling properties, easy writing properties and appropriate viscosity.

[0011] The ink of the present invention has excellent adhesion, color stability and water washability, and can be applied to painting on substrates such as paper, ceramics, glass, textiles, etc., and is particularly suitable for children's painting, teaching demonstrations and craft production. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is a comparison diagram of the coloring effect of the washable acrylic ink of the present invention and the common acrylic ink on the market on white cotton cloth; Figure 2 This is a comparison diagram of the coloring effect of the washable acrylic ink of the present invention and the common acrylic ink on the market on leather; Figure 3 This is a comparison chart of the coloring effects of the washable acrylic ink of the present invention and the common acrylic ink on the market on white paper, black paper and glass; Figure 4 This is a comparison diagram before and after washing when the water-washable acrylic ink of Example 1 is used to test the skin washability; Figure 5 This is a comparison chart before and after washing when using commercially available ordinary acrylic ink to test the skin washability; Figure 6 This is a comparison diagram before and after washing when the washable acrylic ink of Example 1 is used to test the water washability of fabric; Figure 7 This is a comparison chart before and after washing when testing the water-washing performance of fabrics using commercially available ordinary acrylic ink. DETAILED DESCRIPTION

[0013] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations. Example 1

[0014] 1. A formula composition (by weight) of a washable acrylic ink is as follows: Sulfonic acid acrylic-polyurethane composite emulsion: 15 parts; latex pigment slurry (titanium dioxide): 35 parts; thickener (hydroxyethyl cellulose): 0.5 parts; defoaming agent (silicone): 0.2 parts; dispersant (polymer hyperdispersant): 1.0 parts; builder (sodium citrate): 10 parts; bactericide (phenoxyethanol): 0.5 parts; distilled water: 37.8 parts.

[0015] 2. The specific preparation process is as follows: Step 1) Prepare the pigment paste Take 10 parts of silicone-modified acrylic emulsion, mix with 88 parts of titanium dioxide, add 2 parts of dispersant, stir at 2000 r / min for 20 minutes; grind with a sand mill to a particle size of 200-300 nm to obtain a stable emulsion-encapsulated pigment slurry; Step 2) Ink preparation Take 39.8 parts of distilled water, add 0.5 parts of thickener, and stir until completely dissolved; add 0.2 parts of polymer superdispersant, 15 parts of sulfonic acid acrylic acid-polyurethane composite emulsion, 35 parts of latex pigment slurry, 8 parts of detergent and 0.5 parts of fungicide in sequence, and stir evenly; adjust the pH to 7-8, stir evenly, filter and remove impurities, and the finished product is obtained.

[0016] 3. The product prepared in this embodiment was tested and compared with similar products on the market for water washability.

[0017] 3.1 Experimental method Experimental design: 20 cotton cloth samples (10 cm × 10 cm) were selected and coated with the ink of the present invention and commercially available ordinary acrylic ink respectively. After drying for 24 hours, water washing test was performed. 3.2 Washing method Pure water rinse: Soak the sample in room temperature water for 2 minutes Washing in a domestic washing machine: Use standard washing machine cycle (30°C, 10 minutes) Soap Hand Wash: Hand wash with regular soap and water for 3 minutes 3.3 Test results (n=20)

[0018] 3.4 Data Analysis 3.4.1 Comparison of Decontamination Rate The stain removal rates of the washable acrylic ink of this embodiment in the three washing methods are significantly higher than those of the commercially available ordinary acrylic ink. In particular, in the household washing machine washing and hand washing tests, the stain removal rates of the ink of the present invention are 98.2% ± 1.3% and 99.6% ± 0.5%, respectively, which are 199% and 118% higher than the 32.8% ± 5.2% and 45.6% ± 6.8% of the commercially available ordinary acrylic ink, respectively, indicating that the washability of the ink of this embodiment is significantly better than that of the existing products.

[0019] After rinsing with pure water for 2 minutes, the decontamination rate of the ink of the present invention is 85.4% ± 2.1%, while that of ordinary commercial acrylic ink is only 10.2% ± 3.5%, indicating that the ink of the present invention has good water washability even in the absence of detergent.

[0020] 3.4.2 Statistical analysis One-way ANOVA was used to compare the decontamination rates of the two inks under three washing methods. The results showed that P The values ​​are all less than 0.05, indicating that the decontamination rate of the water-washable ink of this embodiment is significantly better than that of the commercially available ordinary acrylic ink.

[0021] Example 2 The formula composition (by weight) of a water-washable acrylic ink is as follows: Sulfonic acid acrylic-polyurethane composite emulsion: 20 parts; latex pigment slurry: 25 parts; thickener (hydroxyethyl cellulose): 0.6 parts; defoamer (silicone): 0.2 parts; dispersant (polymer hyperdispersant): 1.0 parts; builder (sodium citrate): 8 parts; bactericide (phenoxyethanol): 0.5 parts; distilled water: 45.7 parts.

[0022] The preparation process and the comparison of the water washability test are the same as those in Example 1. The test results show that the decontamination rate of the water washable acrylic ink of this example under the three washing methods is significantly higher than that of the ordinary acrylic ink on the market.

[0023] Example 3 The formula composition (by weight) of a water-washable acrylic ink is as follows: Sulfonic acid acrylic-polyurethane composite emulsion: 18 parts; latex pigment slurry: 38 parts; thickener (hydroxyethyl cellulose): 0.4 parts; defoamer (silicone): 0.2 parts; dispersant (polymer hyperdispersant): 1.0 parts; builder (sodium citrate): 9 parts; bactericide (phenoxyethanol): 0.4 parts; distilled water: 33 parts.

[0024] The preparation process and the comparison of the water washability test are the same as those in Example 1. The test results show that the decontamination rate of the water washable acrylic ink of this example under the three washing methods is significantly higher than that of the ordinary acrylic ink on the market.

[0025] In addition, the coloring effects of the washable acrylic ink of the present invention and the commercially available common acrylic ink were compared, and the specific coloring effects are as follows: like Figure 1 As shown, the washable acrylic ink of the present invention and the common acrylic ink both have a slight lag when painted on white cloth, and the two are similar in general; like Figure 2 As shown, the washable acrylic ink of the present invention and the common acrylic ink on the market are both relatively smooth when written on leather, and the writing effects of the two on the above two materials are similar; like Figure 3 As shown, the washable acrylic ink of the present invention and the common acrylic ink on the market have comparable writing performance on black and white cardboard and glass, with no obvious difference.

[0026] At the same time, the washable acrylic ink prepared in Example 1 was used to compare the skin washability with the commercially available ordinary acrylic ink: the sample pen was painted on the back of the hand in turn, and after observing at room temperature for half an hour, the back of the hand was rinsed with clean water (without hand sanitizer or other cleaning substances), and the degree of cleaning was observed after simple rubbing. Figure 4 and Figure 5 As shown, the water-washable acrylic ink prepared in Example 1 leaves no traces on the skin after washing, while the comparative example using commercially available ordinary acrylic ink cannot be washed off the skin.

[0027] At the same time, the washable acrylic ink prepared in Example 1 was used to compare the washing performance of fabrics with commercially available ordinary acrylic ink: the sample pen was painted on fabrics (the fabrics were made of six materials: wool / acrylic / polyester / nylon / cotton / acetate fiber), and after observing at room temperature for 72 hours, it was soaked in clean water (without washing liquid or other cleaning substances) for half an hour, and the degree of cleaning was observed after simple rubbing. Figure 6 and Figure 7 As shown, the washable acrylic ink prepared in Example 1 leaves no traces on the fabrics (6 kinds of fabrics) after washing, while the comparative example using commercially available ordinary acrylic ink cannot be washed on the fabrics (6 kinds of fabrics).

[0028] The above implementation modes are only descriptions of the preferred implementation modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary engineering and technical personnel in the field should fall within the protection scope determined by the claims of the present invention.

Claims

1. A water-washable acrylic ink, characterized in that: The following components are included by mass: Sulfonic acid acrylic acid-polyurethane composite emulsion 25-50 parts; 5-35 parts of latex pigment paste; Thickener 0.3-2.0 parts; Defoaming agent 0.1-0.3 parts; Dispersant 0.5-2.0 parts; 3-8 parts of detergent; 0.2-2 parts of fungicide; 8-20 parts of distilled water.

2. The water-washable acrylic ink according to claim 1, characterized in that: The following components are included by mass: 30 parts of sulfonic acid acrylic acid-polyurethane composite emulsion; 20 parts of milk-encapsulated pigment paste; Thickener 0.5 parts; Defoaming agent 0.2 parts; Dispersant 1.0 part; 5 parts of detergent; 0.5 parts of fungicide; 15 parts of distilled water.

3. The water-washable acrylic ink according to claim 1, characterized in that: The latex-coated pigment slurry is coated with an organic silicon-modified acrylic emulsion, and the particle size is controlled at 200-300 nm.

4. The method for preparing the washable acrylic ink according to claim 1, characterized in that: The steps include: Step 1), grinding the organosilicon modified pigment slurry to 200-300 nm; Step 2), prepare thickener solution, add emulsion, pigment slurry, detergent and fungicide, stir evenly, adjust pH to 7-8, filter and remove impurities to obtain the finished product.

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