Acrylic acid adhesive with high washing resistance and preparation method thereof

Abstract

The invention relates to the technical field of acrylic acid adhesives, in particular to a highly washable acrylic acid adhesive and a preparation method thereof.The highly washable acrylic acid adhesive is at least prepared from, by weight, 30-60 parts of isooctyl methacrylate, 200-300 parts of vinyl acetate, 200-300 parts of methyl methacrylate, 1000-2000 parts of butyl acrylate, 30-60 parts of acrylic acid, 3000-4000 parts of diluent and 5-10 parts of initiator. According to the present invention, by optimizing the synthesis formula, the high washing resistance is achieved, the good bonding strength and the good stability are maintained, the wide application prospect and the wide market value are provided, and the requirements of various fields requiring the washing resistance can be met.

Description

Technical Field

[0001] The invention relates to the technical field of acrylic adhesives, in particular to a highly water-resistant acrylic adhesive and a preparation method thereof. Background Art

[0002] Acrylic adhesives are widely used in various fields due to their good adhesion, weather resistance and environmental protection. However, traditional acrylic adhesives are insufficient in terms of water washability, especially in application scenarios that need to withstand multiple water washings, and their bonding strength and stability are often difficult to maintain. Therefore, it is of great significance to develop a highly water-resistant acrylic adhesive. However, in the development process of highly water-resistant acrylic adhesive products, the balance between water resistance and bonding strength is a technical difficulty that needs to be overcome. The Chinese patent application (publication number CN113736259A) discloses the use of hydrophobic monomer silicone-modified acrylate copolymers to improve water resistance, but traditional hydrophobic modification easily leads to brittleness of the adhesive layer and cannot meet the actual application requirements. Summary of the invention

[0003] In order to solve the above problems, the present invention provides a highly water-resistant acrylic adhesive and a preparation method thereof. By optimizing the synthetic formula, high water-resistant performance is achieved while maintaining good bonding strength and stability. It has broad application prospects and market value and can meet the needs of various fields requiring water-resistant performance.

[0004] On one hand, the present invention provides a highly water-resistant acrylic adhesive, wherein the raw materials for preparing the adhesive at least include, by weight, 30-60 parts of isooctyl methacrylate, 200-300 parts of vinyl acetate, 200-300 parts of methyl methacrylate, 1000-2000 parts of butyl acrylate, 30-60 parts of acrylic acid, 3000-4000 parts of diluent, 5-10 parts of initiator, 150-300 parts of tackifier and 10-30 parts of silane coupling agent.

[0005] As a preferred technical solution, the mass ratio of the tackifier to the silane coupling agent is (150-165):(13-20), preferably (150-160):(15-18), and preferably 157.5:16.8.

[0006] As a preferred technical solution, the diluent is selected from at least one of ethyl acetate, toluene, butanone, butyl acetate or n-hexane, preferably ethyl acetate.

[0007] As a preferred technical solution, the initiator at least includes a peroxide initiator.

[0008] Preferably, the peroxide initiator comprises at least dibenzoyl peroxide.

[0009] As a preferred technical solution, the tackifier is selected from at least one of terpene resin, petroleum resin, rosin and its derivatives, phenolic resin or styrene resin.

[0010] Preferably, the rosin and its derivatives include at least one of hydrogenated rosin resin and polyol-modified rosin resin.

[0011] Preferably, the tackifier is a polyol-modified rosin resin, the acid value of the polyol-modified rosin resin is ≤5 mgKOH / g, and the softening point of the polyol-modified rosin resin is 90-110°C.

[0012] Preferably, the acid value of the polyol-modified rosin resin is ≤5, which is 2.5-4.2 mgKOH / g, and the softening point of the polyol-modified rosin resin is 95-102° C. The model is AS-1100G, and it comes from Guangzhou Yabiao Technology Co., Ltd.

[0013] As a preferred technical solution, the silane coupling agent is selected from at least one of aminosilane, epoxysilane, methacryloxysilane, mercaptosilane or vinylsilane, preferably epoxysilane.

[0014] Preferably, the epoxy silane includes at least KH-560.

[0015] The present invention optimizes the amount control of isooctyl methacrylate, vinyl acetate methyl methacrylate, butyl acrylate, and acrylic acid in the acrylic adhesive system, and coordinates the timing of adding the diluent, initiator, tackifier, and silane coupling agent to avoid the phase separation problem caused by the polarity difference of the raw materials in the system, thereby significantly improving the interface bonding performance and environmental stability of the adhesive. In particular, the polyol-modified rosin resin with an acid value of ≤5 mgKOH / g and a softening point of 90-110° C. is used in conjunction with the introduction of epoxy silane, so that the provided product can firmly bond various substrates while improving the water washing resistance of the adhesive, so that it can withstand multiple water washings while maintaining excellent bonding strength and stability. Furthermore, by controlling the mass ratio of the tackifier and the silane coupling agent in the system to (150-165): (13-20), the provided product can meet the actual application requirements of conventional high-brightness micro-bead reflective products, and the adhesive can effectively wrap the aluminum-coated glass beads (coating 60-80μm). Especially when the mass ratio of the tackifier and the silane coupling agent is (150-160): (15-18), the adhesive is applied to conventional high-brightness micro-bead reflective products, and the coating of the aluminum-coated glass beads is 35-45μm, which effectively balances the retro-reflective brightness and water washing performance of conventional high-brightness micro-bead reflective products at various angles, thereby better meeting the actual application requirements.

[0016] Another aspect of the present invention provides a method for preparing a highly water-resistant acrylic adhesive, comprising at least the following steps:

[0017] (1) isooctyl methacrylate, vinyl acetate, methyl methacrylate, butyl acrylate, and acrylic acid are mixed and added to a reaction vessel, and heated to 70° C.-80° C. under nitrogen protection to start a polymerization reaction;

[0018] (2) When the polymerization reaction is carried out for 20-40 minutes, 20-30 wt% of the total amount of initiator is added to continue the polymerization reaction;

[0019] (3) When the polymerization reaction is carried out for 60-70 minutes, 20-30 wt% of the total amount of diluent is added to continue the polymerization reaction;

[0020] (4) When the polymerization reaction is carried out for 100-120 minutes, 40-60wt% of the total amount of initiator and the remaining amount of diluent and tackifier are added to continue the polymerization reaction;

[0021] (5) When the polymerization reaction is carried out for 3-4 hours, the remaining initiator and silane coupling agent are added to react to obtain a product, and a highly water-resistant acrylic adhesive is obtained after cooling and filtering.

[0022] The raw materials used in the highly water-resistant acrylic adhesive provided by the present invention are environmentally friendly materials, do not contain harmful substances, meet environmental protection requirements, and are suitable for various fields requiring water-resistant performance, such as textiles, leather products, packaging materials, architectural glass materials, etc. In particular, in the field of textiles and leather products, the adhesive can withstand multiple water washings while maintaining excellent bonding effects and appearance quality.

[0023] Beneficial Effects

[0024] 1. The present invention provides a highly water-resistant acrylic adhesive and a preparation method thereof. By optimizing the synthetic formula, high water-resistant performance is achieved while maintaining good bonding strength and stability. It has broad application prospects and market value and can meet the needs of various fields requiring water-resistant performance.

[0025] 2. The present invention optimizes the dosage of isooctyl methacrylate, vinyl acetate methyl methacrylate, butyl acrylate and acrylic acid in the acrylic adhesive system, and coordinates the timing of adding the diluent, initiator, tackifier and silane coupling agent to avoid the phase separation problem caused by the polarity difference of the raw materials in the system, thereby significantly improving the interfacial bonding performance and environmental stability of the adhesive.

[0026] 3. The present invention adopts a polyol-modified rosin resin with an acid value of ≤5 mgKOH / g and a softening point of 90-110°C and introduces epoxy silane, so that the provided product can firmly bond various substrates while improving the water washing resistance of the adhesive, so that it can withstand multiple water washings while maintaining excellent bonding strength and stability.

[0027] 4. The present invention controls the mass ratio of the tackifier and the silane coupling agent in the system to (150-165): (13-20), so that the provided product meets the actual application requirements of conventional high-brightness micro-bead reflective products, and the adhesive effectively wraps the aluminum-plated glass micro-beads (coating 60-80μm).

[0028] 5. The raw materials used in the highly water-resistant acrylic adhesive provided by the present invention are environmentally friendly materials, do not contain harmful substances, meet environmental protection requirements, and are suitable for various fields requiring water-resistant performance, such as textiles, leather products, packaging materials, architectural glass materials, etc. In particular, in the field of textiles and leather products, the adhesive can withstand multiple water washings while maintaining excellent bonding effects and appearance quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of the structure of conventional high-brightness micro-bead reflective products on the market, in which 1-glass micro-beads, 2-aluminum layer, 3-highly water-resistant acrylic adhesive, and 4-base fabric.

[0030] Figure 2 This is a SEM characterization image of a high-brightness microbead reflective product prepared using the adhesive provided in Comparative Example 1.

[0031] Figure 3 This is a SEM characterization image of a high-brightness micro-bead reflective product prepared using the highly water-resistant acrylic adhesive provided in Example 1.

[0032] Figure 4 This is a SEM characterization image of a high-brightness micro-bead reflective product prepared using the highly water-resistant acrylic adhesive provided in Example 2. DETAILED DESCRIPTION

[0033] Example 1-2, Comparative Example 1-2

[0034] On the one hand, Examples 1-2 and Comparative Examples 1-2 of the present invention provide a highly water-resistant acrylic adhesive, and the formula thereof is shown in Table 1 in parts by weight.

[0035] Table 1

[0036]

[0037]

[0038] On the other hand, Examples 1-2 and Comparative Examples 1-2 of the present invention provide a method for preparing a highly water-resistant acrylic adhesive, comprising the following steps:

[0039] (1) isooctyl methacrylate, vinyl acetate, methyl methacrylate, butyl acrylate, and acrylic acid are mixed and added to a reaction vessel, and heated to 75° C. under nitrogen protection to start a polymerization reaction;

[0040] (2) When the polymerization reaction lasts for 30 minutes, initiator 1 is added to continue the polymerization reaction;

[0041] (3) When the polymerization reaction is carried out for 60 minutes, diluent 1 is added to continue the polymerization reaction;

[0042] (4) When the polymerization reaction is carried out for 120 min, initiator 2, diluent 2 and tackifier are added to continue the polymerization reaction;

[0043] (5) When the polymerization reaction is carried out for 3.5 hours, initiator 3 and silane coupling agent are added to react to obtain a product, and a highly water-resistant acrylic adhesive is obtained after cooling and filtering.

[0044] Performance Testing Methods

[0045] 1. The highly water-resistant acrylic adhesive provided in the examples and comparative examples was used to prepare conventional high-brightness micro-bead reflective products on the market to obtain test samples (see the schematic diagram of the test sample structure for details). Figure 1 In the figure, the particle size of the glass beads 1 is 80-100μm, the thickness of the aluminum layer 2 is 10nm, the thickness of the highly water-resistant acrylic adhesive 3 is 170±10μm, and the base fabric 4 is made of 190T polyester taffeta with a thickness of 50μm). After washing the test sample according to ISO 63306N, the reflective intensity after washing is tested. The number of washing times and the retroreflective coefficient after washing are shown in Table 2.

[0046] Table 2

[0047]

[0048]

[0049] 2. The test samples obtained in Example 1-2 and Comparative Example 1 were characterized by SEM. The results are shown in Figure 2-4 , Figure 2 The results show that the adhesive provided in Comparative Example 1 has poor encapsulation of microbeads; Figure 3 The results show that the highly water-resistant acrylic adhesive provided in Example 1 fully covers the glass microbeads, and the reflection brightness is lower than that of Example 2; Figure 4The results show that the coating of the glass microbeads by the highly water-resistant acrylic adhesive provided in Example 2 is 35±5 μm, and under this coating, the conventional high-brightness microbead-type reflective products have good retro-reflective brightness at all angles.

Claims

1. A highly water-resistant acrylic adhesive, characterized in that: The raw materials for its preparation include at least 30-60 parts of isooctyl methacrylate, 200-300 parts of vinyl acetate, 200-300 parts of methyl methacrylate, 1000-2000 parts of butyl acrylate, 30-60 parts of acrylic acid, 3000-4000 parts of diluent, 5-10 parts of initiator, 150-300 parts of tackifier and 10-30 parts of silane coupling agent by weight.

2. The highly water-resistant acrylic adhesive according to claim 1, characterized in that: The mass ratio of the tackifier to the silane coupling agent is (150-165):(13-20).

3. The highly water-resistant acrylic adhesive according to claim 1, characterized in that: The diluent is selected from at least one of ethyl acetate, toluene, butanone, butyl acetate or n-hexane.

4. The highly water-resistant acrylic adhesive according to claim 1, characterized in that: The initiator includes at least a peroxide initiator.

5. The highly water-resistant acrylic adhesive according to claim 1, characterized in that: The peroxide initiator includes at least dibenzoyl peroxide.

6. The highly water-resistant acrylic adhesive according to claim 1, characterized in that: The tackifier is selected from at least one of terpene resin, petroleum resin, rosin and its derivatives, phenolic resin or styrene resin.

7. The highly water-resistant acrylic adhesive according to claim 6, characterized in that: The rosin and its derivatives include at least one of hydrogenated rosin resin and polyol-modified rosin resin.

8. The highly water-resistant acrylic adhesive according to claim 7, characterized in that: The acid value of the polyol-modified rosin resin is ≤5 mgKOH / g, and the softening point of the polyol-modified rosin resin is 90-110°C.

9. The highly water-resistant acrylic adhesive according to claim 1, characterized in that: The silane coupling agent is selected from at least one of aminosilane, epoxysilane, methacryloxysilane, mercaptosilane or vinylsilane.

10. A method for preparing a highly water-resistant acrylic adhesive according to any one of claims 1 to 9, characterized in that: At least the following steps are included: (1) isooctyl methacrylate, vinyl acetate, methyl methacrylate, butyl acrylate, and acrylic acid are mixed and added to a reaction vessel, and heated to 70° C.-80° C. under nitrogen protection to start a polymerization reaction; (2) When the polymerization reaction is carried out for 20-40 minutes, 20-30 wt% of the total amount of initiator is added to continue the polymerization reaction; (3) When the polymerization reaction is carried out for 60-70 minutes, 20-30 wt% of the total amount of diluent is added to continue the polymerization reaction; (4) When the polymerization reaction is carried out for 100-120 minutes, 40-60wt% of the total amount of initiator and the remaining amount of diluent and tackifier are added to continue the polymerization reaction; (5) When the polymerization reaction is carried out for 3-4 hours, the remaining initiator and silane coupling agent are added to react to obtain a product, and a highly water-resistant acrylic adhesive is obtained after cooling and filtering.

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