阅读说明：本技术 一种适用于尼龙加玻纤塑胶材质用底漆涂料及其制备方法和应用 (Primer coating suitable for nylon and glass fiber plastic material and preparation method and application thereof ) 是由 罗春韶 石二峰 郭猛 杨科 卢礼灿 陈朝岚 于 2021-08-09 设计创作，主要内容包括：本发明涉及一种适用于尼龙加玻纤塑胶材质用底漆涂料及其制备方法和应用,所述适用于尼龙加玻纤塑胶材质用底漆涂料,主要由主剂和固化剂制备得到,其中主剂和固化剂的质量比为100:1-5；其中主剂按重量百分比计,包括以下组分：低羟基丙烯酸聚合物树脂15～30％；热塑型丙烯酸树脂10～30％；聚乙烯蜡浆0～10％；气相二氧化硅1～5％；流平剂0.1～1％；混合溶剂Ⅰ40～60％；固化剂按以下重量百分比计：含双键脂肪族异氰酸酯聚合物70～80％,混合溶剂Ⅱ20～30％。所述适用于尼龙加玻纤塑胶材质用底漆涂料烘烤后,能在尼龙加玻纤塑胶材质表面形成一层涂料层,其与配套的PVD真空电镀涂料附着力好,配套后性能优异、表面质感强烈,颜色丰富多彩,增加了智能穿戴、手机等使用了尼龙加玻纤塑胶材质的3C产品的表面装设效果。(The invention relates to a primer coating for a nylon and glass fiber plastic material, and a preparation method and application thereof, wherein the primer coating for the nylon and glass fiber plastic material is mainly prepared from a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 100: 1-5; the main agent comprises the following components in percentage by weight: 15-30% of low-hydroxyl acrylic polymer resin; 10-30% of thermoplastic acrylic resin; 0-10% of polyethylene wax slurry; 1-5% of fumed silica; 0.1-1% of a leveling agent; 40-60% of a mixed solvent I; the curing agent comprises the following components in percentage by weight: 70-80% of double-bond aliphatic isocyanate polymer and 20-30% of mixed solvent II. The paint is suitable for baking the priming paint for the nylon and glass fiber plastic material, can form a layer of paint layer on the surface of the nylon and glass fiber plastic material, has good adhesive force with the matched PVD vacuum electroplating paint, has excellent performance after matching, strong surface texture and rich and colorful colors, and increases the surface installation effect of 3C products using the nylon and glass fiber plastic material, such as intelligent wearing and mobile phones.)

1. The primer coating for the nylon and glass fiber plastic material is characterized by comprising a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 100: 1-5;

wherein, the main agent comprises the following components in percentage by weight:

15-30% of low-hydroxyl acrylic polymer resin;

5-25% of thermoplastic acrylic resin;

0-10% of polyethylene wax slurry;

1-5% of fumed silica;

0.1-1% of a leveling agent;

40-60% of a mixed solvent I;

the curing agent comprises the following components in percentage by weight:

60-80% of double-bond-containing aliphatic isocyanate polymer;

and 20-40% of a mixed solvent II.

2. The primer coating suitable for nylon and glass fiber plastic material as claimed in claim 1, wherein the main agent comprises the following components by weight percent:

20-30% of low-hydroxyl acrylic polymer resin;

5-15% of thermoplastic acrylic resin;

2-10% of polyethylene wax slurry;

1-5% of fumed silica;

0.1-1% of a leveling agent;

50-60% of a mixed solvent I;

the curing agent comprises the following components in percentage by weight:

65-80% of double bond-containing aliphatic isocyanate polymer;

and 20-35% of a mixed solvent II.

3. The primer coating composition for nylon-glass fiber plastic material according to claim 1, wherein the low hydroxyl acrylic polymer resin is at least one of LR7609, synthesized by DIC of Mitsubishi corporation, ZHP-1276, or TCA-6013, which is a Tagchang resin, and has a viscosity of X-Z2-25 ℃, a solid OH value of 10-50, and a solid content of 50 ± 10%.

4. The primer coating suitable for nylon and glass fiber plastic material of claim 1, wherein the thermoplastic acrylic resin is at least one of ZHL-1063 synthesized by DIC, KDD MR14890 of Keding Gong material, or AP-108B of Point chemical engineering; the thermoplastic acrylic resin has a TG point of 50, a viscosity of 10000-15000 cps/25 ℃, and a solid content of 45 +/-10%.

5. The primer coating suitable for nylon and glass fiber plastic materials as claimed in claim 1, wherein the main agent comprises the following mixed solvent I in percentage by weight:

6. the primer coating for nylon-fiberglass plastic material of claim 1, wherein the polyethylene wax slurry has a particle size of 3 to 5 μm; the particle size of the fumed silica is 1-3 mu m.

7. The primer coating for nylon-glass fiber plastic material as claimed in claim 1, wherein the leveling agent is a modified polyacrylate compound;

the viscosity of the double-bond-containing aliphatic isocyanate polymer in the curing agent is 550 +/-200-25 ℃, the NCO content is 19 +/-1%, and the solid content is 90 +/-10%.

8. The primer coating suitable for nylon and glass fiber plastic materials as claimed in claim 1, wherein the curing agent comprises the following components in percentage by weight:

40-60% of butyl acetate;

and 40-60% of ethyl acetate.

9. The method for preparing the primer coating suitable for the nylon-glass fiber plastic material according to any one of claims 1 to 8, comprising: the components of the main agent can be directly used after being uniformly stirred according to the weight percentage.

10. The use of the primer coating for nylon-glass fiber plastic material according to any one of claims 1 to 8, wherein the specific application process is as follows:

(1) cleaning a substrate: cleaning and drying the surface of the material;

(2) diluting the coating: mixing and diluting the main agent and the curing agent according to the weight ratio of 100:1-5 to obtain a mixed solution;

(3) spraying: coating the mixed solution obtained in the step (2) on the surface;

(4) and (3) drying: leveling for 2-5 min at normal temperature; and IR baking at 70-80 ℃ for 10-15 min.

Technical Field

The invention belongs to the field of chemical coatings, and particularly relates to a primer coating suitable for nylon and glass fiber plastic materials, and a preparation method and application thereof.

Background

At present, watch, bracelet, earphone shell etc. that use PC material or PC + GF material as main material in intelligence wearing field use, but the mechanical strength of PC or PC + GF material is not enough, easily falls to split, corrosion resistance subalternation has caused the use of intelligence wearing product to experience not good. The nylon and glass fiber plastic materials have very excellent comprehensive performance, no toxicity, light weight, excellent mechanical strength, excellent wear resistance, corrosion resistance and low price, and the tensile strength, the bending strength, the thermal deformation temperature, the modulus of the materials and the like are greatly improved compared with PC or PC + GF, so that watches, earphone shells and the like which are made of the nylon and glass fiber plastic materials become a trend at the present stage.

PVD vacuum plating spraying is a common effect in the smart wearing and mobile phone manufacturing industries. The general intelligent wearing and mobile phone processing technology comprises the following steps: raw material → injection molding → cleaning → spraying → packaging. The main purpose of spraying is to make various appearance effects on the surface of the material, and simultaneously play a certain role in protection, and enhance the aesthetic practicability of the mobile phone. However, the existing coating has poor adhesion on special plastic materials such as nylon and glass fiber, and is difficult to pass strict unconventional tests.

The basic requirements of the primer coating suitable for the nylon and glass fiber plastic material are as follows: the nylon and glass fiber plastic material has stable adhesive force effect; passing various non-conventional test standards; the process has strong operability. Meanwhile, the intelligent wearable device is a general name for applying wearable technology to intelligently design daily wearable devices and develop wearable devices, such as watches, bracelets, glasses, clothing and the like. Along with the popularization of intelligent wearing equipment at the present stage, the selection of electronic product outward appearance is also more and more, and people focus on visual feelings such as appearance effect, color of product more and more.

However, all be nylon with under the prerequisite of glass fiber plastic material at intelligence wearing equipment shell material basically, the molecular structure degree of crystallinity of nylon is high, and surface energy is low, and after the glass fiber reinforcement, the attribute polarity on glass fiber nylon surface is comparatively complicated, shows for the polarity low, and paint and coating are hardly attached to the reason of crystal structure in addition. How to ensure stable adhesion force is an aspect of urgent need for improvement and development in the prior art through strict and unconventional performance tests.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a primer coating suitable for nylon and glass fiber plastic materials, and a preparation method and application thereof.

The primer coating provided by the invention is a baking-type primer coating with excellent adhesive force on a nylon and glass fiber plastic material, and aims to solve the problems of poor adhesive force, severe paint drop in hundreds of cases, NG in unconventional tests and the like caused by insufficient adhesive force between the conventional primer coating and the nylon and glass fiber plastic material.

In order to achieve the purpose, the invention is realized by the following technical scheme:

the primer coating for the nylon and glass fiber plastic material comprises a main agent and a curing agent, wherein the mass ratio of the main agent to the curing agent is 100: 1-5;

wherein, the main agent comprises the following components in percentage by weight:

15-30% of low-hydroxyl acrylic polymer resin;

5-25% of thermoplastic acrylic resin;

0-10% of polyethylene wax slurry;

1-5% of fumed silica;

0.1-1% of a leveling agent;

40-60% of a mixed solvent I;

the curing agent comprises the following components in percentage by weight:

60-80% of double-bond-containing aliphatic isocyanate polymer;

and 20-40% of a mixed solvent II.

Preferably, the main agent comprises the following components in percentage by weight:

20-30% of low-hydroxyl acrylic polymer resin;

5-15% of thermoplastic acrylic resin;

2-10% of polyethylene wax slurry;

1-5% of fumed silica;

0.1-1% of a leveling agent;

50-60% of a mixed solvent I;

the curing agent comprises the following components in percentage by weight:

65-80% of double bond-containing aliphatic isocyanate polymer;

and 20-35% of a mixed solvent II.

Preferably, the low-hydroxyl acrylic polymer resin is at least one of LR7609, synthesized by Mitsubishi corporation, ZHP-1276 by DIC, or TCA-6013, which is a Takachang resin.

Preferably, the thermoplastic acrylic resin is at least one of ZHL-1063 synthesized by DIC, KDD MR14890 of Coding Kong material or AP-108B of dotting chemical industry.

Preferably, the low hydroxyl acrylic polymer resin has a viscosity of X-Z2 & 25 ℃, a solid OH value of 10-50 and a solid content of 50 +/-10%.

Preferably, the thermoplastic acrylic resin has a TG point of 50, a viscosity of 10000-15000 cps/25 ℃, and a solid content of 45 +/-10%.

Preferably, the mixed solvent I in the main agent comprises the following components in percentage by weight:

preferably, the particle size of the polyethylene wax slurry is 3-5 μm; the particle size of the fumed silica is 1-3 mu m.

Preferably, the leveling agent is a modified polyacrylate compound;

the viscosity of the double-bond-containing aliphatic isocyanate polymer in the curing agent is 550 +/-200-25 ℃, the NCO content is 19 +/-1%, and the solid content is 90 +/-10%.

Preferably, the curing agent contains the following mixed solvent II in percentage by weight:

40-60% of butyl acetate;

and 40-60% of ethyl acetate.

According to the preparation method of the primer coating suitable for the nylon and glass fiber plastic material, all the components of the main agent are uniformly stirred according to the weight percentage and then can be directly used.

The primer coating for the nylon and glass fiber plastic material has the following specific application process:

(1) cleaning a substrate: cleaning and drying the surface of the material;

(2) diluting the coating: mixing and diluting the main agent and the curing agent according to the weight ratio of 100:1-5 to obtain a mixed solution;

(3) spraying: coating the mixed solution obtained in the step (2) on the surface;

(4) and (3) drying: leveling for 2-5 min at normal temperature; and IR baking at 70-80 ℃ for 10-15 min.

In order to achieve the purpose, the invention is realized by the following technical scheme:

preferably, the low-hydroxyl acrylic polymer resin is at least one of LR7609, synthesized by DIC, ZHP-1276, and TCA-6013, which are resins of Takaki-Mitsubishi corporation, Japan.

Preferably, the thermoplastic acrylic resin is at least one of ZHL-1063 synthesized by DIC, KDD MR14890 of Coding Kong material, and AP-108B of Point chemical engineering.

Preferably, the leveling agent is a modified polyacrylate leveling agent.

Preferably, the mixed solvent I is one or more of ethyl acetate, methyl isobutyl ketone, isopropanol, butyl cellosolve, acetone or diisobutyl ketone.

Preferably, the double-bond aliphatic isocyanate polymer is at least one of kesichu (virgin bayer) Desmodur N3390, and asahi-formed TKA-75B.

Preferably, the mixed solvent II is one or two of ethyl acetate and butyl acetate.

Compared with the prior art, the invention has the beneficial effects that:

the primer coating for the nylon and glass fiber plastic material is sprayed on the nylon and glass fiber plastic material, and a compact film is formed on the nylon and glass fiber plastic material after baking for 10-15 min at 70-80 ℃, wherein the film can change the surface polarity of the nylon and glass fiber plastic material and improve the adhesion effect of the primer coating on the nylon and glass fiber plastic material by improving intermolecular force. The adhesion of the PVD vacuum plating coating promotes the formation of a bi-directional hydroxyl bond by the primer coating film layer, linking the primer coating with the PVD vacuum plating coating resin molecules to each other, thereby promoting adhesion. Therefore, the primer coating for the nylon and glass fiber plastic material can be effectively applied to the surface coating of the nylon and glass fiber plastic material, has the advantages of low odor, no methylbenzene, no halogen, no heavy metal, no organic tin and the like, meets the RoHS standard, and has little harm to the environment. The primer coating suitable for the nylon and glass fiber plastic material is sprayed on the surface of the nylon and glass fiber plastic material, and is matched with the PVD vacuum electroplating coating, so that the effect of high quality sense of vacuum electroplating is shown on the nylon and glass fiber plastic material. The paint is suitable for baking the priming paint for the nylon and glass fiber plastic material, can form a layer of paint layer on the surface of the nylon and glass fiber plastic material, has good adhesive force with the matched PVD vacuum electroplating paint, has excellent performance after matching, strong surface texture and rich and colorful colors, and increases the surface installation effect of 3C products using the nylon and glass fiber plastic material, such as intelligent wearing and mobile phones.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The present invention is described in detail below with reference to examples:

example 1:

the primer coating suitable for the nylon and glass fiber plastic material comprises the following main agents in percentage by weight:

the weight percentage of the mixed solvent I is as follows:

the curing agent comprises the following components in percentage by weight:

kesichu (virgin bayer) Desmodur N339070%;

the mixed solvent II accounts for 30%

The weight percentage of the mixed solvent II is as follows:

50 percent of butyl acetate

50 percent of butyl acetate

Example 2:

a primer coating suitable for nylon and glass fiber plastic materials comprises the following main agents in percentage by weight:

the weight percentage of the mixed solvent I is as follows:

the curing agent comprises the following components in percentage by weight:

kesichu (virgin bayer) Desmodur N339070%;

the mixed solvent II accounts for 30%

The weight percentage of the mixed solvent II is as follows:

50 percent of butyl acetate

50 percent of butyl acetate

Example 3:

the primer coating suitable for the nylon and glass fiber plastic material comprises the following main agents in percentage by weight:

the weight percentage of the mixed solvent I is as follows:

the curing agent comprises the following components in percentage by weight:

kesichu (virgin bayer) Desmodur N339070%;

the mixed solvent II accounts for 30%

The weight percentage of the mixed solvent II is as follows:

50 percent of butyl acetate

50 percent of butyl acetate

Example 4:

the primer coating suitable for the nylon and glass fiber plastic material comprises the following main agents in percentage by weight:

the weight percentage of the mixed solvent I is as follows:

the curing agent comprises the following components in percentage by weight:

kesichu (virgin bayer) Desmodur N339070%;

the mixed solvent II accounts for 30%

The weight percentage of the mixed solvent II is as follows:

50 percent of butyl acetate

50 percent of butyl acetate

Comparative example 1:

the primer coating suitable for the nylon and glass fiber plastic material comprises the following main agents in percentage by weight:

the weight percentage of the mixed solvent I is as follows:

the curing agent comprises the following components in percentage by weight:

kesichu (virgin bayer) Desmodur N339070%;

the mixed solvent II accounts for 30%

The weight percentage of the mixed solvent II is as follows:

50 percent of butyl acetate

50 percent of butyl acetate

The primer coating for nylon and glass fiber plastic materials of the 5 examples is subjected to performance test, and the results are as follows:

1. temperature cycle: 25 ℃, 95% RH, 3H to 55 ℃; 95% RH, hold 9H, then 3H down to 25 ℃; the test is carried out for 3 times by using 95% RH and maintaining 9H, the test is carried out for 3 times, the paint film has no abnormal phenomena such as falling, cracks, discoloration and the like after the test of example 1/2/3/4, the adhesive force is not less than 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

2. QUV: the lamp tube is UVB313nm, and the light intensity is 0.63W/m²After the temperature is 60 ℃/4H, the condensation is 50 ℃/4H, one cycle is 12 cycles in total, the paint film has no abnormal phenomena such as falling, cracks, obvious discoloration and the like after the test of example 1/2/3/4, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

3. and (3) low-temperature storage: 30 ℃ below zero/6H, 40 ℃ below zero/16H, 30 ℃ below zero/15 min, 25 ℃/2H, no abnormal phenomena such as falling, cracks, discoloration and the like exist in the paint film after the test of example 1/2/3/4, the adhesive force is not less than 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

4. and (3) high-temperature storage: 55 ℃/6H, 70 ℃/16H, 25 ℃/2H, the paint film has no abnormal phenomena such as falling, cracks, discoloration and the like after the test of example 1/2/3/4, the adhesive force is not less than 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

5. temperature impact: the temperature is 40 ℃ below zero, the temperature is 2H, the temperature is 70 ℃ and the temperature is 2H, the cycle is 5 cycles, the paint film has no abnormal phenomena such as falling, cracks, discoloration and the like after the test of example 1/2/3/4, the adhesive force is more than or equal to 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

6. pencil hardness: 1Kg/F Mitsubishi pencil, no scratch after the test;

7. cosmetic resistance test: uniformly coating vaseline and skin lotion on the surface of a product, raising the temperature of 25 ℃, 95% RH and 3H to 55 ℃, 95% RH, keeping the temperature at 9H, lowering the temperature of 3H to 25 ℃, 95% RH, keeping the temperature at 9H, repeating for 2 times in a cycle, placing the product at 25 ℃, 75% RH for 2H, and testing the product in case 1/2/3/4, wherein the paint film has no abnormal phenomena such as falling, cracks, discoloration and the like, the adhesive force is not less than 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

8. testing for hand sweat resistance: soaking a piece of dust-free cloth on the surface of the sample by sweat with the pH value of 6.5 for 2min, and then placing the sample at room temperature for 2H, wherein the product has no obvious change after the test of example 1/2/3/4, the adhesive force is more than or equal to 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

9. adhesion force: a hundred grid knife was cut at 1.0mm 10X 10 and pulled 3 times with 3M610 tape, example 1/2/3/4/5 test was 5B;

10. boiling test: the temperature is 100 ℃/30min, the paint film has no abnormal phenomena such as falling, cracks, discoloration and the like after the test of example 1/2/3/4, the adhesive force is more than or equal to 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

11. RCA: 175g, 200 times, example 1/2/3/4/5 product was impermeable;

12. and (3) salt spray testing: continuously spraying 5% sodium chloride solution for 48 hours in a sealed environment at 35 ℃ with the humidity of more than 85% and the pH value of 6.5-7.2; the product has no obvious change after the test of example 1/2/3/4, the adhesion test reaches more than 4B, and the test is OK; comparative example 1 test was followed with paint film peel, adhesion B, test NG;

12. vibration and wear resistance: the product is put into a vibration mill 2H, the appearance of the product is not peeled off after the test of example 1/2/3/4, the paint is removed, and the test is OK; comparative example 1 after the test the paint film fell off, the paint was removed and NG was tested.

The application method of the primer coating suitable for the nylon and glass fiber plastic material comprises the following steps:

the process sequence is as follows:

substrate cleaning → coating dilution → spraying → IR baking process parameters:

dilution ratio: coating: curing agent is 100: 3;

film thickness: 6-10 μm (Mitutoyo);

IR temperature: the temperature is 70-80 ℃ and the time is 10-15 min.

It is to be emphasized that: the above embodiments only show the preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention, and all technical solutions obtained by using the technical essence of the present invention in the above embodiments in the form of equivalent replacement or equivalent transformation are still within the scope of the technical solution of the present invention.