A matte coating material and a preparation method and application thereof

Abstract

The present application relates to the technical field of paint, especially to the field of IPC C09D175, and more particularly to a matte coating material, a preparation method and application thereof. The components include a matte varnish, a first solvent and a catalyst. The components of the matte varnish include a hydroxyl acrylic polymer resin, a dispersing agent, an isocyanate curing agent, fumed silica and a second solvent. The hydroxyl acrylic polymer resin with a hydroxyl value of 20-100 mg KOH / g, a specific viscosity of 0.1-0.3 dL / g at 25 DEG C and a glass transition temperature of 30-80 DEG C can improve the film forming performance. The weight ratio of the catalyst and the isocyanate curing agent is 0.1:(2.8-22.4), and the activation period of the paint can be greater than 6 h, meeting the requirements of the process for preparing an electrochemical aluminum by holographic stamping technology. The coating material prepared by the present application is applied to the electrochemical aluminum, and plays a role of protecting the color layer and reflecting light.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to the field of IPC C09D175, and more particularly to a matte coating material and a preparation method and application thereof. BACKGROUND

[0002] In recent years, matte electrochemical aluminum has gradually been favored by the market for its unique extinction effect, and has become a new hot choice in the market. The traditional matte electrochemical aluminum is formed by adding silicon powder in the colored layer to form a coating layer with certain hiding power, which blocks the light reflected by the aluminum plating layer, causing the light on the film surface to be diffusely reflected to achieve extinction. Therefore, after hot stamping, the surface of the printed product of the matte holographic electrochemical aluminum produced by this process still has a high gloss, only the metallic feeling is weak, and the desired matte decorative effect is not achieved. At the same time, this process also has a serious surface defect: the solubility of silicon powder in resin coating is not ideal, and when the coating is formed, its surface often appears not fine enough. Visually, the protruding silicon powder particles can be clearly seen, which not only greatly reduces the appearance of the package, but also may affect the realization of the anti-counterfeiting effect.

[0003] Chinese patent CN103849308A discloses a new type of matte electrochemical aluminum hot stamping foil coating prepared from the following materials in a certain weight ratio: acrylic modified polyurethane 20-40 parts, tributyl citrate 2-5 parts, pure acrylic ester 1-10 parts, benzoic acid diallyl acid resin 10-20 parts, butanone 30-60 parts, butyl ester 5-20 parts, and matte powder 10-20 parts. The new type of matte electrochemical aluminum hot stamping foil coating obtained by the present application has a simple production process, is conducive to large-scale production, and the electrochemical aluminum hot stamping foil produced by it has low gloss, but it is not suitable for holographic hot stamping technology. SUMMARY

[0004] The present application provides a matte coating material, which comprises a matte varnish, a first solvent and a catalyst drier. The matte varnish comprises a hydroxyl acrylic polymer resin, a dispersing agent, an isocyanate curing agent, fumed silica and a second solvent.

[0005] The hydroxyl acrylic polymer resin has a hydroxyl value of 20-100 mg KOH / g, a specific viscosity of 0.1-0.3 dL / g at 25°C, and a glass transition temperature of 30-80°C.

[0006] Preferably, the hydroxyl acrylic polymer resin has a hydroxyl value of 20-100 mg KOH / g, a specific viscosity of 0.1-0.2 dL / g at 25°C, and a glass transition temperature of 40-70°C.

[0007] The hydroxyl acrylic polymer resin includes a first hydroxyl acrylic polymer resin having a hydroxyl value of 50-100 mg KOH / g and a second hydroxyl acrylic polymer resin having a hydroxyl value of 20-50 mg KOH / g, and the weight ratio of the first and second hydroxyl acrylic polymer resins is (1-3):(3-1).

[0008] Preferably, the weight ratio of the first and second hydroxyl acrylic polymer resins is (1-2):(2-1).

[0009] Further preferably, the weight ratio of the first and second hydroxyl acrylic polymer resins is (1-1.5):(1.5-1).

[0010] Still further preferably, the weight ratio of the first and second hydroxyl acrylic polymer resins is 1:1.

[0011] The first and second solvents each include at least one of butanone, ethyl acetate, n-propyl acetate, propylene glycol methyl ether, dimethyl succinate, dimethyl glutarate, methyl butanone, methyl isobutyl ketone, and cyclohexanone.

[0012] The first and second solvents each include at least one of butanone, ethyl acetate, n-propyl acetate.

[0013] Preferably, the second solvent includes butanone and n-propyl acetate, and the weight ratio of the butanone and n-propyl acetate is 1:(0.5-1.5).

[0014] Further preferably, the second solvent includes butanone and n-propyl acetate, and the weight ratio of the butanone and n-propyl acetate is 1:(0.9-1.3).

[0015] Preferably, the isocyanate curing agent includes an aliphatic polyisocyanate.

[0016] Preferably, the aliphatic polyisocyanate has an NCO content of 20-30 wt% (DIN EN ISO 11909).

[0017] Further preferably, the aliphatic polyisocyanate has an NCO content of 20-25 wt%.

[0018] Preferably, the drier includes an organic tin drier.

[0019] The fumed silica has a D50 particle size of 10-80 micrometers.

[0020] Preferably, the fumed silica has a D50 particle size of 10-50 micrometers.

[0021] Further preferably, the D50 particle size of the fumed silica is 10-30 microns.

[0022] Further preferably, the D50 particle size of the fumed silica is 10-20 microns.

[0023] The fumed silica is added to the matte topcoat in an amount of 5-15 wt%.

[0024] Preferably, the fumed silica is added to the matte topcoat in an amount of 8-12 wt%.

[0025] Further preferably, the fumed silica is added to the matte topcoat in an amount of 8 wt%.

[0026] The dispersant has an amine value of 5-30 mg KOH / g.

[0027] Preferably, the dispersant has an amine value of 5-25 mg KOH / g.

[0028] Preferably, the dispersant is added to the matte topcoat in an amount of 0.1-1 wt%.

[0029] Preferably, the dispersant is added to the matte topcoat in an amount of 0.5 wt%.

[0030] Preferably, the dispersant comprises at least one of the following types: BYK-164, BYK-167, BYK-170, BYK-2164, and BYK-163.

[0031] The siccatives are added to the matte coating material in an amount of 0.05-3 wt%, and the weight ratio of the siccatives to isocyanate curing agent is (0.05-0.15):(5-15).

[0032] Preferably, the siccatives are added to the matte coating material in an amount of 0.05-0.15 wt%, and the weight ratio of the siccatives to isocyanate curing agent is (0.05-0.15):(5-12).

[0033] Further preferably, the weight ratio of the siccatives to isocyanate curing agent is 0.1:(2.8-22.4).

[0034] Further preferably, the weight ratio of the siccatives to isocyanate curing agent is 0.1:5.6.

[0035] Further preferably, the dispersant comprises at least one of BYK-167, BYK-170, and BYK-2164.

[0036] The present applicant found that the hydroxyl value of the hydroxyl acrylic polymer resin is 20-100 mg KOH / g, the intrinsic viscosity at 25 DEG C is 0.1-0.3 dL / g, and the glass transition temperature is 30-80 DEG C, which can improve the film forming performance, possibly reduce the reaction by-product oligomer and residual monomer, improve the reaction efficiency, thereby providing better chemical resistance and hardness, and further research found that the hydroxyl value of the first hydroxyl acrylic polymer resin is 50-100 mg KOH / g, the hydroxyl value of the second hydroxyl acrylic polymer resin is 20-50 mg KOH / g, and the weight ratio of the first hydroxyl acrylic polymer resin to the second hydroxyl acrylic polymer resin is (1-3):(3-1), which can control the system viscosity to be 25-30 s, and the different molecular weight resin ratio may have different effects on the viscosity of the coating system, and when the amount of the resin with high molecular weight is too high, the viscosity is high, which cannot meet the requirements.

[0037] The second aspect of the present application provides a preparation method of a matte coating material, comprising the following steps:

[0038] S1, mixing the hydroxyl acrylic polymer resin with the second solvent, adding the dispersing agent and the fumed silica, and then adding the isocyanate curing agent to obtain the matte gloss oil;

[0039] S2, mixing the first solvent and the drier uniformly, adding the matte gloss oil, and stirring uniformly to obtain the product.

[0040] Preferably, the method comprises the following steps:

[0041] S1, adding the second solvent, starting stirring at a speed of 300-800 rpm, adding the hydroxyl acrylic polymer resin, raising the solution to 40-60 DEG C, stirring at a speed of 1200-2000 rpm for 1-3 h until the resin is fully dissolved, turning off the heating, and reducing the stirring speed to 300-800 rpm. Add the dispersing agent and the fumed silica, stir for 3-15 min, raise the speed to 2000-2800 rpm after the fumed silica powder is fully wetted, stir for 10-40 min, add the isocyanate curing agent, stir for 10-30 min, and filter the product with a 100-500 mesh filter bag;

[0042] S2, adding the first solvent, starting stirring at a speed of 300-800 rpm. Add the drier, stir for 3-15 min to mix the solvent and the additive uniformly, increase the stirring speed to 800-1600 rpm, add the matte gloss oil, stir for 10-30 min, and filter the product with a 100-500 mesh filter bag.

[0043] The third aspect of the present application provides an application of the matte coating material, which is applied in the process of preparing an anodized aluminum in a holographic stamping technology.

[0044] Beneficial effects

[0045] 1. Selecting hydroxyl acrylic polymers with a hydroxyl value of 20-100 mg KOH / g, an intrinsic viscosity of 0.1-0.3 dL / g at 25℃, and a glass transition temperature of 30-80℃ can improve film-forming properties.

[0046] 2. Select a first-hydroxyl acrylic polymer with a hydroxyl value of 50-100 mg KOH / g and a hydroxyl value of 20-50 mg KOH / g.

[0047] The second hydroxyl acrylic polymer resin has a KOH content of mg / g, and the weight ratio of the first hydroxyl acrylic polymer resin to the second hydroxyl acrylic polymer resin is (1-3):(3-1). This can control the viscosity of the system to be between 25-30s and provide processing performance.

[0048] 3. The D50 particle size of fumed silica is 10-80 micrometers, which can increase the amount of fumed silica added to matte varnish by 5-15wt%. The viscosity at 25℃ is 25-30s, while giving the coating both excellent matte effect (60° gloss ≤20) and abrasion resistance.

[0049] 4. The amount of drier added to the matte coating material is 0.05-0.15wt%, and the weight ratio of drier to isocyanate curing agent is (0.05-0.15):(5-12), which can improve the solvent resistance and adhesion of the coating, and the activation period is not less than 2h.

[0050] 5. The amine value of the dispersant is 5-30 mg KOH / g, which can reduce the viscosity of the resin system, improve the gloss, color intensity, transparency and hiding power of the coating, effectively prevent the accumulation and flocculation of pigments, make the fineness of the coating no greater than 25 microns, and at the same time make the surface tension of the system greater than 38 dynes, thus improving the processing performance.

[0051] 6. The weight ratio of the drying agent to the isocyanate curing agent is 0.1:(2.8-22.4), and the activation period of the coating can be greater than 6 hours, which meets the process requirements for preparing electroplated aluminum using holographic hot stamping technology.

[0052] 7. The coating material prepared in this application is applied to electroplated aluminum, which plays a role in protecting its color layer and reflecting light. Detailed Implementation

[0053] Examples 1-18

[0054] A kind of matte coating material, component is matte gloss oil, first solvent and catalyst drier;The component of the matte gloss oil is as follows: hydroxyl acrylic acid polymer resin, dispersant, isocyanate curing agent, fumed silica and second solvent;The amount of each component is shown in Table 1 (matte coating material) and Table 2 (matte gloss oil) by weight parts.

[0055] Wherein the catalyst drier is organic tin catalyst drier, model: T12, purchased from Guangdong Sandingjia New Material Technology Co., Ltd.

[0056] Table 1

[0057]

[0058] Table 2

[0059]

[0060]

[0061] A kind of preparation method of the matte coating material according to claim 1, is the following steps:

[0062] S1, in stirred tank, open stirring, set speed to 500 rpm, put in hydroxyl acrylic acid polymer resin, raise solution to 50 DEG C, under the condition that stirring speed is 1500 rpm, stir 2h, until resin is fully dissolved, close heating, reduce stirring speed to 500 rpm. Add dispersant and fumed silica, stir 5 min, after fumed silica powder is fully wetted, increase speed to 2500 rpm, stir 30 min;Add isocyanate curing agent, stir 15 min, filter the discharge with 200 mesh filter bag;

[0063] S2, in stirred tank, open stirring, set speed to 500 rpm. Put in catalyst drier, stir 5 min, so that solvent and adjuvant are fully mixed uniformly, increase stirring speed to 1000 rpm, add matte gloss oil, stir 15 min, filter the discharge with 200 mesh filter bag, i.e.

[0064] Performance test method and data

[0065] The coating material prepared in examples 1-18 is respectively prepared into sample strip: cut 6cm×60cm PET film (biaxially oriented polyester film PET, model: 1310, thickness 12 microns, purchased from Foshan Dupont Hongji Film Co., Ltd.) sample strip, use the absorbent cotton dipped with anhydrous ethanol to gently wipe the stains and dust on the film surface, and dry in natural conditions.

[0066] The corona treated film samples were printed by IGT F1 to simulate the printing process. The plastic film was fixed on the printing machine track, then the right amount of matte varnish was added between the anilox roller and the doctor blade, and make sure there was no bubble in the varnish. After starting the machine, every time the anilox roller rotated for two weeks, the plate cylinder completed a rotation, and the printing track was pushed forward. Every time the plate cylinder completed a rotation, the varnish was transferred from the anilox roller to the flexible plate, and then to the plastic film, which marked the end of the simulated printing process. The effective length of the sample was 50 cm. Then, these samples were placed in an oven set at 135°C for 10 seconds to complete the sample preparation process.

[0067] 1. 60° glossiness test: The glossiness meter (YG268, 3nh Shenzhen Sen Times Technology Co., Ltd.) measures the intensity of reflected light to obtain the glossiness of the object surface. When measuring, the light shines on the object surface at a certain angle, the reflected light enters the detector, and then the reflected light intensity is converted into an electrical signal, and the glossiness value is calculated, as shown in Table 3, the glossiness / matte of 18 examples can meet the matte requirements of this project (glossiness ≤20).

[0068] Table 3

[0069] Example Gloss (60°) Example Gloss (60°) 1 18.2 10 19.1 2 17.8 11 18.4 3 18.4 12 17.8 4 18.6 13 18.4 5 19.0 14 18.5 6 18.5 15 18.6 7 17.8 16 18.2 8 18.2 17 17.7 9 18.3 18 19.1

[0070] 2. Fineness measurement: The doctor blade fineness meter (De Du Instrument Co., Ltd.), as shown in Table 4, the paint fineness is not greater than 25 microns.

[0071] Table 4

[0072] Example Fineness (microns) Example Fineness (microns) 1 22 10 23 2 23 11 22 3 20 12 21 4 22 13 23 5 21 14 24 6 23 15 21 7 22 16 22 8 21 17 22 9 23 18 22

[0073] 3. Viscosity test (s): 25°C, rotational viscometer, No. 4 (Pusen Test Instrument (Shanghai) Co., Ltd.), as shown in Table 5, the proportion of resins with different molecular weights has the greatest impact on the viscosity of the paint. When the amount of resin with large molecular weight reaches 9wt%, the viscosity of the coating is significantly improved, which meets the project requirements. When the amount of resin with large molecular weight reaches 12wt%, the viscosity is too high and cannot meet the requirements.

[0074] When the ratio of 261 and 262 resins is 2:1, the viscosity of the paint is too low; when the ratio of 261 and 262 resins is 1:1, the viscosity of the paint meets the project requirements; when the ratio of 261 and 262 resins is 1:1, the viscosity of the paint is too low.

[0075] In the experiment, the proportion of the resin with lower molecular weight (BM261) is too high, resulting in the viscosity of Examples 1, 7 and 13 being too low. The proportion of the resin with higher molecular weight (BM262) is too high, resulting in the viscosity of Examples 3, 9 and 15 being too high. The viscosity of the remaining examples meets the project requirements (25-30 s).

[0076] Example Viscosity (s) Example Viscosity (s) 1 18.2 10 27.6 2 27.5 11 26.8 3 35.2 12 27.2 4 26.6 13 19.3 5 27.4 14 27.2 6 28.2 15 34.5 7 19.7 16 26.8 8 26.8 17 25.9 9 33.8 18 27.5

[0077] 4. Adhesion (grade) measurement: Peeling force tester, SHK-101, Suzhou Jianzhu Instrument Technology Co., Ltd. As shown in Table 6, the addition amount of the catalyst and the addition amount of the isocyanate curing agent both have a great influence on the adhesion of the coating. When the addition amount of the catalyst reaches 0.1%, the adhesion of the coating is obviously improved. When the addition amount of the isocyanate curing agent reaches 7%, the adhesion of the coating is obviously improved. The comparative tests of Examples 1-6 and 7-12, 13-18 prove the influence of the addition amount of the catalyst on the adhesion of the coating. The greater the addition amount of the catalyst, the faster the reaction of the coating during heat curing, and the higher the adhesion of the coating. The tests of Examples 2, 4, 5, 6 and 8, 10, 11, 12 and 14, 16, 17, 18 prove the influence of the addition amount of the isocyanate curing agent on the adhesion of the coating. The higher the addition amount of the isocyanate curing agent, the higher the adhesion.

[0078] Table 6

[0079] Example Adhesion (scale) Example Adhesion (scale) 1 2 10 2 2 2 11 1 3 2 12 1 4 3 13 1 5 2 14 1 6 2 15 1 7 1 16 2 8 1 17 1 9 1 18 1

[0080] 5. Rubbing resistance (grade) test: The principle of testing the rubbing resistance of the coating is to use a rubbing tester (MH305, Xinyu Yian) to test the rubbing of the coating film. The rubbing head is used to reciprocally rub the surface of the coating film, and the rubbing times or rubbing distance required for the coating to wear to a certain extent are recorded to evaluate the rubbing resistance of the coating. As shown in Table 7, the addition amount of the catalyst has a great influence on the rubbing resistance of the coating. When the addition amount of the catalyst reaches 0.1%, the rubbing resistance of the coating is obviously improved. The comparative tests of Examples 1-6 and 7-12, 13-18 prove the influence of the addition amount of the catalyst on the rubbing resistance of the coating. The greater the addition amount of the catalyst, the faster the reaction of the coating during heat curing, and the higher the rubbing resistance of the coating.

[0081] Table 7

[0082] Example Abrasion resistance (scale) Example Abrasion resistance (scale) 1 4 10 5 2 4 11 5 3 4 12 5 4 4 13 5 5 4 14 5 6 4 15 5 7 5 16 5 8 5 17 5 9 5 18 5

[0083] 6. Solvent resistance test: The test solvent is butanone. As shown in Table 8, the addition amount of the catalyst drier has a great influence on the solvent resistance of the coating. When the addition amount of the catalyst drier reaches 0.1%, the solvent resistance of the coating is obviously improved. The comparative test of Examples 1-6 and 7-12, 13-18 proves the influence of the addition amount of the catalyst drier on the solvent resistance of the coating. The greater the addition amount of the catalyst drier, the faster the reaction of the coating during the heat curing, and the better the solvent resistance of the coating.

[0084] Table 8

[0085] Example Solvent resistance (scale) Example Solvent resistance (scale) 1 4 10 5 2 4 11 5 3 4 12 5 4 4 13 5 5 4 14 5 6 4 15 5 7 5 16 5 8 5 17 5 9 5 18 5

[0086] 7. Coating uniformity test: The uniformity of the coating thickness, color, gloss, etc. is evaluated by observing the uniformity and defect of the coating in the color box (standard light source). The coating with good uniformity should have consistent coating thickness, color, gloss, etc. in each area of the coating surface without obvious fluctuation or difference. As shown in Table 9, the coating uniformity is divided into 1-6 levels, and the greater the number, the worse the uniformity. In the experiment, the coating uniformity of the 18 examples meets the project index requirement (1 level).

[0087] Table 9

[0088] Example Uniformity (scale) Example Uniformity (scale) 1 1 10 1 2 1 11 1 3 1 12 1 4 1 13 1 5 1 14 1 6 1 15 1 7 1 16 1 8 1 17 1 9 1 18 1

[0089] 8. Surface tension test: The surface tension value of the coating is determined by drawing the largest uniform line on the coating film surface using a da Vinci pen. As shown in Table 10, the surface tension of the 18 examples is 42 dynes, which meets the requirement of 38 dynes or more required by the project.

[0090] Table 10

[0091] Example Surface tension (dynes) Example Surface tension (dynes) 1 42 10 42 2 42 11 42 3 42 12 42 4 42 13 42 5 42 14 42 6 42 15 42 7 42 16 42 8 42 17 42 9 42 18 42

[0092] 9. Open time (activation period) test: The coating is applied on the test panel, and the time from the flowable state to the unlevelable state of the coating is recorded. As shown in Table 11, the addition amount of the catalyst drier and the addition amount of the isocyanate curing agent have a great influence on the open time (activation period) of the coating. When the addition amount of the catalyst drier reaches 0.1%, the open time (activation period) of the coating is obviously shortened. When the addition amount of the catalyst drier reaches 0.15%, the open time is less than 6 hours. When the addition amount of the isocyanate curing agent reaches 7%, the open time of the coating is obviously shortened.

[0093] The comparative test of Examples 1-6 and 7-12, 13-18 proves the influence of the addition amount of the catalyst drier on the open time of the coating. The greater the addition amount of the catalyst drier, the shorter the open time of the coating.

[0094] Examples 2, 4, 5, 6 and 8, 10, 11, 12 and 14, 16, 17, 18 three groups of experiments show that the amount of isocyanate curing agent added to the coating layer, the higher the amount of isocyanate curing agent, the shorter the open time.

[0095] In the experiment, the open time of examples 1-10 is greater than 6 hours, which meets the requirements.

[0096] Table 11

[0097] Example Open time (hours) Example Open time (hours) 1 16 10 10 2 16 11 6 3 16 12 4 4 18 13 4 5 14 14 4 6 12 15 4 7 8 16 6 8 8 17 4 9 8 18 2

Claims

1. A matte coating material, characterized in that, The components include a matte varnish, a first solvent, and a drier; the matte varnish comprises: a hydroxyl acrylic polymer resin, a dispersant, an isocyanate curing agent, fumed silica, and a second solvent; the hydroxyl acrylic polymer resin has a hydroxyl value of 20-100 mg KOH / g, an intrinsic viscosity of 0.1-0.3 dL / g at 25℃, and a glass transition temperature of 30-80℃; the hydroxyl acrylic polymer resin comprises a first hydroxyl acrylic polymer resin with a hydroxyl value of 50-100 mg KOH / g and a second hydroxyl acrylic polymer resin with a hydroxyl value of 20-50 mg KOH / g, and the weight ratio of the first hydroxyl acrylic polymer resin to the second hydroxyl acrylic polymer resin is (1-3):(3-1); the fumed silica has a D50 particle size of 10-20 micrometers; the drier is added to the matte coating material at an amount of 0.05-0.1 wt%, and the weight ratio of the drier to the isocyanate curing agent is (0.05-0.1):(5-15).

2. The matte coating material according to claim 1, characterized in that, Both the first solvent and the second solvent include at least one of methyl ethyl ketone, ethyl acetate, n-propyl acetate, propylene glycol methyl ether, dimethyl succinate, dimethyl glutarate, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

3. The matte coating material according to claim 2, characterized in that, The isocyanate curing agent includes aliphatic polyisocyanates.

4. The matte coating material according to claim 1, characterized in that, The amine value of the dispersant is 5-30 mgKOH / g.

5. A method for preparing the matte coating material according to claim 1, characterized in that, Includes the following steps: S1, hydroxyl acrylic polymer resin is mixed with a second solvent, a dispersant and fumed silica are added, and then an isocyanate curing agent is added to obtain a matte varnish; S2, mix the first solvent and the drying agent evenly, add the matte varnish, and stir evenly to obtain the final product.

6. An application of the matte coating material according to claim 1, characterized in that, It is applied in the process of preparing electroplated aluminum using holographic hot stamping technology.

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