TWI693262B - Anti-whitening primer and preparation method thereof - Google Patents

Abstract

An anti-whitening primer includes a hydrogen-containing silicone oil, a titanate coupling agent, a primer solvent, an anti-whitening agent, and organic silicone-acrylic acid copolymer. The hydrogen-containing silicone oil accounts for 0.01 to 5 % by weight, the titanate coupling agent accounts for 0.01 to 5 % by weight, the primer solvent accounts for 70 to 90% by weight, and the anti-whitening agent accounts for 5 to15% by weight. The whitening agent comprises at least a whitening agent solvent, a vinyl silicone oil, a hydrogen terminated phenyl silicone oil, and an inhibitor. The whitening agent solvent accounts for 4.5 to 14.7% by weight, the vinyl silicone oil accounts for 0.005 to 0.3% by weight, the inhibitor accounts for 0.0025 to 0.015% by weight, and the hydrogen-terminated phenyl silicone oil accounts for 0.005 to 0.3% by weight. The organic silicone-acrylic acid copolymer accounts for 5 to 15% by weight, and the molecular formula of the organic silicone-acrylic acid copolymer is:

Description

Anti-bleaching primer and preparation method thereof

This application relates to the field of chemistry, in particular to an anti-whitening primer and its preparation method.

Silicone rubber, that is, rubber with a silicone chain, because of its unique molecular structure, has low water absorption, high heat resistance, high fluidity, can be cured at room temperature or can be cured by heating, so it can be widely used in nipples, Mobile phone protective sleeves, etc. However, when used in a hot and humid environment, silicone rubber is prone to peeling and peeling, which requires the assistance of primers.

The primers on the market are easily deteriorated during heating, baking, etc., which causes whitening, which affects the appearance of transparent products. When the primer is used in the form of a film, when the whitening phenomenon occurs, it is usually accompanied by adhesiveness. The decrease in strength and the decrease in water and weather resistance cause the product to crack.

。 Here, an anti-whitening primer is provided. The anti-whitening primer includes hydrogen-containing silicone oil, a titanate coupling agent, a primer solvent, an anti-whitening agent, and an organic silicon-acrylic acid copolymer. Hydrogen-containing silicone oil accounts for 0.01 to 5wt%, titanate coupling agent accounts for 0.01 to 5wt%, primer solvent accounts for 70 to 90wt%, and anti-whitening agent accounts for 5 to 15wt%. The anti-whitening agent contains at least an anti-whitening agent solvent, vinyl silicone oil, hydrogen-terminated phenyl silicone oil, and an inhibitor. Anti-whitening agent solvent accounts for 4.5 to 14.7 wt%, vinyl silicone oil accounts for 0.005 to 0.3 wt%, inhibitor accounts for 0.0025 to 0.015 wt%, and hydrogen-terminated phenyl silicone oil accounts for 0.005 to 0.3 wt%. The silicone-acrylic copolymer accounts for 5 to 15% by weight. The molecular formula of the silicone-acrylic copolymer is:

.

In some embodiments, the anti-whitening agent further includes a platinum catalyst, and the platinum catalyst accounts for 0.0025 to 0.015 wt%.

In some embodiments, the hydrogen content in the hydrogen-terminated phenyl silicone oil is 0.35 to 0.75 mole%, and the phenyl content in the hydrogen-terminated phenyl silicone oil is 10 to 15 mole%.

In some embodiments, the primer solvent is selected from the group consisting of ester solvents, ether solvents, ketone solvents, alcohol solvents, benzene solvents, and alkane solvents.

In some embodiments, the anti-whitening agent solvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and 2-butoxyethanol acetate).

In some embodiments, the titanate coupling agent is selected from tetra-n-butyl titanate, tetraisobutyl titanate, tetrapropylorthotitanate, And the group formed by tetraisopropyl titanate.

In some embodiments, the hydrogen-containing silicone oil is selected from tetramethyl-disiloxane, tetramethyl-disiloxane, dodeca methylcyclohexasiloxane, and dimethyl dihydrogen A group consisting of dimethyl dichlorosilane and methyl hydrogen polysiloxane with a hydrogen content of 0.1 to 2 mole%.

Here, a method for preparing an anti-whitening primer is also provided. The preparation method of the anti-whitening primer includes a preparation step of a silicone-acrylic acid copolymer, a preparation step of the anti-whitening agent, and a preparation step of the primer.

。 The preparation step of the silicone-acrylic copolymer is to add 5 to 25 parts by mass of acrylic monomer, 0.5 to 2 parts by mass of coupling agent, 8 to 15 parts by mass of organic solvent, and 0.05 to 0.3 parts by mass of initiator to In the first reactor, after inert gas is introduced, the reaction is carried out at a speed of 300 to 600 rpm and a temperature of 60°C to 85°C for 1 to 3 hours. After cooling at normal temperature, an organosilicon-acrylic acid copolymer is obtained. The molecular formula of the silicone-acrylic copolymer is:

.

The preparation step of the anti-whitening agent is to add 90 to 98 parts by mass of the anti-whitening agent solvent and 0.05 to 1 part by mass of the inhibitor to the second reactor, and to react at a speed of 300 to 600 rpm and a temperature of 15 to 25°C for 0.5 To 1 hour. Then add 0.1 to 2 parts by mass of vinyl silicone oil and 0.1 to 2 parts by mass of hydrogen-terminated phenyl silicone oil, react at a speed of 300 to 600 rpm and a temperature of 15 to 25°C for 0.5 to 4 hours to obtain an anti-whitening agent .

The preparation step of the primer is to select 5 to 15 parts by mass of silicone-acrylic acid copolymer, 70 to 90 parts by mass of the primer solvent, 0.01 to 5 parts by mass of hydrogen-containing silicone oil, and 0.1 to 5 parts by mass of titanic acid The ester coupling agent is mixed in the third reactor, reacted at a speed of 300 to 600 rpm and a temperature of 75 to 85°C for 1.5 to 3 hours, cooled to room temperature, and then added to 5 to 15 parts by mass of anti-whitening The agent is reacted at a rotation speed of 300 to 600 rpm and a temperature of 75°C to 85°C for 0.1 to 1 hour to obtain an anti-whitening primer.

In some embodiments, a method for preparing an anti-whitening primer, wherein in the preparation step of the anti-whitening agent, before adding vinyl silicone oil and hydrogen-terminated phenyl silicone oil, a platinum catalyst of 0.05 to 0.15 parts by mass is first added to The reaction speed is 300 to 600 rpm and the temperature is 15 to 25°C for 0.1 to 1 hour.

In some embodiments, the acrylic single system is selected from methyl methacrylate (MMA), methyl acrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate ), butyl acrylate, and butyl methacrylate.

In some embodiments, the coupling agent is selected from vinyltriethoxysilane (vinyltriethoxysilane), vinyltrimethoxy(vinyl)silane, vinyltri-(2-methoxyethoxy) -Vinyl-tri-(2-methoxyethoxy)-silicane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane A group consisting of 3-(methacryloxy)propyltrimethoxysilane and 3-methacryloyl propyltrimethoxysilane.

In some embodiments, the initiator is selected from benzoyl peroxide (BPO), tert-butylperoxy 2-ethylhexyl carbonate, diisoperoxide Propylbenzene (dicumyl peroxide), dilauroyl peroxide, tert-amyl peroxyacetate, azodiisobutyrodinitrile (AIBN), and azobisisovaleronitrile ( Azobisisovaleronitrile, ABVN).

In some embodiments, the organic solvent is selected from the group consisting of ester solvents, ether solvents, ketone solvents, alcohol solvents, benzene solvents, and alkane solvents.

In some embodiments, the hydrogen content in the hydrogen-terminated phenyl silicone oil is 0.35 to 0.75 mole%, and the phenyl content in the hydrogen-terminated phenyl silicone oil is 10 to 15 mole%.

In some embodiments, the primer solvent is selected from the group consisting of ester solvents, ether solvents, ketone solvents, alcohol solvents, benzene solvents, and alkane solvents.

In some embodiments, the anti-whitening agent solvent is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol butyl ether, and ethylene glycol butyl ether acetate.

In some embodiments, the titanate coupling agent is selected from the group consisting of n-butyl titanate, tetraisobutyl titanate, tetrapropyl titanate, and isopropyl titanate.

In some embodiments, the hydrogen-containing silicone oil is selected from the group consisting of tetramethyldihydrodisilaxane, dodecyldihydrohexasiloxane, and dimethyldihydrosiloxane. Hydrogen silicone oil has a hydrogen content of 0.1 to 2 mole%.

In the foregoing embodiments, by adding an anti-whitening agent to the primer, the anti-whitening effect can be achieved, and the whitening phenomenon caused by high humidity can be eliminated. In addition, it can increase the product's long service life, improve the aging resistance, and enhance the sticking effect.

。 This application provides an anti-whitening primer. The anti-whitening primer includes hydrogen-containing silicone oil, a titanate coupling agent, a primer solvent, an anti-whitening agent, and an organic silicon-acrylic acid copolymer. The hydrogen-containing silicone oil accounts for 0.01 to 5 wt%, preferably 0.05 to 2 wt%. The titanate coupling agent accounts for 0.01 to 5 wt%, preferably 0.001 to 2 wt%. The primer solvent accounts for 70 to 90 wt%, preferably 75 to 85 wt%. The anti-whitening agent accounts for 5 to 15 wt%, preferably 8 to 12 wt%. The anti-whitening agent contains at least an anti-whitening agent solvent, vinyl silicone oil, hydrogen-terminated phenyl silicone oil, and an inhibitor. Anti-whitening agent solvent accounts for 4.5 to 14.7 wt%, vinyl silicone oil accounts for 1.85 to 9 wt%, inhibitor accounts for 0.5 to 3 wt%, and hydrogen-terminated phenyl silicone oil accounts for 0.5 to 3 wt%. The silicone-acrylic copolymer accounts for 5 to 15% by weight. The molecular formula of the silicone-acrylic copolymer is:

.

Here, the anti-whitening agent further includes a platinum catalyst, and the platinum catalyst accounts for 0.0025 to 0.015 wt%, which is used to accelerate the mixing reaction of the anti-whitening agent solvent, vinyl silicone oil, hydrogen-terminated phenyl silicone oil, and inhibitor.

More specifically, the primer solvent is selected from the group consisting of ester solvents, ether solvents, ketone solvents, alcohol solvents, benzene solvents, and alkane solvents. Here, the primer solvent may be mixed in multiple types. Preferably, it can be selected from one or more of propylene glycol methyl ether, dimethyl carbonate, and ethyl acetate.

In more detail, the titanate-based coupling agent is selected from the group consisting of n-butyl titanate, tetraisobutyl titanate, tetrapropyl titanate, and isopropyl titanate. Through the titanate coupling agent, it can have a good coupling effect on the thermoplastic polymer and the dry filler.

In more detail, the hydrogen-containing silicone oil is selected from the group consisting of tetramethyldihydrodisilaxane, dodecyldihydrohexasiloxane, and dimethyldihydrosiloxane.

In more detail, the anti-whitening agent solvent in the anti-whitening agent is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol butyl ether, and ethylene glycol butyl ether acetate. In addition, the hydrogen content of the hydrogen-terminated phenyl silicone oil in the anti-whitening agent is 0.35 to 0.75 mole%, and the phenyl content of the hydrogen-terminated phenyl silicone oil is 10 to 15 mole%. Hydrogen silicone oil has a hydrogen content of 0.1 to 2 mole%. The vinyl silicone oil in the anti-whitening agent is an organosilicon polysiloxane containing vinyl groups, wherein the vinyl group concentration is 0.1 to 0.25 mol/kg. However, the above is only an example, not a limitation. The inhibitor includes at least one of a polysiloxane having a hydrocarbyloxy group, a polyvinylsiloxane, a maleate compound, and an amide compound. However, the above is only an example and is not intended to be limiting.

Fig. 1 is a flow chart of a method for preparing an anti-whitening primer. As shown in FIG. 1, the preparation method S1 of the anti-whitening primer includes a step S10 of preparing a silicone-acrylic acid copolymer, a step S20 of preparing an anti-whitening agent, and a step S30 of preparing a primer. Here, the preparation step S10 of the silicone-acrylic acid copolymer and the preparation step S20 of the anti-whitening agent may be performed simultaneously without any order.

。 The preparation step S10 of the silicone-acrylic copolymer is to add 5 to 25 parts by mass of acrylic monomer, 0.5 to 2 parts by mass of coupling agent, 8 to 15 parts by mass of organic solvent, and 0.05 to 0.3 parts by mass of initiator. After the inert gas is introduced into the first reactor, the reaction is carried out at a speed of 300 to 600 rpm and a temperature of 60° C. to 85° C. for 1 to 3 hours. After cooling at normal temperature, an organosilicon-acrylic acid copolymer is obtained. The molecular formula of the silicone-acrylic copolymer is:

.

The anti-whitening agent preparation step S20 may include step S21 and step S25 in more detail. Step S21 is to first mix the anti-whitening agent solvent and the inhibitor. 90 to 98 parts by mass of the anti-whitening agent solvent and 0.05 to 1 part by mass of the inhibitor are added to the second reactor, and the reaction is performed at a rotation speed of 300 to 600 rpm and a temperature of 15 to 25° C. for 0.5 to 1 hour. Step S25 is to add vinyl silicone oil and hydrogen-terminated phenyl silicone oil. Add another 0.1 to 2 parts by mass of vinyl silicone oil and 0.1 to 2 parts by mass of hydrogen-terminated phenyl silicone oil into the second reactor, and react at a speed of 300 to 600 rpm and a temperature of 15 to 25°C for 0.5 to 4 hours An anti-whitening agent is obtained.

Further, step S20 of preparing the anti-whitening agent may further include step S23. Step S23 is to add a platinum catalyst. Before performing step S25, add a platinum catalyst with 0.05 to 0.15 parts by mass, react at a speed of 300 to 600 rpm and a temperature of 15 to 25°C for 0.1 to 1 hour. Thus, the reaction rate is increased through the platinum catalyst, step S25 The anti-whitening agent can be obtained by reducing the reaction time to 0.5 to 1 hour.

The primer preparation step S30 includes step S31 and step S35. Step S31 is a primer mixing step, which is to select 5 to 15 parts by mass of silicone-acrylic acid copolymer, 70 to 90 parts by mass of primer solvent, 0.01 to 5 parts by mass of hydrogen-containing silicone oil, and 0.01 to 5 Mass parts of the titanate-based coupling agent are mixed in the third reactor, reacted at a rotation speed of 300 to 600 rpm and a temperature of 75°C to 85°C for 1.5 to 3 hours, and cooled to room temperature. Step S35 is to add an anti-whitening agent, add 5 to 15 parts by mass of the anti-whitening agent to the third reactor, and react at a speed of 300 to 600 rpm and a temperature of 75 to 85 degrees C for 0.1 to 1 hour to obtain an anti-whitening primer Agent.

Further, in some embodiments, step S31 can also be divided into step S311 and step S313. Step S311 is to mix the silicone-acrylic copolymer and the primer solvent. First select 5 to 15 parts by mass of the silicone-acrylic copolymer and 70 to 90 parts by mass of the primer solvent to add to the third reactor. The rotation speed is controlled at 300 to 600 rpm, and it is stirred at 15 to 40°C for 0.1 to 1 hour to make it thoroughly mixed. Step S313 is a temperature-increasing reaction step. In the third reactor, 0.01 to 5 parts by mass of hydrogen-containing silicone oil and 0.01 to 5 parts by mass of titanate coupling agent are added. The temperature is increased to 70 to 90°C, and the reaction speed is controlled to 300 to 600 rpm.

Here, the first reactor, the second reactor and the third reactor may be the same reactor or different reactors.

In more detail, the acrylic single system in the preparation step S10 of the silicone-acrylic copolymer is selected from methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and methyl The group formed by butyl acrylate.

In more detail, the coupling agent in the preparation step S10 of the silicone-acrylic copolymer is selected from vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-(2-methoxyethoxy)- Silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethylsilane, and 3-methacryloxypropyltrimethoxysilane Group.

In more detail, the initiator in the preparation step S10 of the silicone-acrylic acid copolymer is selected from benzoyl peroxide, t-butyl-2-ethylhexyl peroxycarbonate, dicumyl peroxide, diperoxide The group consisting of laurel, tert-amyl peroxyacetate, azobisisobutyronitrile, and azobisisovaleronitrile.

More specifically, the organic solvent in the preparation step S10 of the silicone-acrylic copolymer is selected from the group consisting of ester solvents, ether solvents, ketone solvents, alcohol solvents, benzene solvents, and alkane solvents.

The following will illustrate the efficacy of the anti-whitening primer in this case with several examples and comparative examples. Here, Example 1 includes 10wt% of silicone-acrylic acid copolymer, 59.8wt% of propylene glycol methyl ether and 20wt % Primer solvent of dimethyl carbonate mixed solvent, 0.1 wt% of methylhydrogenpolysiloxane, and 0.1 wt% of n-butyl titanate, and 10 wt% of anti-whitening agent, including A The hydrogen content of the base hydrogen polysiloxane is 1 mole%. The production method is to first stir the silicone-acrylic acid copolymer and the primer solvent at 300 rpm and 25°C for 0.5 hours, then add methylhydrogenpolysiloxane, and n-butyl titanate at 300 rpm, first Stir at 25°C for 0.5h and then warm to 80°C for 1.5 hours. After cooling to room temperature, add an anti-whitening agent, control the rotation speed at 600 rpm and stir for 1 hour, and then stand for 48 hours to prepare.

Example 2 contains 15 wt% of silicone-acrylic acid copolymer, a primer solvent with a mixed solvent of 25 wt% of propylene glycol methyl ether and 44.82 wt% of dimethyl carbonate, and 0.1 wt% of methylhydrogen polysilicon Oxane, and 0.08% by weight of n-butyl titanate, and 15% by weight of anti-whitening agent, in which the hydrogen content of methylhydrogen polysiloxane is 1 mole%. The production method is to first stir the silicone-acrylic acid copolymer and the primer solvent at 300 rpm and 25°C for 0.5 hours, then add methylhydrogenpolysiloxane, and n-butyl titanate at 300 rpm, first Stir at 25°C for 0.5h and then warm to 80°C for 1.5 hours. After cooling to room temperature, add an anti-whitening agent, control the rotation speed at 600 rpm and stir for 1 hour, and then stand for 48 hours to prepare.

Example 3 A primer solvent containing a mixed solvent of 10wt% silicone-acrylic acid copolymer, 59.8wt% propylene glycol methyl ether, 15wt% dimethyl carbonate, and 5wt% ethyl acetate, 0.05wt% Methylhydrogen polysiloxane, and 0.15wt% of n-butyl titanate, and 10wt% of anti-whitening agent, of which methylhydrogenpolysiloxane has a hydrogen content of 1mole%. The production method is to first stir the silicone-acrylic acid copolymer and the primer solvent at 300 rpm and 25°C for 0.5 hours, then add methylhydrogenpolysiloxane, and n-butyl titanate at 300 rpm, first Stir at 25℃ for 0.5h and then warm to 80℃ for 1.6 hours. After cooling to room temperature, add an anti-whitening agent, control the rotation speed at 600 rpm and stir for 1 hour, and then stand for 48 hours to prepare.

Comparative Example 1 contains a primer solvent of a mixed solvent of 10 wt% silicone-acrylic acid copolymer, 68.6 wt% propylene glycol methyl ether, 15 wt% dimethyl carbonate, and 5 wt% ethyl acetate, 0.6 wt% N-butyl titanate, and 0.8 wt% of methylhydrogenpolysiloxane, of which the hydrogen content of methylhydrogenpolysiloxane is 1mole%. The production method is to first stir the silicone-acrylic acid copolymer and the primer solvent at 300 rpm and 25°C for 0.5 hours, then add methylhydrogenpolysiloxane and n-butyl titanate, and control the speed at 300 rpm. Stir at 25°C for 0.5h, then increase the temperature to 80°C, and react for 1.6 hours. After cooling down to room temperature, it was prepared after standing for 48 hours.

Comparative Example 2 contains a primer solvent of a mixed solvent of 15% by weight of silicone-acrylic acid copolymer, 46.5% by weight of propylene glycol methyl ether, 15% by weight of dimethyl carbonate, and 10% by weight of ethyl acetate, 0.85% by weight N-butyl titanate and 0.5 wt% of methylhydrogen polysiloxane, of which methylhydrogen polysiloxane has a hydrogen content of 1 mole%. The production method is to first stir the silicone-acrylic acid copolymer and the primer solvent at 300 rpm and 25°C for 0.5 hours, then add methylhydrogenpolysiloxane and n-butyl titanate, and control the speed at 300 rpm. Stir at 25°C for 0.5h, then increase the temperature to 80°C, and react for 1.6 hours. After cooling down to room temperature, it was prepared after standing for 48 hours.

The organosilicon-acrylic acid copolymers of Example 1, Example 2, Example 3, Comparative Example 1, and Comparative Example 2 are 10 parts by mass of methyl methacrylate and 1 part by mass of 3-methacrylic acid Acetyloxypropyltriethoxysilane, 10 parts by mass of n-butyl acetate and 0.18 parts by mass of benzoyl oxide were added to the reactor, protected by nitrogen, controlled at 380 rpm, and reacted at 80°C for 1.8h, then cooled with ice water Obtained to room temperature. In addition, the anti-whitening agent of Example 1, Example 2 and Example 3 is to add 98 parts of diethylene glycol butyl ether to the container, add 0.1 parts by mass of inhibitor, control the rotation speed of 600 rpm, temperature 25 ℃, stirring 0.5h ; Then add 0.1 parts by mass of platinum catalyst, control the speed of 600rpm, temperature 25℃, stir for 0.5h; add 1 part by mass of vinyl silicone oil and 1.2 parts by mass of hydrogen-terminated phenyl silicone oil in sequence, control the speed of 500rpm, temperature 25℃ , Stir for 1h.

Here, according to ASTM D2295, the shear force test was carried out. The preparation of the test specimen was to wipe the PC sheet (80 mm long and 25 mm thick and 3 mm thick) with absolute ethanol and wipe the surface of the PC sheet dirty. After wiping, put it at 110 ℃ After drying in the oven for 10 minutes, under the conditions of a temperature of 30°C and a humidity of 70%, a primer (anti-whitening) is sprayed on the surface of the PC sheet with a film thickness of 1 to 5 μm, and then baked at 80°C for one hour , And observe if there is albino phenomenon. The whitening phenomenon must be observed as shown in Table 1. Table 1

In addition, multiple groups were prepared for the aforementioned test pieces, and the general LSR AB agent was selected to be mixed and defoamed at a weight ratio of 1:1, and then coated between two PC test pieces, the coating area was controlled to be 30mm×20mm, and the thickness 2mm. After fixing the sheet, put it in an oven at 130°C for 10min, take it out and cool it to room temperature, let it stand for 24h to complete the test piece sample.

After completing the test piece samples of each example and comparative example, the test piece samples were placed for 0 days, 7 days, 14 days, 20 days and 27 days, clamped up and down with a universal tensile machine jig, and the pull-up speed was set 50mm/min, start the test and record the maximum shear strength value.

The comparison results of the shear strength test for the sample placed for 0 days are shown in Table 2. Table 2

In addition, for another group of test pieces in Example 1, the experimental results of the shear strength test after being placed differently are shown in Table 3 below. table 3

Understandably, the shear strength will gradually decrease as the placement time increases. By adding an anti-whitening agent to the primer, compared to the comparative example without addition, it can achieve the prevention of whitening during spraying, drying or baking, and has the ability to enhance the shear strength, that is, the adhesive strength, so , Can improve the product's anti-aging, increase the product's life cycle.

Although the technical content of the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with this art and makes some changes and retouching without departing from the spirit of the present invention should be covered in the present invention. Within the scope of the invention, so the scope of protection of the present invention shall be deemed as defined by the scope of the attached patent application

S1: Preparation method of anti-whitening primer S10: Preparation steps of silicone-acrylic copolymer S20: Preparation steps of anti-whitening agent S21: Mixed anti-whitening agent solvent and inhibitor S23: Add platinum catalyst S25: Add vinyl silicone oil and hydrogen-terminated phenyl silicone oil S30: Preparation steps of primer S31: Primer base mixing step S311: mixed silicone-acrylic acid copolymer and primer solvent S313: Step of heating reaction S35: Add anti-whitening agent

Fig. 1 is a flow chart of a method for preparing an anti-whitening primer.

S1: Preparation method of anti-whitening primer

S10: Preparation steps of silicone-acrylic copolymer

S20: Preparation steps of anti-whitening agent

S21: Mixed anti-whitening agent solvent and inhibitor

S23: Add platinum catalyst

S25: Add vinyl silicone oil and hydrogen-terminated phenyl silicone oil

S30: Preparation steps of primer

S31: Primer base mixing step

S311: mixed silicone-acrylic acid copolymer and primer solvent

S313: Step of heating reaction

S35: Add anti-whitening agent

Claims (18)

An anti-whitening primer, comprising: a hydrogen-containing silicone oil, accounting for 0.01 to 5wt%; a titanate coupling agent, accounting for 0.01 to 5wt%; a primer solvent, accounting for 70 to 90wt%; one anti-whitening Agent, accounting for 5 to 15 wt%, wherein the anti-whitening agent contains at least an anti-whitening agent solvent, a vinyl silicone oil, a hydrogen-terminated phenyl silicone oil, and an inhibitor, wherein the anti-whitening agent solvent accounts for 4.5 to 14.7 wt %, the vinyl silicone oil accounts for 0.005 to 0.3wt%, the inhibitor accounts for 0.0025 to 0.015wt%, the hydrogen-terminated phenyl silicone oil accounts for 0.005 to 0.3wt%; and an organosilicon-acrylic acid copolymer accounts for 5 to 15wt% %, the molecular formula of the silicone-acrylic copolymer is:

. The anti-whitening primer according to claim 1, wherein the anti-whitening agent further comprises a platinum catalyst, and the platinum catalyst accounts for 0.005 to 0.015 wt%. The anti-bleaching primer according to claim 1, wherein the hydrogen-terminated phenyl silicone oil has a monohydrogen content of 0.35 to 0.75 mole%, and the hydrogen-terminated phenyl silicone oil has a monophenyl content of 10 to 15 moles %. The anti-whitening primer according to any one of claims 1 or 2, wherein the primer solvent is selected from an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, and a benzene A group of solvents and monoalkane solvents. The anti-whitening primer according to claim 1, wherein the anti-whitening agent solvent is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol butyl ether, and ethylene glycol butyl ether acetate. The anti-whitening primer according to claim 1, wherein the titanate-based coupling agent is selected from n-butyl titanate, tetraisobutyl titanate, tetrapropyl titanate, and isopropyl titanate The formed group. The anti-bleaching primer according to claim 1, wherein the hydrogen-containing silicone oil is selected from the group consisting of tetramethyl dihydro disilaxane, dodecyl dihydrohexasiloxane, dimethyl dihydrogen silicon oxide Alkane and methyl hydrogen polysiloxane with a hydrogen content of 0.1 to 2 mole%, and a hydrogen content of the hydrogenated silicone oil is 0.1 to 2 mole%. A method for preparing an anti-whitening primer, comprising: an organosilicon-acrylic acid copolymer preparation step, combining 5 to 25 parts by mass of an acrylic monomer, 0.5 to 2 parts by mass of a coupling agent, and 8 to 15 parts by mass An organic solvent and 0.05 to 0.3 parts by mass of an initiator are added to a first reactor, after passing an inert gas, the reaction is carried out at a speed of 300 to 600 rpm and a temperature of 60 to 85 °C for 1 to 3 After cooling at room temperature for an hour, an organosilicon-acrylic acid copolymer is obtained. The molecular formula of the organosilicon-acrylic acid copolymer is:

; An anti-whitening agent preparation step, adding 90 to 98 parts by mass of an anti-whitening agent solvent and 0.05 to 1 part by mass of an inhibitor to a second reactor at a speed of 300 to 600 rpm and a temperature of 15 ℃ Reaction at ~25°C for 0.5 to 1 hour, then add 0.1 to 2 parts by mass of a vinyl silicone oil and 0.1 to 2 parts by mass of a hydrogen-terminated phenyl silicone oil at a speed of 300 to 600 rpm and a temperature of 15°C to 25°C The reaction is carried out for 0.5 to 4 hours to obtain an anti-whitening agent; and a primer preparation step, selecting 5 to 15 parts by mass of the silicone-acrylic copolymer, 70 to 90 parts by mass of a primer solvent, 0.01 to 5 parts by mass of a hydrogen-containing silicone oil and 0.01 to 5 parts by mass of a titanate-based coupling agent are mixed in a third reactor, and the reaction is carried out at a speed of 300 to 600 rpm and a temperature of 75 to 85°C for 1.5 to 3 hours, cool it to room temperature, then add 5 to 15 parts by mass of the anti-whitening agent, react at a speed of 300 to 600 rpm and a temperature of 75 to 85 degrees C for 0.1 to 1 hour to obtain an anti-whitening primer . The method for preparing an anti-whitening primer as described in claim 8, wherein in the preparation step of the anti-whitening agent, before adding the vinyl silicone oil and the hydrogen-terminated phenyl silicone oil, first add 0.05 to 0.15 parts by mass of A platinum catalyst is reacted at a rotation speed of 300 to 600 rpm and a temperature of 15°C to 25°C for 0.1 to 1 hour. The method for preparing an anti-whitening primer according to any one of claim 8 or claim 9, wherein the acrylic single system is selected from methyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid A group consisting of ethyl ester, butyl acrylate, and butyl methacrylate. The method for preparing the anti-whitening primer according to claim 8, wherein the coupling agent is selected from vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri-(2-methoxyethoxy Group)-silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethylsilane, and 3-methacryloxypropyltrimethoxysilane The formed group. The method for preparing an anti-whitening primer according to claim 8, wherein the initiator is selected from benzoyl peroxide, tert-butyl-2-ethylhexyl peroxycarbonate, dicumyl peroxide, The group consisting of dilauryl peroxide, tert-amyl peroxyacetate, azobisisobutyronitrile, and azobisisovaleronitrile. The method for preparing an anti-whitening primer according to claim 8, wherein the organic solvent is selected from an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, a benzene solvent, and a Group of alkanes. The method for preparing the anti-bleaching primer according to claim 8, wherein the hydrogen-terminated phenyl silicone oil has a monohydrogen content of 0.35 to 0.75 mole%, and the hydrogen-terminated phenyl silicone oil has a monophenyl content of 10 ~15mole%. The method for preparing the anti-whitening primer according to claim 8, wherein the primer solvent is selected from an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, a benzene solvent, And a group of alkane solvents. The method for preparing an anti-whitening primer according to claim 8, wherein the anti-whitening agent solvent is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol butyl ether, and ethylene glycol butyl ether acetate group. The method for preparing an anti-whitening primer according to claim 8, wherein the titanate coupling agent is selected from n-butyl titanate, tetraisobutyl titanate, tetrapropyl titanate, and titanic acid Isopropyl ester group. The method for preparing an anti-whitening primer according to claim 8, wherein the hydrogen-containing silicone oil is selected from tetramethyl dihydro disilaxane, dodecyl dihydrohexasiloxane, and dimethyl dihydrogen Hydrosiloxanes, and the hydrogen content of the hydrogen-containing silicone oil is 0.1 to 2 mole%.

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