CN112080184A

CN112080184A - Anti-whitening primer and preparation method thereof

Info

Publication number: CN112080184A
Application number: CN201910506808.XA
Authority: CN
Inventors: 周国涛; 伍星星
Original assignee: Suzhou Yingta Electronic Technology Co ltd; Megaforce Co Ltd
Current assignee: Suzhou Yingta Electronic Technology Co ltd; Megaforce Co Ltd
Priority date: 2019-06-12
Filing date: 2019-06-12
Publication date: 2020-12-15
Also published as: TW202045644A; TWI693262B

Abstract

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

Description

Anti-whitening primer and preparation method thereof

Technical Field

The invention relates to the field of chemistry, in particular to an anti-whitening primer and a preparation method thereof.

Background

The silicone rubber, i.e., the rubber having a silicone chain, has a unique molecular structure, has low water absorption, high heat resistance, and high fluidity, and can be cured at room temperature or heated, so that it can be widely used in nipples, mobile phone protective covers, and the like. However, silicone rubber is likely to peel off or peel off when used in a hot and humid environment, and the primer needs to be assisted.

The primer on the market is easy to deteriorate in the processes of heating, baking and the like, so that a whitening phenomenon is generated, the appearance of a transparent product is influenced, and when the primer is used in a film mode, the whitening phenomenon is generated, and the product is generally cracked along with the reduction of adhesive strength and the reduction of water resistance and weather resistance.

Disclosure of Invention

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

in some embodiments, the anti-blooming agent further comprises a platinum catalyst comprising 0.0025 to 0.015 wt%.

In some embodiments, the hydrogen content of the hydrogen-terminated phenyl silicone oil is 0.35 to 0.75 mole%, and the phenyl content of 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-blooming agent solvent is selected from the group consisting of ethylene glycol monobutyl ether (ethylene glycol monobutyl ether), diethylene glycol butyl ether (diethylene glycol monobutyl ether), and ethylene glycol butyl ether acetate (2-butyl-ethyl acetate).

In some embodiments, the titanate-based coupling agent is selected from the group consisting of n-butyl titanate (tetra-n-butyl titanate), tetraisobutyl titanate (tetra isobuty titanate), tetrapropyl titanate (tetra propylphosphate), and isopropyl titanate (tetra isopropyltitanate).

In some embodiments, the hydrogen-containing silicone oil is selected from the group consisting of tetramethyldihydrodisiloxane (tetra methyl-disiloxane), dodecamethylhexasiloxane (dodeca methylhexasiloxane), dimethyldihydrosiloxane (dimethyldichlorosiloxane), and methylhydropolysiloxane having a hydrogen content of 0.1 to 2 mole%.

The preparation method of the anti-whitening primer is also provided. The preparation method of the anti-whitening primer comprises the steps of preparing the organic silicon-acrylic acid copolymer, preparing the anti-whitening agent and preparing the primer.

The preparation method of the organic silicon-acrylic acid copolymer comprises the steps of adding 5-25 parts by mass of acrylic acid monomer, 0.5-2 parts by mass of coupling agent, 8-15 parts by mass of organic solvent and 0.05-0.3 part by mass of initiator into a first reactor, introducing inert gas, reacting at the rotation speed of 300-600 rpm and the temperature of 60-85 ℃ for 1-3 hours, and cooling at normal temperature to obtain the organic silicon-acrylic acid copolymer. The molecular formula of the organosilicon-acrylic acid copolymer is:

the preparation step of the anti-blooming agent is to add 90 to 98 mass parts of the anti-blooming agent solvent and 0.05 to 1 mass part of the inhibitor into the second reactor and react for 0.5 to 1 hour at the rotation speed of 300 to 600rpm and the temperature of 15 to 25 ℃. Then adding 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, and reacting at the rotating speed of 300 to 600rpm and the temperature of 15 to 25 ℃ for 0.5 to 4 hours to obtain the anti-whitening agent.

The preparation method of the primer comprises the steps of selecting 5-15 parts by mass of an organic silicon-acrylic acid copolymer, 70-90 parts by mass of a primer solvent, 0.01-5 parts by mass of hydrogen-containing silicone oil and 0.1-5 parts by mass of a titanate coupling agent, mixing the mixture in a third reactor, reacting at the rotation speed of 300-600 rpm and the temperature of 75-85 ℃ for 1.5-3 hours, cooling the mixture to room temperature, adding 5-15 parts by mass of an anti-whitening agent, and reacting at the rotation speed of 300-600 rpm and the temperature of 75-85 ℃ for 0.1-1 hour to obtain the anti-whitening primer.

In some embodiments, the anti-blooming primer is prepared by adding 0.05 to 0.15 parts by mass of a platinum catalyst to a vinyl silicone oil and a hydrogen-terminated phenyl silicone oil, and reacting the mixture at a rotation speed of 300 to 600rpm and a temperature of 15 to 25 ℃ for 0.1 to 1 hour.

In some embodiments, the acrylic monomer is selected from the group consisting of Methyl Methacrylate (MMA), methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), ethyl methacrylate (ethyl methacrylate), butyl acrylate (butyl acrylate), and butyl methacrylate (butyl methacrylate).

In some embodiments, the coupling agent is selected from the group consisting of vinyltriethoxysilane (vinyltriethoxysilane), vinyltrimethoxysilane (vinyloxy) silane, vinyltris- (2-methoxyethoxy) -silane (Vinyl-tri- (2-methacryloxy) -silane), 3-methacryloxypropyltriethoxysilane (3-methacryloxypropylmethyldimethylsilane), 3-methacryloxypropyldimethylsilane (3-methacryloxypropyltrimethoxysilane), and 3-methacryloxypropyltrimethoxysilane (3-methacryloxypropylpropyltrimethoxysilane).

In some embodiments, the initiator is selected from the group consisting of Benzoyl Peroxide (BPO), 2-ethylhexyl tert-butylperoxycarbonate (tert-butyl peroxide 2-ethylhexyl carbonate), dicumyl peroxide (dicumyl peroxide), dilauroyl peroxide (dilauroyl peroxide), amyl peroxyacetate (tert-amyl peroxide), Azobisisobutyronitrile (AIBN), and 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 anti-blooming 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-based 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 tetramethyldihydrodisiloxane, dodecamethylhydrohexasiloxane, and dimethyldihydrosiloxane, and the hydrogen content of the hydrogen-containing silicone oil is 0.1 to 2 mole%.

In the above embodiments, the anti-whitening effect can be achieved by adding the anti-whitening agent to the primer, and the whitening phenomenon due to high humidity can be eliminated. In addition, the service cycle of the product is prolonged, the aging resistance is improved, and the pasting effect can be improved.

The invention is described in detail below with reference to the drawings and specific examples, but the invention is not limited thereto.

Drawings

FIG. 1 is a flow chart of a method for preparing an anti-blooming primer. Wherein the reference numerals

Preparation method of S1 anti-whitening primer

S10 Silicone-acrylic acid copolymer preparation step

S20 preparation step of anti-whitening agent

S21 Mixed anti-blooming agent solvent and inhibitor

S23 adding platinum catalyst

S25 vinyl silicone oil and hydrogen terminated phenyl silicone oil are added

S30 primer preparation step

S31 primer substrate mixing step

S311 hybrid silicone-acrylic copolymer and primer

Solvent(s)

S313 temperature-rising reaction step

S35 anti-whitening agent

Detailed Description

The invention provides an anti-whitening primer. The anti-whitening primer comprises 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 is 0.01 to 5 wt%, preferably 0.05 to 2 wt%. The titanate coupling agent is present in an amount of 0.01 to 5 wt%, preferably 0.001 to 2 wt%. The primer solvent is present in an amount of 70 to 90 wt%, preferably 75 to 85 wt%. The anti-blooming agent is present in an amount of 5 to 15 wt%, preferably 8 to 12 wt%. The anti-blooming agent contains at least an anti-blooming agent solvent, a vinyl silicone oil, a hydrogen-terminated phenyl silicone oil, and an inhibitor. 4.5 to 14.7 weight percent of anti-whitening agent solvent, 1.85 to 9 weight percent of vinyl silicone oil, 0.5 to 3 weight percent of inhibitor and 0.5 to 3 weight percent of hydrogen terminated phenyl silicone oil. The organic silicon-acrylic acid copolymer accounts for 5 to 15 weight percent, and the molecular formula of the organic silicon-acrylic acid copolymer is as follows:

the anti-whitening agent further comprises a platinum catalyst in an amount of 0.0025 to 0.015 wt% for accelerating a mixing reaction of the anti-whitening agent solvent, the vinyl silicone oil, the hydrogen-terminated phenyl silicone oil, and the 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 by plural kinds. Preferably, the solvent is selected from one or more of propylene glycol methyl ether, dimethyl carbonate and ethyl acetate.

More specifically, the titanate-based coupling agent is selected from the group consisting of n-butyl titanate, tetraisobutyl titanate, tetrapropyl titanate, and isopropyl titanate. The titanate coupling agent has good coupling effect on thermoplastic polymers and dry fillers.

More specifically, the hydrogen-containing silicone oil is selected from the group consisting of tetramethyldihydrodisiloxane, dodecamethylhydrohexasiloxane, and dimethyldihydrosiloxane.

More specifically, the anti-blooming agent solvent in the anti-blooming 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-containing end-capped phenyl silicone oil in the anti-whitening agent is 0.35-0.75 mole%, and the phenyl content of the hydrogen-containing end-capped phenyl silicone oil is 10-15 mole%. The hydrogen content of the hydrogen silicone oil is 0.1 to 2 mole%. The vinyl silicone oil in the whitening inhibitor is vinyl-containing silicone, wherein the concentration of vinyl is 0.1-0.25 mol/kg, however, the above is only an example and is not intended to be limiting. The inhibitor includes at least one of a polysiloxane having a hydrocarbyloxy group, a polyvinyl siloxane, a maleate-based compound, and an amide compound, however, the above is merely an example and is not intended to be limiting.

FIG. 1 is a flow chart of a method for preparing an anti-blooming primer. As shown in fig. 1, the preparation method S1 of the anti-blooming primer includes a silicone-acrylic copolymer preparation step S10, an anti-blooming primer preparation step S20, and a primer preparation step S30. Here, the silicone-acrylic copolymer preparation step S10 and the anti-blooming agent preparation step S20 may be performed simultaneously, and not sequentially.

The silicone-acrylic acid copolymer preparation step S10 is to add 5 to 25 parts by mass of an acrylic acid monomer, 0.5 to 2 parts by mass of a coupling agent, 8 to 15 parts by mass of an organic solvent, and 0.05 to 0.3 part by mass of an initiator to a first reactor, introduce an inert gas, react at a rotation speed of 300 to 600rpm at a temperature of 60 to 85 ℃ for 1 to 3 hours, and cool at room temperature to obtain a silicone-acrylic acid copolymer. The molecular formula of the organosilicon-acrylic acid copolymer is:

the anti-blooming agent preparation step S20 may more specifically include steps S21 and S25. In step S21, the anti-blooming agent solvent and the inhibitor are mixed. Adding 90 to 98 parts by mass of an anti-whitening agent solvent and 0.05 to 1 part by mass of an inhibitor into a second reactor, and reacting at the rotation speed of 300 to 600rpm and the temperature of 15 to 25 ℃ for 0.5 to 1 hour. Step S25 is to add vinyl silicone oil and hydrogen-terminated phenyl silicone oil. Adding 0.1 to 2 mass portions of vinyl silicone oil and 0.1 to 2 mass portions of hydrogen-terminated phenyl silicone oil into a second reactor, and reacting for 0.5 to 4 hours at the rotation speed of 300 to 600rpm and the temperature of 15 to 25 ℃ to obtain the anti-whitening agent.

Further, the anti-whitening agent preparation step S20 may further include step S23. Step S23 is the addition of a platinum catalyst. Before the step S25, the platinum catalyst is added in an amount of 0.05 to 0.15 parts by mass, and the mixture is reacted at a rotation speed of 300 to 600rpm at a temperature of 15 to 25 ℃ for 0.1 to 1 hour, so that the reaction rate is increased by the platinum catalyst, and the step S25 can reduce the reaction time to 0.5 to 1 hour to obtain the anti-whitening agent.

The primer preparation step S30 includes steps S31 and S35. Step S31 is a primer base mixing step, in which 5 to 15 parts by mass of an organosilicon-acrylic acid 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, reacted at 75 to 85 ℃ for 1.5 to 3 hours at a rotation speed of 300 to 600rpm, and cooled to room temperature. And step S35, adding an anti-whitening agent, adding 5 to 15 parts by mass of the anti-whitening agent into a third reactor, and reacting at the rotation speed of 300 to 600rpm and the temperature of 75 to 85 ℃ for 0.1 to 1 hour to obtain the anti-whitening primer.

Further, in some embodiments, step S31 can be further divided into step S311 and step S313. Step S311 is to mix the silicone-acrylic acid copolymer and the primer solvent, and add 5 to 15 parts by mass of the silicone-acrylic acid copolymer and 70 to 90 parts by mass of the primer solvent to the third reactor, and stir at 15 to 40 ℃ for 0.1 to 1 hour at a controlled rotation speed of 300 to 600rpm, so as to mix them sufficiently. Step S313 is a temperature-raising reaction step, in which 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 to the third reactor, and the mixture is continuously stirred at the original temperature and the rotation speed, and then the temperature is raised to 70 to 90 ℃, and the rotation speed is controlled to 300 to 600rpm to carry out the reaction.

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

In more detail, the acrylic monomer in the silicone-acrylic acid copolymer preparation step S10 is selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.

In more detail, the coupling agent in the silicone-acrylic acid copolymer preparation step S10 is selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris- (2-methoxyethoxy) -silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethylsilane, and 3-methacryloxypropyltrimethoxysilane.

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

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

The efficacy of the anti-blooming primer of the present invention will be described below by way of several examples and comparative examples, wherein the examples comprise a primer solvent comprising 10 wt% of a silicone-acrylic acid copolymer, a mixed solvent of 59.8 wt% of propylene glycol methyl ether and 20 wt% of dimethyl carbonate, 0.1 wt% of methylhydrogenpolysiloxane, and 0.1 wt% of n-butyl titanate, and 10 wt% of an anti-blooming agent, wherein the hydrogen content of the methylhydrogenpolysiloxane is 1 mole%. The preparation method comprises the steps of firstly stirring the organic silicon-acrylic acid copolymer and the primer solvent for 0.5 hour at the rotating speed of 300rpm and at the temperature of 25 ℃, then adding the methyl hydrogen polysiloxane and the n-butyl titanate, stirring for 0.5 hour at the temperature of 25 ℃ and then heating to 80 ℃ for reaction for 1.5 hours under the control of the rotating speed of 300 rpm. After the temperature is reduced to room temperature, adding an anti-whitening agent, controlling the rotating speed to be 600rpm, stirring for 1 hour, and standing for 48 hours to obtain the product.

Example two primer solvents containing 15 wt% of a silicone-acrylic copolymer, a mixed solvent of 25 wt% of propylene glycol methyl ether and 44.82 wt% of dimethyl carbonate, 0.1 wt% of methylhydrogenpolysiloxane having a hydrogen content of 1 mole%, and 0.08 wt% of n-butyl titanate, and 15 wt% of an anti-whitening agent. The preparation method comprises the steps of firstly stirring the organic silicon-acrylic acid copolymer and the primer solvent for 0.5 hour at the rotating speed of 300rpm and at the temperature of 25 ℃, then adding the methyl hydrogen polysiloxane and the n-butyl titanate, stirring for 0.5 hour at the temperature of 25 ℃ and then heating to 80 ℃ for reaction for 1.5 hours under the control of the rotating speed of 300 rpm. After the temperature is reduced to room temperature, adding an anti-whitening agent, controlling the rotating speed to be 600rpm, stirring for 1 hour, and standing for 48 hours to obtain the product.

Example three contains 10 wt% of a silicone-acrylic copolymer, a primer solvent having a mixed solvent of 59.8 wt% of propylene glycol methyl ether, 15 wt% of dimethyl carbonate, and 5 wt% of ethyl acetate, 0.05 wt% of methylhydrogenpolysiloxane, and 0.15 wt% of n-butyl titanate, and 10 wt% of an anti-whitening agent, wherein the hydrogen content of the methylhydrogenpolysiloxane is 1 mole%. The preparation method comprises the steps of firstly stirring the organic silicon-acrylic acid copolymer and the primer solvent for 0.5 hour at the rotating speed of 300rpm and at the temperature of 25 ℃, then adding the methyl hydrogen polysiloxane and the n-butyl titanate, stirring for 0.5 hour at the temperature of 25 ℃ and then heating to 80 ℃ for reaction for 1.6 hours under the control of the rotating speed of 300 rpm. After the temperature is reduced to room temperature, adding an anti-whitening agent, controlling the rotating speed to be 600rpm, stirring for 1 hour, and standing for 48 hours to obtain the product.

Comparative example one primer solvent comprising 10 wt% of a silicone-acrylic acid copolymer, a mixed solvent of propylene glycol methyl ether having 68.6 wt%, dimethyl carbonate having 15 wt%, and ethyl acetate having 5 wt%, 0.6 wt% of n-butyl titanate, and 0.8 wt% of methylhydrogenpolysiloxane having a hydrogen content of 1 mole%. The preparation method comprises the steps of firstly stirring the organic silicon-acrylic acid copolymer and the primer solvent for 0.5 hour at the rotation speed of 300rpm and at the temperature of 25 ℃, then adding the methyl hydrogen polysiloxane and the n-butyl titanate, stirring for 0.5 hour at the rotation speed of 300rpm, then heating to 80 ℃ and reacting for 1.6 hours. Cooling to room temperature, and standing for 48 hr.

Comparative example two contain 15 wt% of silicone-acrylic acid copolymer, primer solvent having a mixed solvent of propylene glycol methyl ether 46.5 wt%, dimethyl carbonate 15 wt%, and ethyl acetate 10 wt%, 0.85 wt% of n-butyl titanate, and 0.5 wt% of methylhydrogenpolysiloxane, wherein the hydrogen content of methylhydrogenpolysiloxane is 1 mole%. The preparation method comprises the steps of firstly stirring the organic silicon-acrylic acid copolymer and the primer solvent for 0.5 hour at the rotation speed of 300rpm and at the temperature of 25 ℃, then adding the methyl hydrogen polysiloxane and the n-butyl titanate, stirring for 0.5 hour at the rotation speed of 300rpm, then heating to 80 ℃ and reacting for 1.6 hours. Cooling to room temperature, and standing for 48 hr.

The organosilicon-acrylic acid copolymer of the first embodiment, the second embodiment, the third embodiment, the first comparative embodiment and the second comparative embodiment is obtained by adding 10 mass parts of methyl methacrylate, 1 mass part of 3-methacryloxypropyltriethoxysilane, 10 mass parts of n-butyl acetate and 0.18 mass part of benzoyl oxide into a reactor, introducing nitrogen for protection, controlling the rotation speed to 380rpm, reacting at 80 ℃ for 1.8h, and cooling ice water to normal temperature. In addition, the whitening prevention agent of the first embodiment, the second embodiment and the third embodiment is prepared by adding 98 parts of diethylene glycol butyl ether into a container, adding 0.1 part by mass of an inhibitor, controlling the rotation speed of 600rpm and the temperature of 25 ℃, and stirring for 0.5 h; then 0.1 part by mass of platinum catalyst is added dropwise, the rotation speed is controlled to be 600rpm, the temperature is controlled to be 25 ℃, and the stirring is carried out for 0.5 h; and (3) sequentially dropwise adding 1 part by mass of vinyl silicone oil and 1.2 parts by mass of hydrogen-terminated phenyl silicone oil, controlling the rotating speed to be 500rpm and the temperature to be 25 ℃, and stirring for 1 hour.

Here, the shear force test was carried out in accordance with ASTM D2295, and a test piece sample was prepared by wiping a PC sheet (80 mm in length, 25mm in width, and 3mm in thickness) with absolute ethanol to remove stains on the surface of the PC sheet, drying the cleaned PC sheet in a 110 ℃ oven for 10 minutes, spraying (anti-whitening) primer on the surface of the PC sheet at a temperature of 30 ℃ and a humidity of 70% to a film thickness of 1 to 5 μm, baking the PC sheet at 80 ℃ for one hour, and observing whether whitening occurred. The whitening phenomenon was observed as shown in table 1.

TABLE 1

	Film thickness	Whitening phenomenon
			Example one	3μm	Is free of
ExamplesII	2μm	Is free of
			EXAMPLE III	1μm	Is free of
Comparative example 1	3μm	Is provided with
			Comparative example II	2μm	Is provided with

In addition, a plurality of sets of the test pieces were prepared, and a general LSR AB agent was mixed and defoamed at a weight ratio of 1:1, and then coated between two PC test pieces, with a coating area of 30mm × 20mm and a thickness of 2mm being controlled. Fixing the sheet, putting the sheet into an oven at 130 ℃ for 10min, taking out the sheet, cooling the sheet to room temperature, and standing the sheet for 24h to finish the test piece sample.

After the test piece samples of the examples and comparative examples were finished, the test piece samples were left for 0 day, 7 days, 14 days, 20 days, and 27 days, respectively, and clamped up and down by a jig of a universal tensile machine, and the maximum shear strength value was measured and recorded by setting the pull-up speed to 50 mm/min.

Wherein the comparative results of the shear strength test for the sample placed for 0 day are shown in table 2.

TABLE 2

	Shear strength	Film thickness
			Example one	2.3MPa (100% LSR cohesive failure)	3μm
Example two	2.4Mpa (100% LSR cohesive failure)	2μm
			EXAMPLE III	1.8Mpa (80% LSR cohesive failure)	1μm
Comparative example 1	1.2MPa (50% cohesive failure)	3μm
			Comparative example II	1MPa (30% cohesive failure)	2μm

In addition, for another set of test pieces of example, the results of the test conducted on the shear strength after the test pieces were placed differently are shown in Table 3 below.

TABLE 3

Time/day	Shear strength	Film thickness
			0	2.5MPa (100% LSR cohesive failure)	2μm
7	2.4Mpa (100% LSR cohesive failure)	2μm
			14	2.1Mpa (100% LSR cohesive failure)	2μm
20	2.0Mpa (100% LSR cohesive failure)	2μm
			27	1.5MPa (50% LSR cohesive failure)	2μm

It is understood that the shear strength gradually decreases with increasing standing time. By adding the anti-whitening agent to the primer, the whitening phenomenon generated during spraying, drying or baking can be prevented, and the shear strength, namely, the adhesive strength can be enhanced, compared with the non-added comparative example, so that the anti-whitening agent can improve the aging resistance of the product and prolong the service life of the product.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. An anti-blooming primer characterized by comprising:

hydrogen-containing silicone oil accounting for 0.01 to 5 weight percent;

a mono-titanate coupling agent accounting for 0.01 to 5 wt%;

a primer solvent, accounting for 70 to 90 wt%;

an anti-whitening agent, which accounts for 5 to 15 wt%, wherein the anti-whitening agent at least comprises 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 0.3 wt%, the inhibitor accounts for 0.0025 to 0.015 wt%, and the hydrogen-terminated phenyl silicone oil accounts for 0.005 to 0.3 wt%; and

5 to 15 wt% of a silicone-acrylic copolymer having the formula:

2. the anti-blooming primer according to claim 1 wherein the anti-blooming primer further comprises a platinum catalyst, the platinum catalyst comprising 0.0.0025 to 0.015 wt%.

3. The anti-blooming primer coating composition as claimed in claim 1, wherein the hydrogen-terminated phenyl silicone oil has a mono-hydrogen content of 0.35 to 0.75 mole%, and the hydrogen-terminated phenyl silicone oil has a mono-phenyl content of 10 to 15 mole%.

4. The anti-blooming primer according to any one of claims 1 or 2 wherein the primer solvent is selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, a benzene solvent, and an alkane solvent.

5. The anti-blooming primer as claimed in claim 1 wherein the anti-blooming solvent is selected from the group consisting of butyl glycol ether, butyl diglycol ether and butyl glycol acetate.

6. The anti-blooming primer coating of claim 1 wherein the titanate-based coupling agent is selected from the group consisting of n-butyl titanate, tetraisobutyl titanate, tetrapropyl titanate, and isopropyl titanate.

7. The anti-blooming primer as claimed in claim 1, wherein the hydrogen-containing silicone oil is selected from the group consisting of tetramethyldihydrodisiloxane, dodecamethylhydrohexasiloxane, dimethyldihydrosiloxane, and methylhydrogenpolysiloxane having a hydrogen content of 0.1 to 2 mole%, and a hydrogen content of the hydrogen-containing silicone oil is 0.1 to 2 mole%.

8. A method for preparing an anti-whitening primer is characterized by comprising the following steps:

a step of preparing an organosilicon-acrylic acid copolymer, which is to add 5 to 25 parts by mass of an acrylic acid monomer, 0.5 to 2 parts by mass of a coupling agent, 8 to 15 parts by mass of an organic solvent and 0.05 to 0.3 part by mass of an initiator into a first reactor, introduce an inert gas, react at a rotating speed of 300 to 600rpm and a temperature of 60 to 85 ℃ for 1 to 3 hours, and cool at normal temperature to obtain the organosilicon-acrylic acid copolymer, wherein the molecular formula of the organosilicon-acrylic acid copolymer is as follows:

a whitening preventive preparation step, adding 90 to 98 parts by mass of a whitening preventive solvent and 0.05 to 1 part by mass of an inhibitor into a second reactor, reacting at the rotation speed of 300 to 600rpm and the temperature of 15 to 25 ℃ for 0.5 to 1 hour, then adding 0.1 to 2 parts by mass of monovinyl silicone oil and 0.1 to 2 parts by mass of monohydrogen terminated phenyl silicone oil, and reacting at the rotation speed of 300 to 600rpm and the temperature of 15 to 25 ℃ for 0.5 to 4 hours to obtain a whitening preventive; and

a primer preparation step, selecting 5 to 15 parts by mass of the organic silicon-acrylic acid copolymer, 70 to 90 parts by mass of a primer solvent, 0.01 to 5 parts by mass of hydrogen-containing silicone oil and 0.01 to 5 parts by mass of a titanate coupling agent, mixing the mixture in a third reactor, reacting for 1.5 to 3 hours at the rotating speed of 300 to 600rpm and the temperature of 75 to 85 ℃, cooling the mixture to room temperature, adding 5 to 15 parts by mass of the anti-whitening agent, and reacting for 0.1 to 1 hour at the rotating speed of 300 to 600rpm and the temperature of 75 to 85 ℃ to obtain the anti-whitening primer.

9. The method for preparing an anti-blooming primer as claimed in claim 8, wherein in the anti-blooming agent preparation step, before the vinyl silicone oil and the hydrogen-terminated phenyl silicone oil are added, 0.05 to 0.15 parts by mass of a platinum catalyst is added and reacted at a rotation speed of 300 to 600rpm and a temperature of 15 to 25 ℃ for 0.1 to 1 hour.

10. The method of producing the anti-blooming primer as claimed in claim 8 or 9, wherein the acrylic monomer is selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate.

11. The method of claim 8, wherein the coupling agent is selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris- (2-methoxyethoxy) -silane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethylsilane, and 3-methacryloxypropyltrimethoxysilane.

12. The method of claim 8, wherein the initiator is selected from the group consisting of benzoyl peroxide, 2-ethylhexyl tert-butylperoxycarbonate, dicumyl peroxide, dilauroyl peroxide, pivaloyl peroxide acetate, azobisisobutyronitrile, and azobisisovaleronitrile.

13. The method of claim 8, wherein the organic solvent is selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, a benzene solvent, and an alkane solvent.

14. The method for preparing an anti-blooming primer as claimed in claim 8, wherein the hydrogen-terminated phenyl silicone oil has a mono-hydrogen content of 0.35 to 0.75 mole% and a mono-phenyl content of 10 to 15 mole%.

15. The process for preparing an anti-blooming primer as claimed in claim 8, wherein the primer solvent is selected from the group consisting of an ester solvent, an ether solvent, a ketone solvent, an alcohol solvent, a benzene solvent, and an alkane solvent.

16. The method for producing an anti-blooming primer as claimed in claim 8, wherein the anti-blooming solvent is selected from the group consisting of butyl cellosolve, butyl cellosolve and butyl cellosolve acetate.

17. The method of claim 8, wherein the titanate-based coupling agent is selected from the group consisting of n-butyl titanate, tetraisobutyl titanate, tetrapropyl titanate, and isopropyl titanate.

18. The method according to claim 8, wherein the hydrogen-containing silicone oil is selected from the group consisting of tetramethyldihydrodisiloxane, dodecamethylhydrohexasiloxane, and dimethyldihydrosiloxane, and the hydrogen content of the hydrogen-containing silicone oil is 0.1 to 2 mole%.