WO2009000189A1

WO2009000189A1 - The process of producing lucite with high resistance to abrasion and impact via membrane-transfer method

Info

Publication number: WO2009000189A1
Application number: PCT/CN2008/071260
Authority: WO
Inventors: Minrui Zhang; Shaohua Zhang; Xiongfei Wu; Xiangyun Ouyang
Original assignee: Minrui Zhang; Shaohua Zhang; Xiongfei Wu; Xiangyun Ouyang
Priority date: 2007-06-26
Filing date: 2008-06-11
Publication date: 2008-12-31
Also published as: CN101104701A

Abstract

The process of producing lucite with high resistance to abrasion and impact via membrane-transfer method, which comprise applying methacrylic ester, pentaerythritol triacrylate, trimethylol triacrylate, neopentilglycol diacrylate, polyglycol diacrylate(200,400,600), hexandiol diacrylate, photoinitiator, leveling agent and antifoaming agent to toughened glass by spraying, partially polymerizing these material to form membrane, taking the glass with the membrane as the mold, then introducing methacrylic ester to produce lucite with the nomal process. The lucite with the membrane has enough hardness, enough surface resistance, good light transmittance, good antistatic ability and good capacity to resist impact. Compared with nomal lucite, such kind of lucite has a higher resistance to abrasion and lower hygroscopicity.

Description

Method for preparing high wear-resisting and high-impact plexiglass by film transfer method

Technical field

The invention relates to a method for preparing a plexiglass sheet, in particular to a method for preparing a high abrasion resistance and high impact plexiglass by a film transfer method, which comprises a transfer of a functional layer of an abrasion resistant layer, a formulation of a wear resistant coating, UV curing and spray coating technology for wear resistant layers.

Background technique

Ordinary plexiglass is prepared by: using two pieces of inorganic tempered glass as a template, adding a prepolymer of methyl methacrylate to the film plate, and polymerizing polymerization at a temperature of 45 to 50 ° C for several hours, and then passing through 100 to 125 After about several hours at a high temperature of about °C, ordinary plexiglass is obtained. This ordinary plexiglass has a surface hardness of only 2 3H (pencil hardness), and has a large surface resistance and is liable to generate static electricity. The wear-resistant plexiglass with anti-static and anti-static functions for liquid crystal display and plasma display has a surface hardness of more than 6H and a surface resistance of 10 ⁹ Ω. At present, domestic wear-resistant plexiglass used for making liquid crystal displays and plasma displays is dependent on imports. Foreign wear-resistant plexiglass is a surface coating method (for example, Chinese patent CN1439665A, CN1127695 A, CN1168148A) by: applying a wear-resistant coating on the surface of ordinary plexiglass, that is, obtaining wear-resistant plexiglass . The disadvantages of using the surface coating method to produce wear-resistant plexiglass are: low yield of the product, and poor impact resistance of the surface coating of the plexiglass, which is liable to cause refractive deformation. In China, the research on the microstructure and material properties of plexiglass is still in its infancy. The surface coating method has been used to prepare wear-resistant plexiglass. Summary of the invention

The object of the present invention is to provide a method for preparing a high wear-resistant and high-impact plexiglass by a film transfer method, which overcomes the above-mentioned deficiencies of the prior art, and solves the problem of producing a product of wear-resistant plexiglass by the existing surface coating method. The problem is that the rate is low, the surface coating is poor in impact resistance, and the deformation of the refractive index is liable to occur.

The technical proposal of the invention is: a method for preparing a high wear-resisting and high-impact plexiglass by a film transfer method, which first forms a wear-resistant layer coating on an inorganic tempered glass film plate, and then wears a wear-resistant layer coating The wear-resistant layer functional film is cured on the inorganic tempered glass, and then the inorganic tempered glass which is formed into the wear-resistant layer functional film is used as a template, and the high wear-resistant and high-impact plexiglass is prepared according to the preparation method of the common plexiglass.

A further technical solution of the present invention is: forming a wear-resistant layer coating on the inorganic tempered glass by ultraviolet light to form a wear-resistant layer functional film having an interpenetrating network structure, and controlling one side of the functional film cannot be fully cured to ensure sufficient A plurality of double bonds are combined with the bulk of the plexiglass in the next reaction.

A further technical solution of the present invention is: The wear layer coating of the present invention comprises the following parts: (1) an acrylic prepolymer, usually a methyl methacrylate prepolymer, in an amount of 5% to 40% (based on the weight of the abrasion resistant coating layer coating, the same below), preferably 15% to 30%;

(2) Polyfunctional acrylate reactive diluent, the acrylate which can be used in the wear-resistant coating is pentaerythritol triacrylate in an amount of 0% to 40%, preferably 4% to 25%; the amount of dipentaerythritol tetraacrylate is 0%〜30%, preferably 5%~15%; trimethylolpropane triacrylate is used in an amount of 0%~45%, preferably 10%~40%; neopentyl glycol acrylate is used in an amount of 0%~20 %, preferably 5% to 15%; polyethylene glycol acrylate is used in an amount of 0% to 50%, preferably 20% to 40%, and the degree of polymerization of the polyethylene glycol of the polyethylene glycol acrylate used is n=200. 400 or 600, preferably having a degree of polymerization of 200 or 400;

The amount and type of reactive diluent in the composition are limited, and the viscosity of the wear-resistant layer coating should not be too high. If the viscosity is too high, the hardness and production conditions of the wear-resistant layer may be adversely affected, and low-viscosity is used as much as possible. The monomer is very useful for controlling the viscosity of the composition, but the low-viscosity monomer affects the physicochemical properties of the functional film, the polyfunctional monomer content increases, the cross-linking double bond is greatly increased, and the crack is generated due to the increase of the shrinkage rate. Generally, a polyfunctional acrylate is used as a functional group, so it is necessary to ensure that the functional film has good hardness to improve abrasion resistance;

(3) Photoinitiator, the photoinitiator of the present invention produces a radical and catalyzes a polymerization reaction, it can also be used as an initiator for radical polymerization, and can increase the polymerization rate, and the initiator of the present invention includes 2-hydroxyl -2-methyl-1-phenyl-propan-1-one (1173), 1-hydroxy-cyclohexyl-benzophenone (184) or a mixture thereof, in an amount of 1% by weight based on the total weight of the abrasion resistant coating;

(4) Other additives: For example, the ratio of release agent, antifoaming agent and leveling agent is 0.01%~1%.

A still further technical solution of the present invention is: The method for preparing the abrasion resistant coating of the present invention comprises:

Add the multifunctional acrylate reactive diluent to the reactor equipped with stirring and heating equipment, start stirring and raise the temperature to 40~50 °C, then add methyl methacrylate prepolymer, photoinitiator and release agent. After dissolving, the mixture is thoroughly stirred to obtain a wear-resistant layer coating.

The thickness of the functional film in the present invention is preferably 10 to 50 μm, and when the thickness of the functional film exceeds 50 μm, cracks are liable to occur, and when the functional film is less than ΙΟμηη, the obtained sheet has uneven wear resistance.

Commonly used coating methods such as blade coating, dip coating, shower coating, and spray coating can be used in the present invention, the specificity of the plexiglass production process, and the requirements of the functional film and the coating properties to determine the coating method; In particular, air spray coating can make the functional film coating very uniform, and the thickness of the functional film can be well controlled. The spraying method used in the present invention is air spray coating. The wear resistant coating is sprayed in the form of a gas spray or a pressure spray; preferably air spray, especially air spray, allows the wear resistant coating to be sprayed very thin and evenly. Undiluted wear-resistant coatings can also be used in the production of plexiglass, but the uniformity of the functional film is not guaranteed. After the addition of methyl methacrylate prepolymer, the wear-resistant coating can be sprayed evenly. Further, the thickness is in accordance with the requirements, and the methyl methacrylate prepolymer is used in an amount of 0.2 to 3 times, preferably 0.5 to 1.5 times, based on the total mass of the material.

The present invention has the following features in comparison with the prior art: The surface hardness and surface resistance of the plexiglass sheet described in the present invention are sufficient, the impact resistance and the antistatic effect are excellent, and the light transmittance is also good. Thus, the sheet material is adapted to a display panel that allows light to be transmitted from the display screen. The wear-resistant plexiglass sheet of the present invention has significant wear resistance and low moisture absorption as compared with the case of a conventional methacrylate sheet. detailed description

Example 1

Spray the spray coating on the surface of 300mm x 300mm inorganic tempered glass to form a thick ΙΟμη thick coating. The wear-resistant coating mixture contains 20% methyl methacrylate prepolymer, 5% pentaerythritol triacrylate. Ester, 5% dipentaerythritol triacrylate, 40% neopentyl glycol acrylate, 20% polyethylene glycol acrylate, 0.5% stearic acid, 1.5% free radical photoinitiator 184, 0.5% silicone Leveling agent, 0.5% silicone defoamer.

The wear resistant coating layer of the formulation was polymerized using a lOOOOw UV lamp at a moving speed of 2 m/min.

Then, tempered glass coated with a wear-resistant coating is used as a template, and a plexiglass of 3 mm is produced according to a production method of ordinary plexiglass, and an plexiglass excellent in abrasion resistance and impact resistance can be obtained.

Carrying out the pencil hardness test: The pencil hardness is greater than 6H, the yellowness index remains unchanged, the wear layer does not have silver streaks, and the adhesion of the functional film is good.

Example 2

Spray the spray coating on the surface of 300mmx300mm inorganic tempered glass to form a thick ΙΟμη thick coating. The abrasion resistant coating mixture contains 25% methyl methacrylate prepolymer, 5% pentaerythritol triacrylate. Ester, 10% trimethylolpropane triacrylate, 40% neopentyl glycol acrylate, 20% polyethylene glycol acrylate, 0.5% stearic acid, 1.5% free radical photoinitiator 184, 0.5% Silicone leveling agent, 0.5% silicone defoamer.

Then, tempered glass coated with wear-resistant coating is used as a template, and 3 mm of plexiglass is produced according to the production method of ordinary plexiglass, and plexiglass excellent in wear resistance and impact resistance can be obtained. Pencil hardness test: The pencil hardness is greater than 6H, the yellowness index remains unchanged, the wear layer does not appear silver, and the adhesion of the functional film is good.

Example 3

Spraying the spray coating on the surface of 450mm x 450mm inorganic tempered glass to form a thick ΙΟμη thick coating. The wear resistant coating mixture contains 20% methyl methacrylate prepolymer, 10% pentaerythritol triacrylate. Ester, 30% Trimethylolpropane triacrylate, 40% polyethylene glycol acrylate, 0.5% stearic acid, 1.5% free radical photoinitiator 184, 0.5% silicone leveling agent, 0.5% Silicone defoamer.

Example 4

Spray the spray coating on the surface of the 1310mmx l 510mm inorganic tempered glass to form a 15μηη thick coating. The wear-resistant coating mixture contains 20% methyl methacrylate prepolymer and 10% pentaerythritol. Triacrylate, 30% trimethylolpropane triacrylate, 20% neopentyl glycol acrylate, 20% polyethylene glycol acrylate, 0.5% stearic acid, 1.5% free radical photoinitiator 184, 0.5% silicone leveling agent, 0.5% silicone defoamer.

The wear-resistant coating layer of the formulation was polymerized at a moving speed of 2 m/min using an 11 KW UV lamp.

Comparative example 1

Using two pieces of 1310mmx2510mm tempered glass as a template, adding a prepolymer of methyl methacrylate

10KG, after polymerization at 60 ° C for 24 hours, and then at 115 ° C for 2 hours, 3 mm of ordinary organic glass was obtained.

Perform pencil hardness test: Pencil hardness is 2H.

The wear-resistant and high-impact resistant organic glass of the invention has high wear resistance and high impact resistance, and can be larger Normal production under the area.

The highly wear-resistant and high-impact plexiglass of the present invention can be used for the safety glass of the LCD/TV display panel and the protective cover, and can also be used for a portable telephone.

The inventors of the present invention conducted research to develop a highly wear-resistant and high-impact plexiglass. By adjusting the formulation of the wear layer, using the film transfer method, ultraviolet light curing at low temperature to form a functional film with an interpenetrating network structure, and then closely bonding with the plexiglass body through the process of making ordinary plexiglass, obtaining high wear resistance and high The present invention has been completed by the impact-resistant plexiglass and maintaining the constant mechanical properties and transparency of the plexiglass without the appearance of undesired yellow color.

The invention is not limited to the above specific technical solutions, as long as a wear-resistant layer coating is first formed on the inorganic tempered glass template, and then cured to form a wear-resistant layer functional film, and then the inorganic tempered glass with the wear-resistant layer is used as a template. It is within the scope of the present invention to prepare a highly wear-resistant and high-impact plexiglass according to the preparation method of ordinary plexiglass.

Claims

Rights request

A method for preparing a highly wear-resistant and high-impact plexiglass by a film transfer method, which is characterized in that a wear-resistant layer coating is first formed on an inorganic tempered glass film plate, and the wear-resistant layer coating is applied to the inorganic tempered glass. The upper layer is cured to form a wear-resistant layer functional film, and then the inorganic tempered glass which is cured to form a wear-resistant layer functional film is used as a template, and a high wear-resistant and high-impact plexiglass is prepared according to a common plexiglass preparation method.

2. The method for preparing a highly wear-resistant and high-impact plexiglass according to the film transfer method according to claim 1, wherein the wear-resistant layer coating is cured by ultraviolet light on the inorganic tempered glass to form an interpenetrating network structure. The wear layer functional film, and one side of the control function film, cannot be fully cured to ensure that enough double bonds are combined with the body of the plexiglass in the next reaction.

3. A method of preparing a highly abrasion-resistant and high-impact plexiglass according to the film transfer method according to claim 1 or 2, wherein the wear-resistant layer coating comprises the following components:

(1) an acrylic prepolymer, usually a methyl methacrylate prepolymer, in an amount of 5% to 40%, preferably 15% to 30% by weight of the abrasion resistant coating layer coating;

(2) Polyfunctional acrylate reactive diluent, the acrylate which can be used in the wear-resistant coating is pentaerythritol triacrylate in an amount of 0% to 40%, preferably 4% to 25%; the amount of dipentaerythritol tetraacrylate is 0%~30%, preferably 5%~15%; trimethylolpropane triacrylate is used in an amount of 0%~45%, preferably 10%~40%; neopentyl glycol acrylate is used in an amount of 0%~20 %, preferably 5% to 15%; polyethylene glycol acrylate is used in an amount of 0% to 50%, preferably 20% to 40%, and the degree of polymerization of the polyethylene glycol of the polyethylene glycol acrylate used is n=200. 400 or 600, preferably having a degree of polymerization of 200 or 400;

(3) Photoinitiators, including 2-hydroxy-2-methyl-1-phenyl-propan-1-one (1173), 1-hydroxy-cyclohexyl-benzophenone

(184) or a mixture thereof, in an amount of from 0.1% to 3% by weight based on the total weight of the abrasion resistant coating;

(4) Other additives: such as mold release agent, defoaming agent and leveling agent, the amount is 0.01%~1% of the total weight of the wear-resistant layer coating.

A method for producing a highly wear-resistant and high-impact plexiglass according to the film transfer method according to claim 1 or 2, wherein the release agent of the wear-resistant layer functional film is conventional stearic acid and Polyethylene glycol acrylate, the amount of stearic acid is 0.01%~1%; the amount of polyethylene glycol acrylate is 0%~50%.

5. The method for preparing a highly wear-resistant and high-impact plexiglass according to the film transfer method according to claim 3, wherein the release agent of the wear-resistant layer functional film is conventional stearic acid and polyethylene. The diol acrylate has a stearic acid content of 0.01% to 1%; and the polyethylene glycol acrylate is used in an amount of 0% to 50%. 6. The method for preparing a highly abrasion-resistant and high-impact plexiglass according to the film transfer method according to claim 3, wherein the polyethylene glycol acrylate has a degree of polymerization of n=200, 400 or 600.

A method of preparing a highly abrasion-resistant and high-impact plexiglass according to the film transfer method according to claim 3, wherein the abrasion-resistant layer coating is sprayed in the form of an air spray or a pressure spray.

8. The method according to claim 3, wherein the wear-resistant layer coating is methyl methacrylate as a diluent solvent, and the amount thereof is 0.2-3 times of wear-resistant layer coating.

A method for producing a highly wear-resistant and high-impact plexiglass according to the film transfer method according to claim 1 or 2, wherein the wear-resistant layer coating has a thickness of 10 to 50 μm.

A method of producing a highly abrasion-resistant and high-impact plexiglass according to the film transfer method according to claim 3, wherein the abrasion-resistant layer coating has a thickness of 10 to 50 μm.