CN117209827A

CN117209827A - Coated organic glass, preparation method thereof and optical device

Info

Publication number: CN117209827A
Application number: CN202311098161.4A
Authority: CN
Inventors: 张运生; 欧孝宇; 何东升; 李旭; 林娜; 郑会
Original assignee: Beijing Hangbo New Material Technology Co ltd; China Helicopter Research and Development Institute; China Building Materials Academy CBMA
Current assignee: Beijing Hangbo New Material Technology Co ltd; China Helicopter Research and Development Institute; China Building Materials Academy CBMA
Priority date: 2023-08-29
Filing date: 2023-08-29
Publication date: 2023-12-12

Abstract

The application belongs to the field of organic glass products, and particularly relates to coated organic glass, a preparation method thereof and an optical device. The coated organic glass comprises an organic glass base layer and a film layer which are sequentially arranged, and further comprises: a primer layer arranged on the film layer; the primer layer is a cured product of a primer layer polymer comprising a segment provided by a first siloxane monomer and a segment provided by a second siloxane monomer; a top coat layer disposed on the bottom coat layer; the surface coating is made of polyurethane, and HAs a thickness of 200-250 μm and a hardness of 55-65 HA. When the primer polymer is applied to coated organic glass, the primer polymer is matched with the surface coating made of polyurethane, so that the adhesive force can be improved, the product has excellent sand-wind resistance, and the properties such as transmittance and haze of the product can be prevented from being greatly deteriorated due to the increase of the thickness of the product.

Description

Coated organic glass, preparation method thereof and optical device

Technical Field

The application belongs to the technical field of organic glass products, and particularly relates to coated organic glass, a preparation method thereof and an optical device.

Background

The organic glass has high light transmittance, and can be used for manufacturing various optical parts, in particular to coating products; the transmittance of the organic glass after being coated with a single-layer film or a composite film is about 70-75%. The coated product of the organic glass is required to be provided with the protective coating, because if the protective coating is not provided, vapor and the like possibly permeate between the coated layer and the organic glass base layer in the using process of the coated product, so that the coated layer is separated from the organic glass base layer, and the service life of the product is reduced; therefore, in order to improve the mechanical properties of the coated product, a protective coating is usually disposed on the surface of the organic glass coated product.

In the prior art, a hard protective layer is reported to be used as a protective coating, and although the protective coating has better adhesive force, the adhesive force of the protective coating on organic glass can reach 0 level through a hundred-lattice test, but the protective coating is not resistant to wind and sand blowing. In order to improve the sand-blast resistance of the protective coating, it is reported that a flexible sand-blast resistant coating can be directly coated on an organic glass single-layer film or a composite film as the protective coating, and the protective coating has better sand-blast resistance, but the adhesive force of the protective coating on the organic glass is poor, and the adhesive force can not reach the level 0 after being tested by a hundred-grid method. In order to make the protective coating have good sand-blast resistance and good adhesion, those skilled in the art expect to be able to solve the technical problem by providing a transition layer between the flexible sand-blast resistant coating and the organic glass coated product. However, if a conventional material is used as a connecting layer between the coated film and the sand-blast resistant coating, not only is the adhesion force not ideal, but also the performances such as the transmittance and the haze of the organic glass coated product are difficult to meet.

Disclosure of Invention

The application aims to provide coated organic glass, a preparation method thereof and an optical device. The product provided by the application has excellent adhesive force, can avoid the substantial deterioration of the transmittance of the product due to the increase of the thickness of the product, and has excellent sand-wind resistance.

In order to achieve the above object, a first aspect of the present application provides a coated organic glass, which includes an organic glass base layer and a film layer disposed in this order, further including:

a primer layer disposed on the film layer; the primer layer is a cured product of a primer layer polymer, the primer layer polymer comprises a chain segment provided by a first siloxane monomer and a chain segment provided by a second siloxane monomer, the chain segment provided by the first siloxane monomer is shown as a formula (I), the chain segment provided by the second siloxane monomer is shown as a formula (II), and R ₁ Is amino or epoxy, A is selected from C2-C7 alkylene or-R ₂ -O-R ₃ -，R ₂ 、R ₃ Alkylene of C1-C7;

a topcoat layer disposed on the primer layer; the surface coating is made of polyurethane, and HAs a thickness of 200-250 μm and a hardness of 55-65 HA.

Preferably, the top coating is a cured product of an elastic coating, and the elastic coating comprises the following components in parts by weight: 5-30 parts of hydroxy acrylic resin; 5-30 parts of polyether polyol prepolymer; 0.2-2 parts of drier; 0.2 to 1 part of leveling agent; 0.1-1 part of defoaming agent; 0.1 to 0.5 part of light stabilizer; 0 to 0.5 part of antioxidant; 40-60 parts of solvent; 0.5-10 parts of curing agent; wherein,

the hydroxyl acrylic resin is a copolymer of hydroxyl ester and acrylic ester, the mass fraction of hydroxyl in the copolymer is 0.1-10%, and the number average molecular weight of the copolymer is 1000-30000;

the polyether polyol prepolymer is obtained by adding polytetrahydrofuran glycol, polyoxypropylene triol and isocyanate, the number average molecular weight of the polyether polyol prepolymer is 1000-30000, and the mass fraction of solids in the polyether polyol prepolymer is 40-60%.

Preferably, the elastic coating further comprises an antistatic agent, wherein the antistatic agent is at least one selected from anionic antistatic agents, cationic antistatic agents and nonionic antistatic agents.

Preferably, the topcoat is at least one layer.

Preferably, the molar ratio of functional groups in the first siloxane monomer to functional groups in the second siloxane monomer is 4:1 to 23; wherein the functional group in the first siloxane monomer is phenyl, and the functional group in the second siloxane monomer is amino or epoxy.

Preferably, the first siloxane monomer is selected from at least one of phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, and diphenyldimethoxysilane.

Preferably, the second siloxane monomer is selected from at least one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3- (2, 3-glycidoxypropyl) methyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

Preferably, the film layer is made of an ITO film, a composite film of ITO and metal or an aluminum-doped zinc oxide composite film.

The second aspect of the present application provides a method for preparing a coated organic glass, the coated organic glass comprising an organic glass base layer and a film layer sequentially arranged, comprising the steps of:

1) Providing an undercoat layer on the surface of the film layer; the primer layer is a cured product of a primer layer polymer, the primer layer polymer comprises a chain segment provided by a first siloxane monomer and a chain segment provided by a second siloxane monomer, the chain segment provided by the first siloxane monomer is shown as a formula (I), the chain segment provided by the second siloxane monomer is shown as a formula (II), and R ₁ Is amino or epoxy, A is selected from C2-C7 alkylene or-R ₂ -O-R ₃ -，R ₂ 、R ₃ Alkylene of C1-C7;

2) Providing a top coat on the surface of the bottom coat; the surface coating is made of polyurethane, and HAs a thickness of 200-250 μm and a hardness of 55-65 HA.

The third aspect of the application provides an optical device, wherein the optical device comprises the coated organic glass according to the first aspect of the application.

Through the technical scheme, the coated organic glass, the preparation method and the optical device provided by the application have the following beneficial effects:

(1) The application prepares the primer polymer by adopting specific raw materials for combination and reaction. When the primer polymer is applied to coated organic glass, the primer formed by curing the primer polymer can firmly connect the adjacent film layer and the polyurethane surface coating, and compared with the prior art, the product has excellent adhesive capability.

(2) Compared with the existing connecting layer and protective coating, the coating organic glass can avoid the great deterioration of the performances such as transmittance, haze and the like of the coating organic glass product due to the increase of the thickness of the product by introducing the bottom coating and the polyurethane top coating, for example, compared with the prior art, the whole coating system in the application can improve the transmittance of the product by about 1% -2% in part of the scheme.

(3) According to the application, the specific elastic coating is adopted as the surface coating, so that the wind and sand resistance of the product can be effectively improved, for example, after sand with the speed of 17-19 m/s impacts a sample of the wind and sand resistance layer for 1 minute, the haze increase value is less than 5%; under the same test conditions, the haze increase value of the sample without the wind-resistant sand layer of the application is 39%.

(4) According to the application, the specific raw materials are adopted to prepare the base coat, and the wind-resistant sand layer made of the specific materials is selected, so that the adhesive force, the transmittance, the haze and the wind-resistant sand performance of the product are effectively optimized through the synergistic interaction of the base coat and the wind-resistant sand layer.

The foregoing description is only an overview of the present application, and is intended to provide a better understanding of the present application, as it is embodied in the following description, with reference to the preferred embodiments of the present application and the accompanying drawings.

Drawings

FIG. 1 is a schematic structural view of a coated organic glass according to the present application.

In the figure: 1-an organic glass substrate; 2-a film layer; 3-an undercoat layer; 4-topcoat.

Detailed Description

In order to further describe the technical means and effects adopted for achieving the preset aim of the application, the following detailed description refers to the specific implementation, structure, characteristics and effects of the proposal according to the application with reference to the attached drawings and the preferred embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.

The application will be further described with reference to specific examples, which are not to be construed as limiting the scope of the application, but rather as falling within the scope of the application, since numerous insubstantial modifications and adaptations of the application will now occur to those skilled in the art in light of the foregoing disclosure.

Unless otherwise indicated, materials, reagents, and the like referred to below are commercially available products well known to those skilled in the art; unless otherwise indicated, the methods are all methods well known in the art. Unless otherwise defined, technical or scientific terms used should be given the ordinary meaning as understood by one of ordinary skill in the art to which this application belongs.

The inventors have found during the course of the study that the phenyl-containing siloxane monomer is hydrolyzed with the amino-containing siloxane monomer or the epoxy-containing siloxane monomer to prepare the primer polymer of the present application. The higher the phenyl content in the primer polymer, the greater the refractive index, the more pronounced the increase in light transmittance; the higher the amino group content or the epoxy group content is, the better the adhesion between the top coating and the bottom coating of the polyurethane material is. By adopting the technical scheme disclosed by the application, the phenyl-containing siloxane monomer and the amino-containing siloxane monomer or the epoxy-containing siloxane monomer are combined to play a synergistic interaction between substances to obtain the primer polymer, and the amino or epoxy groups in the primer and the groups in the polyurethane topcoat interact to form chemical bonding, so that the adhesive force is improved. The glass product has excellent adhesive force, can avoid the substantial deterioration of the transmittance of the product due to the increase of the thickness of the product, and has excellent sand-wind resistance.

In order to achieve the above object, a first aspect of the present application provides a coated organic glass, wherein the coated organic glass includes: organic glass substrateThe organic glass substrate comprises an organic glass substrate, a film layer coated on the surface of the organic glass substrate, a bottom coating coated on the film layer and at least one polyurethane top coating coated on the bottom coating; wherein the primer layer is a cured product of a primer layer polymer, the primer layer polymer comprises a chain segment provided by a first siloxane monomer and a chain segment provided by a second siloxane monomer, the chain segment provided by the first siloxane monomer is shown as a formula (I), the chain segment provided by the second siloxane monomer is shown as a formula (II), R1 is amino or epoxy, and A is selected from alkylene groups of C2-C7 or-R ₂ -O-R ₃ -，R ₂ 、R ₃ Alkylene of C1-C7;

the thickness of the surface coating is 200-250 mu m, and the hardness is 55-65 HA.

The cured product in the present application means: and (3) curing the raw materials for forming each layer in the coated organic glass to obtain the product. The specific conditions of the curing treatment are not limited in the present application, and those skilled in the art can select them according to actual needs, and reference is also made to examples.

The primer layer and the topcoat layer described in the present application mean a top coat layer applied on top of the primer layer; it is also possible to apply a multilayer stack of top coats to the surface of the base coat, i.e. at least one of the top coats, if desired.

The number average molecular weight of the primer polymer in the present application is 2000 to 10000. In the application, the specific primer layer, when being matched with the specific polyurethane surface coating, HAs the thickness of 200-250 mu m and the hardness of 55-65 HA; the cooperation mode can effectively optimize the adhesive force, the transmittance, the haze and the sand-wind resistance of the coated organic glass product.

In one embodiment of the present application, the molar ratio of functional groups in the first siloxane monomer to functional groups in the second siloxane monomer is 4:1 to 23; wherein the functional group in the first siloxane monomer is phenyl, and the functional group in the second siloxane monomer is amino or epoxy. As described above, by obtaining a specific primer layer in a specific ratio, a combination of a phenyl group-containing siloxane monomer and an amino group-containing siloxane monomer or an epoxy group-containing siloxane monomer can exert a synergistic interaction between the substances in the specific wind-resistant layer.

The specific structure of the first siloxane monomer in the present application is not particularly limited as long as the technical concept of the present application can be satisfied, and for the convenience of understanding of those skilled in the art, optional materials of the first siloxane monomer used in the present application are exemplified, for example: in one embodiment of the present application, the first siloxane monomer is selected from at least one of phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, and diphenyldimethoxysilane.

The specific structure of the second siloxane monomer in the present application is not particularly limited as long as the technical concept of the present application can be satisfied, and for the convenience of understanding of those skilled in the art, optional materials of the second siloxane monomer used in the present application are exemplified, for example: in one embodiment of the present application, the second siloxane monomer is selected from at least one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane and 3-aminopropyl methyldiethoxysilane; alternatively, the second siloxane monomer is selected from at least one of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3- (2, 3-glycidoxypropyl) methyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

The specific reaction scheme of the first siloxane monomer and the second siloxane monomer is not limited in the present application, and a person skilled in the art can perform the reaction with reference to the conditions of the hydrolytic condensation reaction described in the prior art or develop a new process. For ease of understanding by those skilled in the art, in one embodiment of the present application, the primer polymer comprises the product of a hydrolytic condensation reaction of the first siloxane monomer and the second siloxane monomer in a mixture of ethanol and water. In the hydrolytic condensation reaction, water is used as a reactant, ethanol is used as a diluent, and other kinds of substances can be used as the diluent, for example: isopropyl alcohol, propylene glycol methyl ether, and the like; those skilled in the art will be able to select according to the actual needs. Wherein the conditions of the hydrolytic condensation reaction are as follows: stirring for reaction at 20-50 deg.c and ageing. For example, the conditions of the hydrolytic condensation reaction are: stirring at 20-50 deg.c for over 12 hr and ageing at room temperature for 24 hr.

In one embodiment of the present application, the topcoat HAs a thickness of 200 μm to 250 μm and a hardness of 55 to 65HA. The term "hardness" as used herein refers to the overall hardness value of the topcoat.

In one embodiment of the present application, the topcoat is a wind-resistant sand layer. By adopting the wind-resistant sand layer, the coated organic glass can not only obtain excellent wind-resistant sand performance, but also avoid obvious deterioration of the performances of the product such as transmittance, haze and the like caused by the increase of the thickness of the product by playing the synergistic interaction among the wind-resistant sand layer, the bottom coating and other layers. In the present application, when the thickness and hardness of the topcoat layer are within the above-described ranges, excellent effects can be obtained by cooperating with other technical features. When the hardness is too high, the haze of the coated organic glass is obviously increased after the wind sand is blown away, and when the hardness is too low, the coated organic glass is easily scratched by the wind sand.

In one specific embodiment of the application, the top coating (wind-resistant sand layer) of the polyurethane material is a cured product of an elastic coating, and the elastic coating comprises the following components in parts by weight: 5-30 parts of hydroxy acrylic resin; 5-30 parts of polyether polyol prepolymer; 0.2-2 parts of drier; 0.2 to 1 part of leveling agent; 0.1-1 part of defoaming agent; 0.1 to 0.5 part of light stabilizer; 0 to 0.5 part of antioxidant; 40-60 parts of solvent; 0.5-10 parts of curing agent; wherein,

the polyether polyol prepolymer is obtained by adding polytetrahydrofuran glycol (namely polytetrahydrofuran ether glycol), polyoxypropylene triol (namely polyoxypropylene glycerol ether) and isocyanate, the number average molecular weight of the polyether polyol prepolymer is 1000-30000, and the mass fraction of solids in the polyether polyol prepolymer is 40-60%.

The materials used in the components of the elastomeric coatings described herein can be selected as desired by those skilled in the art. For example: the hydroxy ester is at least one of hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxyethyl acrylate; the acrylic ester can be at least one of methyl methacrylate, butyl methacrylate and butyl acrylate. The isocyanate can be at least one of 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. The drier used in the present application may be at least one selected from triethylenediamine, dibutyltin dilaurate, stannous octoate, and zinc naphthenate. The leveling agent can be selected from organosilicon leveling agents. The defoaming agent can be organic silicon defoaming agent. The light stabilizer can be benzotriazole ultraviolet absorber. The antioxidant is hindered phenol antioxidant. The curing agent used in the present application is at least one selected from the group consisting of 4,4' -dicyclohexylmethane diisocyanate-trimethylolpropane adduct, isophorone diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate biuret, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer.

The solvent used in the present application may be composed of the following proportions, for example: 10 to 20 weight percent of diacetone alcohol, 50 to 60 weight percent of propylene glycol methyl ether acetate and 20 to 30 weight percent of butyl acetate; wherein the sum of the mass fractions of the components is 100wt%.

In one embodiment of the present application, the elastic coating further comprises an antistatic agent selected from at least one of an anionic antistatic agent, a cationic antistatic agent, and a nonionic antistatic agent. In a specific embodiment of the application, the antistatic agent is selected from tetrabromobisphenol a and/or alkyl dicarboxymethylammonium acetolide (dodecyl dimethyl amine acetolide). The antistatic agent can be added to effectively release static electricity generated in the use process of the product. The addition of an antistatic agent to an elastomeric coating increases the haze value, so the amount of antistatic agent needs to be adjusted according to the protocol.

The ITO film layer or the composite film layer of ITO and metal can provide electric heating and electromagnetic shielding functions, and other kinds of films can be applied to the use scene of the application according to actual needs. In an embodiment of the present application, the film layer is made of an ITO film, a composite film of ITO and metal, or an aluminum doped zinc oxide (AZO) composite film.

The second aspect of the application provides a method for preparing the coated organic glass according to the first aspect of the application, wherein the coated organic glass comprises an organic glass base layer and a film layer coated on the surface of the organic glass base layer, and an undercoat layer is arranged on the surface of the film layer; the manner in which the primer layer is disposed is not limited, and one specific operation may be, for example: spraying a primer coating solution on the surface of the film layer, and then curing to form a primer coating; the primer layer is a cured product of a primer layer polymer, the primer layer polymer comprises a chain segment provided by a first siloxane monomer and a chain segment provided by a second siloxane monomer, the chain segment provided by the first siloxane monomer is shown as a formula (I), the chain segment provided by the second siloxane monomer is shown as a formula (II), and R ₁ Is amino or epoxy, A is selected from C2-C7 alkylene or-R ₂ -O-R ₃ -，R ₂ 、R ₃ Alkylene of C1-C7;

then, disposing a topcoat on the surface of the primer layer; the manner of disposing the topcoat is not limited, and one specific operation may be, for example: coating polyurethane paint on the surface of the bottom coat, and then curing; the surface coating is made of polyurethane, and HAs a thickness of 200-250 μm and a hardness of 55-65 HA.

The curtain coating mode used in the application can be selected according to specific requirements by a person skilled in the art, and specific curing parameters, thickness of each layer and the like can be referred to in specific embodiments.

The following is a testing method related to performance parameters in the embodiment of the present application:

(1) Adhesion (hundred method test): GB/T9286-2021 "cross-hatch test of color and varnish paint films".

(2) Transmittance: GB/T2410-2008 "transparent plastics transmittance and haze test method".

(3) Haze: GB/T2410-2008 "transparent plastics transmittance and haze test method".

(4) Surface resistance: ASTM D257-14 Standard test method for DC resistance or conductivity of insulation.

(5) The test method of the wind and sand resistance adopts a non-national standard test method. Compressed air blows sand dust (220 meshes) to pass through a narrow hole (aperture is 5 mm), the speed is 17-19 m/s, the sand blowing time is 1 minute, the change of the haze value is tested, the strong and weak wind-blown sand resistance is represented, the difference between the front and the back of the haze value is increased, and the wind-blown sand resistance is weak; the test results: haze increment/% (difference between haze after test of anti-wind-sand property and haze before test of anti-wind-sand property).

(6) Hardness: the sand-blast resistant layer is coated in a beaker, cured for 6 hours at 80 ℃, and restored to room temperature, and then the cured rubber or thermoplastic rubber indentation hardness test method is carried out according to GB/T531.1-2008, part 1: shore durometer (Shore hardness) test.

Preparation example 1

5kg of 3-aminopropyl triethoxysilane, 1kg of phenyltriethoxysilane, 3kg of deionized water and 5kg of absolute ethanol were added to a 50L glass reaction kettle equipped with a condenser tube at room temperature, and then the reaction mass was heated to 50℃and stirred for 12 hours, after which stirring was stopped and aged for 24 hours to obtain a primer layer solution.

Preparation example 2

2kg of 3-aminopropyl triethoxysilane, 2kg of phenyl trimethoxysilane, 2kg of deionized water and 5kg of absolute ethanol were added to a 50L glass reactor equipped with a condenser at room temperature, the reaction mass was then heated to 50℃and stirred for 12 hours, after which stirring was stopped and aged for 24 hours, to obtain a primer layer solution.

Preparation example 3

2kg of 3-glycidoxypropyl trimethoxysilane, 2kg of phenyl trimethoxysilane, 2kg of deionized water and 5kg of absolute ethanol were charged into a 50L glass reactor equipped with a condenser at room temperature, the reaction mass was then heated to 50℃and stirred for 12 hours, after which stirring was stopped and aged for 24 hours, to obtain a primer layer solution.

Preparation example 4

The top coating is a cured product of an elastic coating, and the elastic coating comprises the following components in parts by weight: 8 parts of hydroxy acrylic resin; 28 parts of polyether polyol prepolymer; 0.5 parts of drier triethylenediamine; 0.5 part of leveling agent; 0.1 part of defoaming agent; 0.1 part of light stabilizer; 0.1 part of antioxidant; 40 parts of propylene glycol methyl ether acetate as a solvent and 10 parts of N-75 curing agent.

Mixing the above materials, homogenizing at room temperature, adding the antistatic agent tetrabromobisphenol A, and mixing, wherein the dosage of the antistatic agent is 0.5% of the total mass of the elastic coating, to obtain the coating of the surface coating. The coating was cured at 80℃for 6 hours with a hardness of 55HA.

The preparation method of the polyether polyol prepolymer comprises the following steps: 10kg of polytetrahydrofuran diol (number average molecular weight 1000) and 2kg of polyoxypropylene triol (number average molecular weight 3000) were mixed with 2kg of 4,4' -dicyclohexylmethane diisocyanate, 21kg of propylene glycol methyl ether acetate was added, and 0.05kg of dibutyltin dilaurate was added, and after stirring uniformly, the mixture was reacted at 70℃for 7 hours to obtain a polyether polyol prepolymer having a solid mass fraction of 40% and a number average molecular weight of 15000.

The preparation method of the hydroxy acrylic ester comprises the following steps: 6kg of hydroxypropyl methacrylate, 1kg of methyl methacrylate, 1kg of butyl methacrylate and 4kg of butyl acrylate are mixed, 18kg of propylene glycol methyl ether acetate is added, 0.3kg of dibenzoyl peroxide is added, and after uniform stirring, the mixture is reacted for 6 hours at 70 ℃ to obtain the hydroxy acrylic resin with the solid mass fraction of about 40%, the number average molecular weight is 10000, and the mass percentage of hydroxy is 5.90%.

Preparation example 5

An elastic coating was prepared in the same manner as in preparation example 4 except that the antistatic agent was replaced with alkyl dicarboxymethylammonium ethyllactone, and the amount of the antistatic agent was 0.5% of the total mass of the elastic coating, to obtain a top-coated coating. The hardness was 56HA.

Preparation example 6

An elastic coating was prepared in the same manner as in preparation example 4 except that no antistatic agent was added to obtain a top-coated coating. The hardness was 56HA.

Preparation example 7

The top coating is a cured product of an elastic coating, and the elastic coating comprises the following components in parts by weight: 30 parts of hydroxy acrylic resin; 30 parts of polyether polyol prepolymer; 0.2 parts of drier triethylenediamine; 0.2 part of leveling agent; 0.1 part of defoaming agent; 0.1 part of light stabilizer; 0.1 part of antioxidant; 40 parts of solvent propylene glycol methyl ether acetate; 10 parts of N-75 curing agent.

Mixing the above materials, and homogenizing at room temperature to obtain the final product. The coating was cured at 80℃for 6h. The hardness was 65HA.

The preparation method of the polyether polyol prepolymer comprises the following steps: 10kg of polytetrahydrofuran diol (number average molecular weight 1000) and 5kg of polyoxypropylene triol (number average molecular weight 3000) were mixed with 1.6kg of 4,4' -dicyclohexylmethane diisocyanate, 23.4kg of propylene glycol methyl ether acetate was added, 0.05kg of dibutyltin dilaurate was added, and after stirring uniformly, the mixture was reacted at 70℃for 7 hours to obtain a polyether polyol prepolymer having a solid mass fraction of 41.5% and a number average molecular weight of 12000.

Preparing hydroxy acrylic ester: 10kg of hydroxypropyl methacrylate, 3kg of methyl methacrylate, 1kg of butyl methacrylate and 2kg of butyl acrylate are mixed, 24kg of propylene glycol methyl ether acetate is added, 0.15kg of dibenzoyl peroxide is added, and after uniform stirring, the mixture is reacted for 6 hours at 70 ℃ to obtain the hydroxy acrylic resin with the solid mass fraction of about 40%, the number average molecular weight is 30000, and the mass percentage of hydroxy is 7.38%.

Preparation example 8

The top coating is a cured product of an elastic coating, and the elastic coating comprises the following components in parts by weight: 30 parts of hydroxy acrylic resin; 10 parts of polyether polyol prepolymer; 0.5 parts of drier triethylenediamine; 1 part of leveling agent; 1 part of defoaming agent; 0.5 parts of light stabilizer; 0.5 parts of antioxidant; 60 parts of solvent propylene glycol methyl ether acetate; 1 part of N-75 curing agent.

And uniformly mixing the materials at room temperature to obtain the coating of the surface coating. The coating was cured at 80℃for 6h. The hardness was 64HA.

The preparation method of the polyether polyol prepolymer comprises the following steps: 10kg of polytetrahydrofuran diol (number average molecular weight 650) and 1kg of polyoxypropylene triol (number average molecular weight 1000) were mixed with 2kg of 4,4' -dicyclohexylmethane diisocyanate, 9kg of propylene glycol methyl ether acetate was added, and 0.1kg of dibutyltin dilaurate as a drier was added, and after stirring uniformly, the mixture was reacted at 70℃for 7 hours to obtain a polyether polyol prepolymer having a solid mass fraction of 60% and a number average molecular weight of 1500.

Preparing hydroxy acrylic ester: 0.5kg of hydroxypropyl methacrylate, 4kg of methyl methacrylate, 2kg of butyl methacrylate and 2kg of butyl acrylate are mixed, 5.5kg of propylene glycol methyl ether acetate is added, 0.4kg of dibenzoyl peroxide is added, and after uniform stirring, the mixture is reacted for 6 hours at 50 ℃ to obtain the hydroxy acrylic resin with the solid mass fraction of 60%, the number average molecular weight is about 2000, and the mass percentage of hydroxy is 0.68%.

In the preparation example, the top coating is a cured product of an elastic coating, and the elastic coating comprises the following components: the leveling agent is as follows: BYK-333 organic silicon leveling agent; the defoamer is as follows: BYK-77 type; the light stabilizer is as follows: UV-328 type; the antioxidant is as follows: type 1010.

Example 1

The organic glass with ITO film coated on one side has a light transmittance of 74.3% and a haze of 0.36%, and the primer solution obtained in preparation example 1 is directly spray-coated on the film layer, and cured for 3 hours at 80 ℃.

Then, the coating material of the top coat layer obtained in preparation example 4 was flow-coated, and cured at 80℃for 6 hours.

Wherein, the thickness of organic glass basic unit, rete, undercoat and top coating respectively is: 5mm, 350nm, 2 μm, 200 μm.

Example 2

The organic glass with one side coated with the ITO and Au composite film has the transmittance of 72.7 percent and the haze of 0.48 percent, the primer solution obtained in the preparation example 2 is directly coated on the film layer in a spraying way, and the organic glass is cured for 3 hours at the temperature of 80 ℃.

Then, the top-coat paint obtained in preparation example 5 was flow-coated and cured at 80℃for 6 hours.

Wherein, the thickness of organic glass basic unit, rete, undercoat and top coating respectively is: 5mm, 100nm, 2.5 μm, 220 μm.

Example 3

The organic glass with one side coated with the ITO and Au composite film has the transmittance of 72.7 percent and the haze of 0.48 percent, the primer solution obtained in the preparation example 3 is directly coated on the film layer in a spraying way, and the organic glass is cured for 3 hours at the temperature of 80 ℃.

Then, the top-coat paint obtained in preparation example 5 was flow-coated and cured at 85℃for 5 hours.

Wherein, the thickness of organic glass basic unit, rete, undercoat and top coating respectively is: 5mm, 100nm, 2.2 μm, 250 μm.

Example 4

A coated organic glass was prepared in the same manner as in example 1, except that the top coat paint of preparation example 6 was used instead of the top coat paint of preparation example 4.

Example 5

A coated organic glass was prepared in the same manner as in example 1, except that the top coat paint of preparation example 7 was used instead of the top coat paint of preparation example 4.

Example 6

A coated organic glass was prepared as in example 1, except that the top coat paint of preparation 8 was used instead of the top coat paint of preparation 4.

Example 7

Coated organic glass was prepared as in example 1, except that the molar ratio of functional groups in the first siloxane monomer to functional groups in the second siloxane monomer was 4:25.

example 8

Coated organic glass was prepared as in example 1, except that the aluminum-doped zinc oxide composite film layer had an initial transmittance of 80.1% and a haze of 0.47%, and the primer layer solution obtained in preparation example 1 was directly spray-coated on the film layer, and cured at 80℃for 3 hours.

Wherein, the thickness of organic glass basic unit, rete, undercoat and top coating respectively is: 5mm, 100nm, 2 μm, 200 μm.

Comparative example 1

A coated organic glass was prepared as in example 1, except that the coated organic glass did not include a primer layer.

Comparative example 2

Coated organic glass was prepared as in example 1, except that the primer solution was: acrylate resin coating (10% propylene glycol methyl ether solution).

Comparative example 3

A coated organic glass was prepared as in example 1, except that the primer solution was prepared by:

2kg of 3-aminopropyl triethoxysilane, 3kg of deionized water and 5kg of absolute ethanol were added to a 50L glass reaction vessel equipped with a condenser at room temperature, and then the reaction mass was heated to 50℃and stirred for 12 hours, after which stirring was stopped and aged for 24 hours to obtain a primer layer solution.

Comparative example 4

2kg of phenyltriethoxysilane, 3kg of deionized water and 5kg of absolute ethanol were added to a 50L glass reaction vessel equipped with a condenser at room temperature, and then the reaction mass was heated to 50℃and stirred for 12 hours, after which stirring was stopped and aged for 24 hours to obtain a primer layer solution.

Comparative example 5

Coated organic glass was prepared as in example 1, except that the topcoat was replaced here with a coating obtained by curing a commercially available stiffening liquid (material: methyl silicone), with a coating thickness of 5um and a coating pencil hardness of 4H.

Comparative example 6

A coated plexiglass was prepared as in example 1, except that the topcoat had a thickness of 120 μm and a hardness of 77HA.

Comparative example 7

A coated plexiglass was prepared as in example 1, except that the topcoat had a thickness of 350 μm and a hardness of 40HA.

The related substances in examples and comparative examples were tested, and the test results are shown in table 1.

TABLE 1

Wherein, transmittance a is: the light transmittance of the organic glass base layer and the film layer as a whole; the transmittance b is: transmittance of the final product in examples or comparative examples.

As can be seen from the table, in examples 1 to 6, the products were obtained, and not only the adhesion force could reach 0 level; and even after the addition of the primer layer and the top coat layer, the thickness of the product is increased, but the haze of the product can be maintained in a proper range, and the transmittance of the product is improved; after the product is tested for the sand-blast resistance, the haze increment is less than 5%, and the product is proved to have excellent sand-blast resistance. Meanwhile, according to the use requirement, an antistatic agent can be optionally added in the preparation process, and the prepared product has certain antistatic performance; the adhesive force, the transmittance and the sand-wind resistance of the product are not greatly affected.

The molar ratio of functional groups in the first siloxane monomer to functional groups in the second siloxane monomer in example 7 was 4:25, from experimental data, the adhesion and sand-wind resistance of the product meet the requirements, but the increase in light transmittance of the product is only 0.3% which is significantly lower than that of the other examples.

Comparative examples and example 1 constitute parallel experiments. No primer was used in comparative example 1 and a conventional primer solution was used in comparative example 2: the adhesive force of the acrylic resin coating is 4 grades, the transmittance is reduced, and the use requirement is difficult to meet. In comparative example 3, the primer layer solution contained no phenyl groups, and the transmittance of the product was significantly reduced. In comparative example 4, the primer layer solution contained only phenyl groups, no amino groups or epoxy groups, and the adhesion of the product was significantly reduced. Comparative example 5 used a hard coat conventional in the art and the haze increase of the product after the wind sand resistance test was as high as 39%. The thickness and hardness of the top coat were adjusted in comparative examples 6 and 7, the above data did not meet the requirements of the present application, and the haze increment of the final product was 46% and 25%, respectively, from the test results of the sand blast resistance, which are difficult to meet the practical requirements.

Through the analysis, the application adopts specific raw materials, wherein the raw materials are siloxane containing phenyl groups and amino groups or epoxy groups, so that the primer polymer is obtained, and the cured product of the primer polymer is assembled with the top coating, so that the glass product has excellent adhesive force, can avoid the substantial deterioration of the transmittance of the product due to the increase of the thickness of the product, and has excellent sand-wind resistance.

The technical features of the claims and/or the description of the present application may be combined in a manner not limited to the combination of the claims by the relation of reference. The technical scheme obtained by combining the technical features in the claims and/or the specification is also the protection scope of the application.

The above description is only of the preferred embodiments of the present application, and is not intended to limit the present application in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present application still fall within the scope of the technical solution of the present application.

Claims

1. The utility model provides a coated organic glass, its includes organic glass basic unit and rete that sets gradually, its characterized in that still includes:

2. The coated organic glass according to claim 1, wherein the top coating is a cured product of an elastic coating, and the elastic coating comprises the following components in parts by weight: 5-30 parts of hydroxy acrylic resin; 5-30 parts of polyether polyol prepolymer; 0.2-2 parts of drier; 0.2 to 1 part of leveling agent; 0.1-1 part of defoaming agent; 0.1 to 0.5 part of light stabilizer; 0 to 0.5 part of antioxidant; 40-60 parts of solvent; 0.5-10 parts of curing agent; wherein,

3. The coated organic glass according to claim 2, wherein the elastic coating further comprises an antistatic agent selected from at least one of anionic antistatic agents, cationic antistatic agents, and nonionic antistatic agents.

4. A coated organic glass according to claim 3, wherein the top coating is at least one layer.

5. The coated organic glass of claim 1, wherein the molar ratio of functional groups in the first siloxane monomer to functional groups in the second siloxane monomer is 4:1 to 23; wherein the functional group in the first siloxane monomer is phenyl, and the functional group in the second siloxane monomer is amino or epoxy.

6. The coated organic glass of claim 5, wherein the first siloxane monomer is selected from at least one of phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, and diphenyldimethoxysilane.

7. The coated organic glass according to claim 5, wherein the second siloxane monomer is selected from at least one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3- (2, 3-glycidoxypropyl) methyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

8. The coated organic glass according to any one of claims 1 to 7, wherein the material of the film layer is an ITO film, a composite film of ITO and metal, or an aluminum-doped zinc oxide composite film.

9. The preparation method of the coated organic glass comprises an organic glass base layer and a film layer which are sequentially arranged, and is characterized by comprising the following steps:

10. An optical device comprising the coated plexiglass of any one of claims 1-8.