JPS60136702A - Window pane made of synthetic resin - Google Patents

Abstract

PURPOSE:To obtain a window pane superior in all of abrasion resistance, close adhesion to a hard coat, resistances to heat, heated water, and chemicals by applying a hard coat layer having photochromic property to the surface of a synthetic resin window pane, drying and hardening it. CONSTITUTION:A window pane superior in durability and good in energy saving effect can be obtained by applying and hardening a coating material consisting of 3 components of (A) benzopyrylospirane compd. as a photochromicity donor represented by formula I in which R<4> is H, F, Cl, or Br, and R<5> is H, F, Cl, NO2, or methoxy: (B) a colloidal silica having 1-100mmu particle diameter as a reinforcing agent and abrasion resisting agent: and (C) an organosilicon compd. represented by formula II in which R<1> is vinyl, amino, epoxy, (meth)acrylyloxy, phenyl, or SH; R<2> is H or 1-6C optionally halogenated hydrocarbon; R<3> is 1- 5C hydrocarbon, alkoxyalkyl, or 1-4C acyl; and a, b are each 0, 1, or 2, and a+b<=2.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synthetic resin window glass having excellent surface hardness, abrasion resistance, durability, and photochromic performance.

Currently, inorganic glass is the material used for window glass.

Although organic glass is considered, most window glass is inorganic glass.

Generally, inorganic glass breaks easily and the broken pieces are sharp, making it extremely dangerous. When inorganic glass for automobile windows breaks, it becomes a small object, but the moment it breaks, it becomes invisible and dangerous. In any case, inorganic glass has the disadvantage that it is less safe than organic glass.

On the other hand, organic glass has advantages that cannot be met by inorganic glass, such as light weight, safety (excellent impact resistance), ease of processing, and resistance to staining, but it also has surface hardness.

However, it has a drawback in terms of abrasion resistance and durability, such as not being able to withstand practical use as glass.

Additionally, colorless glass for architectural and automobile windows does not block light. As a result, the interior of the vehicle may become hotter than necessary. It is dazzling when there is strong sunlight. To solve this problem, there are dyed glasses, but sometimes it is better to use colorless lenses at night.
It does not need to be dyed all the time. .

In order to instantly resolve these drawbacks, the present invention is characterized by applying a hard coat layer that has excellent photochromic performance and also has surface hardness and abrasion resistance that can be used practically as window glass. It is a synthetic patterned window glass,
The purpose is to provide window glass that is effective in energy saving, low in volume, and safe.

The window glass that is the object of this invention is as follows:
It is obtained by coating synthetic resin glass with a coating composition containing B and Q as main components and curing it.

A, Silver halide (halogen except 7i<halogen)
, or a benzobyrillospyran compound represented by the general formula (wherein R4 is hydrogen, 7. tsu, chlorine, and bromine; R5 is hydrogen, fluorine, chlorine, and bromine JJ5), an atom, and a methoxy group. At least one selected type is shown].

B0 Colloidal silica 0 with a particle size of 1 to 100 millimicrons, a hydrolyzate of one or more silicon compounds represented by the general formula (where R1 is vinyl, amine, imino, epoxy, (meth)acryloxy , an organic group containing at least one selected from phenyl and SH group, R2 is hydrogen,
(halogenated) carbon hydrogen group having 1 to 6 carbon atoms; R1 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms; a is 0.1 or 2;
．． b is 0.1° or 2, and a + b J 2).

Next, each component constituting the coating composition of the present invention will be described.

The rotary silver of component A can include silver bromide, silver iodide, silver chloride, and mixtures of two or more of these, and silver bromide and silver bromide and other silver halides can be used. A combination with is suitable.

In addition, specific examples of benzobyrillospirane compounds include:
1,5.5-trimethylindolino-2-6'-nitrobenzobilillospirane, 1,5.5-)dimethylindolino-5-chloro-6'-nitrobenzobilillospirane, 1
,5,5-trimethylindolino-6'-nitro8'
-methoxybenzobilillospirane, 1,5.3-)limethylindolino-7/-nitrobenzobyrillospirane,
1,5°3-trimethylindolino-8-promobenzovirilonubilan, 1. s,S-trimethylindolino-
6'-nitro8'-fluoropensohyryrospirane,
1,3.3-)dimethylindolino-6/-promo8
'-Nitrobenzopyrillospirane, 1,5.3-trimethylindolino-5'-nitro8'-methoxybenzobilillospirane, 1.3.5-)limethylindolino-87-methquinbenzo Examples include benzobyrillospirans such as virillospiran. In addition to this, 0. H
Photochromic spiropyrans described in rPhotochromismJ of oBrOWn can also be used.

Component B, colloidal silica with a particle size of 1 to 100 millimicrons, is produced by dispersing high molecular weight silicic anhydride in a dispersion medium such as water, alcohol, or cellosolve, and is produced by a well-known method and commercially available. This is what is being done. Particle sizes of 5 to 40 mμ are particularly useful in the practice of the present invention. Component B is a silicon compound that improves the abrasion resistance and durability of the film.A silicon compound is an essential component for improving the adhesion, flexibility, and abrasion resistance of the film.A specific example is vinyltrimethoxysilane. , vinyltriethoxysilane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybrobyltriethoxysilane, γ-glycytoxypropylmethyldimethoxy Silane.

β-glycidoxyethyltrimethoxine run, β-(5
, 4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(5,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, Phenyltrimethoxysilane.

γ-mercaptopropyltrimethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, Examples include methyltriethoxysilane, methyltripropoxysilane, methyltriptoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, and phenylmethyljethoxysilane. Hydrolysis of these silane compounds is carried out by a well-known method, for example, in a mixed solvent of water and alcohol in the presence of an acid. When compound C is used without hydrolysis,
Insufficient wear resistance. In addition, when using two or more types of silicon compounds by hydrolyzing them, Ki, and the process of hydrolyzing them separately and mixing them! Better results are often obtained by mixing and cohydrolyzing l at the same time. Further, although it is present in a partially condensed form due to the formation of external hydroxyl groups during hydrolysis, it does not affect the effects of the present invention.゛In order to effectively exhibit the photochromic properties of the present invention, it is preferable to add a trace amount of metal oxide such as copper oxide, antimony oxide, or iron oxide.

Also optionally alkali metal salts of carbonic acids such as sodium acetate, amine carboxylates such as ethanolamine acetate, quaternary ammonium carboxylates such as tetramethylammonium acetate and triethylamine, glycine.

Condensation catalysts such as pyridine and alkali hydroxide, and BF3
．． It is effective to use Lewis acids such as BnOR4, 8nO11, and AnOAB, or plainsted acids, aluminum chelate compounds, other metal chelate compounds, and epoxy curing catalysts such as ammonium perchlorate.

Various solvents, surfactants, chirotroping agents, ultraviolet absorbers, antioxidants, and various polymers can be added for the purpose of improving coating work and imparting necessary properties as a paint. As a solvent or diluent, alcohol, ketone, ester, cellosolve, halogenated hydrocarbon f! Various solvents such as carboxylic acids, aromatic compounds, etc. can be used, and it is also possible to use one type or a mixed solvent of two or more of these.

The composition of the present invention can be applied to synthetic resin glass by a well-known method such as a dipping method, a spray method, a spin coating method, or a flow coating method. The synthetic resin glass coated in this way is heated and dried for 1 time.
It becomes a hardened film.

Conditions such as heating temperature and heating time are determined based on the percentage of resin, but a temperature of 60 to 150° C. is usually applied.

The thickness of the resulting cured film is preferably 1 to 30 microns. If it is less than 1μ, satisfactory wear resistance cannot be obtained, and in order to maintain the required properties,
It is necessary to limit the amount of photochromic substances. On the other hand, even if the thickness is 30 μm or more, the effect of increasing the film thickness is expected to increase, but cracks are likely to occur.

In order to improve the adhesion between the synthetic resin glass and the coating composition, it is not a practice of the present invention to pre-treat the lens surface with various primers, activated gas treatment, acid, alkali, etc. chemical treatment. It is useful for

The coating composition thus obtained is coated on a glass surface with a transparent resin such as polycarbonate resin, acrylic resin, diethylene glycol bisallyl carbonate (hereinafter referred to as 0R-39) resin, polystyrene, etc. It can provide nine synthetic resin photochromic glasses with excellent abrasion resistance, durability and photochromic performance.

The present invention will be explained in more detail below using nine practical examples, but the present invention is not limited to these examples.

In addition, parts in the examples indicate parts by weight. The method shown below was used to evaluate the coating.

Photochromic performance A near-odochromic lens photochromic lens tester HE-225 (manufactured by Hasegawa Biko Co., Ltd.) was used, and those with an average light attenuation rate of 30 inches or more in the visible range were evaluated as good in one test.

Abrasion resistance: A load of 1 kg was applied with +aooo steel wool, the surface was rubbed 10 times, and the degree of scratching was divided into the following grades and evaluated.

A: There are almost no scratches.

B: There will be some damage.

0: Significant damage occurs.

Adhesion of the coating film: In the so-called cross-cut tape test, 11 parallel lines were cut vertically and horizontally at 1-in intervals on the surface of the coating film using a knife. After adhesion, the tape was peeled off, and the number of squares that did not peel off among 100 squares was expressed.

Hot water resistance: The state of the film was visually inspected after being immersed in boiling water for 1 hour.

Heat resistance: Visually inspect the state of the film after storing it in a hot air drying oven at 120°C for 2 hours.

Chemical resistance: ethanol, acetone, monosulfur iml solution,
(The state of the film was visually inspected after immersion in a 15% sodium hydroxide water bath solution for 24F￥f @ Example 1゜(1) Hydrolyzate of γ,-glyndoxyprobyltrimethoxysilane Isopropyl alcohol was added in a reactor equipped with a stirrer.
59 parts, 200 parts of isopropyl alcohol-dispersed colloidal silica (1 Oscar 1432' manufactured by Catalysts & Chemicals Industry Co., Ltd., solid content concentration 50%), and 236 parts of γ-glycidoxypropyltrimethochyne silane.

A silicone surfactant (13 parts) was charged, and while stirring, 1 part of 0.05N nitric acid aqueous solution 'WLB' was added all at once at room temperature.After cooling, stirring was continued for 1 hour.Then, stirring was stopped and the mixture was aged for 1 day and night at room temperature. .

(2) Preparation and coating of paint 50 parts of silver bromide with an average particle size of 50 mμ was added to the hydrolyzate obtained in (1), and the mixture was heated with a homogenizer at 200 (10 rpm).
The mixture was stirred at m for 1 hour to decompose, and a paint was obtained. 0 of this paint
Immersion method on R-59 glass (pulling speed 40 m/
”), then dried in a hot air drying oven at 80℃ for 30 minutes, and then dried for another 1 hour.
Cured by heating at 20°C for 120 minutes fc.

The thickness of the coating after curing was 9μ. In addition, coating liquid B
The initial viscosity measured by a Vc type viscometer was 5.2 centiboise, and the viscosity after one month was 5.8 centiboise, and the liquid life was also good. The properties of the obtained synthetic resin glass are shown in the table.

Example λ Inpropyl alcohol 28% in a reactor equipped with a rotor
0 parts, methanol-dispersed colloidal silica 200 parts (Catalyst Chemical Industry ■Oscar 1152. Solid content concentration 30%), γ
-Glycidoxybuvivirmethyldiethoxonelan 165
Then, 5 parts of 1L of a silicone surfactant were added in this order and stirred. Next, at room temperature, while stirring, 0. 31 parts of O5,N acetic acid aqueous solution was added, and stirring was continued for 1 hour. Thereafter, stirring was stopped, and the mixture was aged at room temperature for one day and night. To the solution thus obtained, 30 parts of silver bromide and 10 parts of silver iodide having an average particle size of somμ were added, and the mixture was heated at 20,000 rpm using a homogenizer.
The mixture was stirred for 1 hour to obtain a dispersed paint.

This paint was applied to polycarbonate glass by dipping (pulling speed: 40 ttn/m), and cured by heating in the same manner as in Example 1. The thickness of the film after curing was 9μ. The properties of the obtained synthetic resin glass are shown in the table. Note that the life of the paint was good even after one month.

Example 5 160 parts of methyl cellosolve, 118 parts of γ-glycidquinpropyltrimethoxysilane, 23 parts of methyltrimethoxysilane, 200 parts of methanol-dispersed colloidal silica (
1 methanol silica sol manufactured by Nichisa Kagaku ■ Solid content concentration 30
%) into a reactor equipped with a rotor, and stirred vigorously using a magnetic stirrer at room temperature [L0
A 5N acetic acid aqueous solution was added all at once, and stirring was continued for 1 hour.

Stirring was stopped, and the mixture was aged at 10°C for one day and night. Add 1 part of silicone surfactant to this solution and 40 parts of silver bromide with an average particle size of 50 mμ.
1 part and 4 parts of acetylacetone zirconium were added and stirred with a homogenizer at 2000 rpm for 1 hour to disperse.
It was made into paint. Obtained:...

Apply the coating liquid to the polymethyl methacrylate glass surface.
It was applied by a spray method and dried and cured at 60°C for 1 hour and at 80°C for 5 hours. The thickness of the coating was 10μ. The liquid life of the paint was good for one month. The properties of the resulting synthetic resin glass are shown in the table. Example 4 67 parts of γ-glycidoxypropyltrimethoxysilane,
Ethanol-dispersed colloidal silica (manufactured by Catalysts & Chemicals Industry Co., Ltd.)
'08CAL-1232' solid content concentration 30%) 112 parts, 2-methylbupanol 40 parts [L
10 parts of 0.05N acetic acid was added dropwise at once, and the mixture was stirred at room temperature for 1 hour. To this solution, α03 parts of a flow control agent (“L-7001” manufactured by Nippon Unicar) was added.

In addition, 1.81 (1,3,5-) dimethylindolino-8-bromo-6'-bromobenzobilillos birane (1,1
, 3,5-trimethylindolino-7'-nitropenzopyrylosyrane α6 part, 1.3.3-)limethylindolino-5'-nitro8'-methoxybenzopyrylosyrane 1 .2 parts were added and stirred at room temperature for 1 hour to prepare a paint. This paint was applied to OR-39 glass by a spray method and cured by heating in a hot air dryer at 70°C for 1 hour and then at 90°C for 2 hours to obtain a film having a thickness of 9μ. The liquid life of the paint was good for one month. The properties of the obtained synthetic resin glass are shown in the table.

Example 5 51 parts of vinyltrimethoxysilane, isopropyl alcohol-dispersed colloidal silica (manufactured by Catalysts & Chemicals Co., Ltd. "08○")
To a solution consisting of 86 parts of AL-1432 (solid content 60%) and 90 parts of methyl cellosolve, 0.05N hydrochloric acid was gradually added dropwise and stirred at room temperature for 1 hour.A flow control agent was added to this solution. (Nippon Unicar 'J, -76
04") was added. Furthermore, fc, 1,3.3
-)su, +tilindolino 6'-nitropenzobilyrospiran 3s, 1,3.3-)rifthylindolino-
5'-nitro-8'-methoxybenzobilirosvirane 1
．． 5 parts were added and stirred at room temperature for 1 hour. This coating liquid was applied to polycarbonate glass by a spray method, and heated and cured in a hot air dryer at 70°C for 1 hour and then at 100°C for 2 hours. The thickness of the obtained film was 10 μm. The liquid life of the paint was good for one month. The properties of the obtained synthetic resin glass are shown in the table.

Table Characteristics of synthetic resin glass that's all

Claims (1)

[Claims] A synthetic resin window glass characterized in that Nodecoat I having photochromic properties is coated on at least one surface of the window glass.