JPH0229329A - Low reflection transparent molding - Google Patents

Abstract

PURPOSE:To prevent surface reflection, enhance dazzle prevention properties, prevent visible beam transmission from dropping and enhance visibility by providing a multi-layer film of specific coating composition on the surface of a transparent plastic base. CONSTITUTION:At least one layer of a coating composition film composed of a formula I component or combination of the formula I component and a formula II component and at least one layer of a coating composition film composed of a formula III component or combination of the formula III component and a formula IV component are provided on the surface of a transparent plastic base. As the transparent plastic base, for example, a polymer or its copolymer of the like of acryl resin, polycarbonate resin, polystyrene resin or the like can be used. For providing the coating combination film, immersion coating, revolving coating, spray coating, flow coating, roll coating or the like can be utilized. A practical, durable cured film is formed by heat treating after coating.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention provides a transparent material that prevents surface reflection, has enhanced anti-glare properties, does not reduce visible light transmittance, and has improved visibility. This invention relates to a low-reflection transparent molded product made of a PlusDeck base material.

[Prior Art] In general, plastic materials, especially transparent plastic materials, are used for building windows, doors, etc. by taking advantage of their properties such as light weight, impact resistance, and easy processability in addition to transparency.
Partitions, show windows/showcases, vehicle windows/
It is applied to a wide range of fields such as lighting lamp lenses, instrument protection plates, motorcycle windshields, office automation equipment housings, optical lenses, and eyeglass lenses.

However, the surface of these plastic materials is susceptible to glare and dazzle due to the reflection of sunlight and illumination light, or the reflection of the surrounding scenery, which impedes transparency and see-through, and the reflection of light reduces the light transmittance, causing the plastic to pass through. There is a problem that the brightness is lost when viewed. Such problems can, for example, lead to an increase in reflection loss on the surface of the transparent material used for the light concentrator in solar light concentrators, which have been promoted in recent years from the perspective of energy saving policy, and may also lead to an increase in reflection loss on the surface of the transparent material used in the condensing part of solar light concentrators, which have been promoted in recent years from the perspective of energy saving policy. This results in a reduction in the visibility of meters, dials, etc. due to the reflection of images on the transparent protection plate intended to prevent damage to the instruments.

Furthermore, it has been known that plastic materials have problems in scratch resistance, heat resistance, and the like.

Therefore, in order to reduce the reflection on the surface of plastic materials and further improve the scratch resistance, many proposals have been made for the use of antireflection films, hard coat films, or multilayer films thereof on the surfaces of plastic materials. For low reflection, mainly inorganic materials having a different refractive index from plastic materials, such as Stow.

It is well known to alternately form low refractive index thin films and high refractive index thin films of metal oxides such as Al2O5, Zr0a, and TiOx by vacuum evaporation, sputtering, ion beam methods, and the like. In addition, a low-reflection treatment agent made of a polymer substance is applied to the surface of the plastic material, sprayed,
Alternatively, a treatment method and a low reflection treatment agent in which a coating film with low reflectivity is formed by immersion in a treatment agent have also been put into practical use. Furthermore, attempts have been made to reduce reflection by processing the surface of a plastic material into a finely textured pattern.

Among the various low-reflection methods mentioned above, the method of forming a thin film of inorganic material requires expensive equipment, making anti-reflection plastic expensive, restricting the applicable materials, and having problems with the adhesion of the thin film. There are problems such as low hardness, deterioration of impact resistance, and deformation and optical distortion caused by thermal history in the thin film forming process. In addition, coating films made of low-reflection treatment agents made of polymeric materials have the problem of being difficult to sufficiently increase anti-reflection ability due to the small degree of freedom in the refractive index of organic materials, and also having poor durability. ing. Furthermore, even if the method of processing the surface of a plastic material into a densely uneven shape is effective in terms of reducing reflection, it results in a decrease in light transmittance, making it difficult to maintain a balance between the two properties. In particular, none of the methods could prevent the antireflection ability from decreasing due to the adhesion of dust to the surface.

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned problems in reducing the reflection of plastic materials. The object of the present invention is to provide a new low-reflection transparent molded product which can be added with prevention ability and which can maintain an appropriate balance with light transmittance. Furthermore, another object of the present invention is to form a low-reflection coating film formed on the surface of a plastic base material, which is tightly and firmly adhered to the base material, and which has excellent scratch resistance and durability. An object of the present invention is to provide a low-reflection transparent molded article.

[Means for Solving the Problems] That is, the present invention provides the following (A) on the surface of a transparent plastic base material.
At least one layer of a coating film of a coating composition comprising component 1) or component (A1) and component (A2), and a coating composition comprising component (B1) or component (B1) and (B2) below. The present invention relates to a low-reflection transparent molded article characterized in that it is formed in a multilayered manner, including at least one coating film of the present invention.

(A1) At least one compound having a repeating unit represented by the general formula
seed.

(However, in the formula, Xl and Xil each represent a halogen excluding fluorine, a methyl group, an ethyl group, or a methoxy group, and may be the same or different, and a and b each represent an integer of O to 4.) (A2) - At least one organosilicon compound represented by the general formula % or a partial hydrolyzate thereof.

(However, in the formula, 11.R1 each represents an organic group having 1 to 16 carbon atoms and may be the same or different, Yl is a hydrolyzable functional organic group, and c and d are each an integer of O to 3. and satisfies 0≦c+d≦3.) (Old) At least one fluorine-containing compound represented by the general formula or a partial hydrolyzate thereof.

(However, in the formula, R" and R' represent hydrogen or an organic group having 1 to 6 carbon atoms, and may be the same or different. x3 represents a hydrolyzable group.

e and f represent integers of 1 to 3. ) (B2) At least one organosilicon compound represented by the general formula % or a partial hydrolyzate thereof.

(However, in the formula, p and 6.16 each represent an organic group having 1 to 16 carbon atoms, and may be the same or different. yg is a hydrolyzable functional organic group, and i and j each represent an organic group having 0 to 3 carbon atoms.) Indicates an integer, 0≦1+j≦
3 is satisfied. ) Examples of the transparent plastic base material in the present invention include acrylic resin, polycarbonate resin, polystyrene resin, diethylene glycol bis(allyl carbonate), etc.
(hereinafter referred to as PPG's product name "CR-39") Polymer, copolymer of CR-39 and styrene, copolymer of C-39 and diallyl phthalate, diallyl carbonate polymer of (halogenated) bisphenol A Polymers and copolymers thereof, (halogenated) di(meth)acrylate polymers of bisphenol A and copolymers thereof, (halogenated)
Examples include urethane-modified (meth)acrylate polymers of bisphenol A and copolymers thereof.

Provided on the surface of the above transparent plastic base material (A1
) component or a coating composition consisting of the (A1) component and (A2) component (hereinafter referred to as coating composition (A))
), the compound of component (A1) is:
For example, +S@5-CI1. cn, -@)-CIl, all, →
Examples include compounds having repeating units such as, and at least one of them is used. Polymers made of these exemplified compounds can be obtained, for example, by reacting divinylbenzene and p-pen7enethiol under ultraviolet irradiation or in the presence of a radical polymerization initiator (Japanese Patent Laid-open No. 62
=Refer to Publication No. 270627).

Component (A1) is an essential component for obtaining a high refractive index coating film, and is also a useful component for improving the adhesion to the substrate.

Coating composition (A) contains (A1) and (A2).
By containing an organosilicon compound represented by the above general formula as a component, the scratch resistance, flexibility, chemical resistance, etc. of the coating film can be improved. Since it is low, it is necessary to consider the balance with the target refractive index.Specific examples of compounds as component (A2) include methyl silicate, ethyl silicate,
Tetraalkoxysilanes such as lopropyl silicate, i-propyl silicate, loobyl silicate, 5ec-butyl silicate and monobutyl silicate, and their hydrolysates, as well as methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxy Silane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane Ethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ
-chloropropyltriacetoxysilane, 3.3.3-
Trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-
β-(aminoethyl)-di-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane 5Chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycide xymethyltriethoxysilane, a-glycytoxyethyltrimethoxysilane, a-glycidoxyethyltriethoxysilane,
β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, a-glycidoxyprobyltrimethoxysilane, a-glycidoxyprobyltriethoxysilane, β-glycidoxyprobyltriethoxysilane Methoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxybrobyltribroboxysilane, γ-glycidoxyprobyltributoxysilane, γ-glycidoxybrobyltrimethoxyethoxysilane, γ-glycidoxyprobyltriphenoxysilane, α-glycid Xybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-
Glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyl Triethoxysilane, β-(3
, 4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoquine silane, β-(3,4-
epoxycyclohexyl)ethyltributoxysilane,
β-(34-epoxycyclohexyl)ethyltrimethoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-
Epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane Trialkoxysilane such as ethoxysilane, triazyloxysilane or triphenoxysilane or their hydrolysates, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, γ-chloropropylmethyldimethoxy Silane, γ-chloropropylmethyljethoxysilane.

Dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyljethoxysilane, γ-aminopropylmethyldimethoxysilane, γ -aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, glycidoxyethylmethyldimethoxysilane, glycidoxymethylmethyljethoxysilane, a-glycidoxyethylmethyldimethoxysilane, α
-glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, a-glycidoxypropylmethyldimethoxysilane, a-glycidoxypropylmethyl Jetoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldibroboxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxybrobyl dimethoxysilane, γ-glycidoxypropylethyljethoxysilane, γ-glycidoxybrobyl ethyldibroboxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ- Dialkoxysilanes or diacyloxysilanes such as glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc., and such organosilicon At least one compound or a partial hydrolyzate thereof is used. In coating composition (A) (All
By varying the ratio of component (A2) to component (A2), it is possible to obtain coating compositions with a wide range of refractive index values.

Coating composition (A) consists of component (A1) alone or (
Component A1) and component (A2) may be simply mixed together, or may be mixed together with additives as described below, which may be added as necessary. Alternatively, a partial hydrolyzate of component (A2) may be obtained and then mixed, and partial hydrolysis is achieved by adding an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid, or pure water.

When preparing coating composition (A), if components (A1) and (A2) are used together, partial hydrolysis can be carried out at the same time, and water etc. can be added at the same time. However, it is preferable to adjust the liquid temperature and addition rate in order to control the hydrolysis rate.

During hydrolysis, alcohol, alkoxy alcohol, etc. are produced, and by removing appropriate amounts of these and water under heating and reduced pressure, the solid content concentration can be adjusted relatively arbitrarily. Further, by adding an appropriate solvent after complete removal, substantially any solvent can be selected.

As the solvent, alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic solvents can be used depending on the purpose, and if necessary, a mixed solvent system can also be used.

Furthermore, there is no problem in adding various additives to this composition depending on the purpose. Various surfactants can be used to improve the smoothness of the coating obtained with this coating composition. Further, various additives such as various metal oxide sols, epoxy resins, butyral resins, etc. can also be added. In addition, ultraviolet absorbers such as benzophenone, triazole, and sarderic acid can be added to prevent yellowing. These various additives are selected in consideration of their compatibility with the coating composition.

In the present invention, (B11 component or (B1) component and (B
In the coating composition consisting of component 2) (hereinafter referred to as coating composition (Bl)), the (old) component and the component (B2) are compounds represented by the above general formula or a partial hydrolyzate thereof. Do (B1)
The component compound is a polyfluoroalkylene group-containing bissilane compound, which has a low polarizability of F atoms, and therefore has a low refractive index, and is a component for exhibiting low reflectivity and high transmittance. This component is also a useful component for improving the scratch resistance of the resulting coating film.

A typical example of the compound of component (B1) is X5SiCxl
14(CFa)nCJ4SiXs (wherein, X is CI
, 0CIIs, 0Czlls, n represents an integer of 4 to 16. ) or their partial hydrolysates, and at least one of them is used.

The properties of the coating film can be improved by containing an organosilicon compound represented by the above general formula as the component (B2) in combination with the component (B1) in the coating composition (B). Such component (B2) may be exemplified by a compound similar to the organosilicon compound of component (A2), and (B2)
The compound of the component and the component (A2) may be of the same type. The coating composition (B) is preferably a fluorine-containing compound since the purpose is to form a coating film with a low refractive index. An example of such a compound is RfCxl14SiX' 5 RfCzl14SiX' * AH.

(IlfCd14) asiX' ffRf CON
II Cx II a S i X '.

RfC port N It C * It , N II Cs
It, S i X”.

RI'SO,N (CL) C,11,C0N11 (
CH,) SiX'.

RfCsllJCO(CIlz) ts (CL) S
iX'5RfC! I1. OC mouth N) lcsllasi
X'5RfCzLNllCitLSiX's (wherein, Rf is a polyfluoroalkyl group having 4 to 16 carbon atoms, %x' is CI, OCL, C, 11, n is 4 to 16
m is an integer of 1 or more. ), or a partial hydrolyzate thereof, and at least one of them is used.

The coating composition (B) is prepared in the same manner as the coating composition (A), and the hydrolysis, selection of solvent, etc. may be the same.

Therefore, when forming a coating film, it is necessary to add a curing catalyst for silanol condensation in order to lower the heating temperature and shorten the heating time to promote curing. Such curing catalysts include conventionally known catalysts such as ethanolamine, jetanolamine,
Organic amines such as ethylenediamine, lead oxide, lead carbonate,
Various lead compounds such as lead stearate, quaternary ammonium compounds such as tetramethylammonium hydroxide, metal chelate compounds such as aluminum acetylacetone, and cobalt acetylacetone can be used.

Furthermore, there is no problem in adding various additives to the coating composition (81) depending on the purpose, and it is possible to use various surfactants to improve the smoothness of the coating film obtained with this composition. That is, depending on the purpose, for example, the following fluorine-containing compounds, polyfluoroalkylene group-containing jepoxy compounds, copolymers of polyfluoroalkyl group-containing methacrylates and methacrylic acid derivatives, for example, A reaction product of a polyfluoroalkyl group-containing alcohol and a melamine derivative, such as a reaction product with Rf(C11□)20H.

In addition, various additives such as metal oxide sols, epoxy resins, butyral resins, and ultraviolet absorbers such as benzophenone, triazole, and salicylic acid absorbers can be added to prevent yellowing. The ultraviolet absorber is selected in consideration of its compatibility with the composition.

Coating composition (A) and coating composition (
To provide the coating film B), conventionally known methods such as dip coating, spin coating, spray coating, flow coating, and roller coating can be employed. After application, apply at a temperature of 70 to 160°C.
A cured coating film that can withstand practical use is formed by heat treatment for 0 to 120 minutes. Therefore, the coating composition (
The coating film B) is a low refractive index coating film containing a coating composition (
By providing it through the coating film of A), low reflectivity is achieved. Further, the coating film of the coating composition (B) is provided on the uppermost layer (air side) with the coating film of the coating composition (A) interposed therebetween. Therefore, at least one layer of the coating film of the coating composition (A) is interposed between the substrate and the coating film of the coating composition (B). Coating composition (
The coating film A) can be designed to have various refractive indexes by changing the mixing ratio of the components (A1) and (A2), for example. Furthermore, it is possible to combine coating films of various refractive indexes and provide them in multiple layers to obtain a coating film with desired characteristics. When forming coating films using coating compositions (A) and (B), there is no limit to the number of layers that can be formed, but as the number of layers increases, it becomes technically difficult to maintain uniformity of the coating film. However, in practical terms, there is also the problem of coating cost, and it is appropriate to use two to three layers. Multi-layered coatings can be achieved by coating each coating after it has completely cured, or by allowing it to air dry for a certain period of time, or by coating it in an incompletely cured state. , can be selected appropriately taking into account post-processes.

[Examples] The present invention will be specifically explained below using Examples, but it goes without saying that the present invention is not limited only to these Examples.

Examples 1 to 3 Comparative Example 1 ■ Preparation of coating composition (^) (A1) Preparation of component 5.0 g of a compound having a repeating unit represented by the following formula (a1) (weight average molecular weight 859 mm) was added to N
It was added to 100 g of -methyl-2-pyrrolidone and dissolved by heating to 75°C. Subsequently, the temperature was maintained at 75° C. for 5 hours, and then left at room temperature. (Hereafter, this solution) IA-(11
It is abbreviated as ) (^2) Preparation of ingredients 5g of γ-glycidoxypropyl trimethoxysilane was
The mixture was dissolved in 65.8 g of -methyl-2-pyrrolidone, and 2.5 g of a 1% aqueous hydrochloric acid solution cooled to 5° C. or lower was gradually added dropwise thereto. After the dropwise addition, the temperature was maintained at 5°C for 2 hours, then the temperature was returned to room temperature, and then 0.1 g of magnesium perchlorate was added.
was added and aged for one week at room temperature. (Hereinafter, this solution will be abbreviated as IIA-02.) HA-01 and IIA-02 prepared as described above were
A coating composition (Al 2 ) was prepared by mixing in the proportions shown in the table.

■ Preparation of coating composition (B) The polyfluoroalkylene group-containing compound represented by the following formula (b1) and the Sujiran compound are used as the (B1) component, and 20g of the same and γ-glycidoxypropyltrimethoxysilane are used as the (B2) component. Dissolve 6.2 g of this in 520 g of diacetone alcohol, and add 1% aqueous hydrochloric acid solution 3 while keeping the temperature of the solution below 10°C.
．． 4 was gradually added dropwise. After the dropwise addition was completed, the liquid temperature was kept at 10° C. or less for 1 hour, and then the temperature was returned to room temperature and left for 5 days. Furthermore, aluminum acetylacetonate! , 1g
was added to prepare a coating composition (B).

■Formation of coating film on base material Diethylene glycol bisallyl carbonate (hereinafter referred to as
1OcrnX IO consisting of (abbreviated as C1+-39)
A plate of cm x 2 mm was immersed in the coating composition (A) prepared as described in 1- above, pulled up at a pulling rate of 15 cn+/min, and then heat-treated at 140°C for 30 minutes to harden the coating film. Formed. Subsequently, this was immersed in the above-mentioned coating composition (B), pulled up at a pulling rate of 6 cm/min, and then heat-treated at 100° C. for 120 minutes to form a coating film.

In this way, the characteristics of the low-reflection transparent molded bodies provided with the coating films made of the coating compositions (A) and (B) were evaluated as follows. The results are shown in Table 1.

1. Resistance test The resistance to scratches caused by rubbing with 'oooo steel wool (trade name: "Bonstar", Nippon Bonstar ■ product) was examined and judged as follows.

A: No scratches even with strong friction B: Slight scratches with strong friction C: Many scratches with strong friction 2 Reflectance measurement self-recording spectrophotometer reflected light measurement accessory (Hitachi model:
323 type) to measure the average reflectance at an incident angle of 5° for wavelengths of 4000μ to 7000μ.

3 Adhesion test Cross-cut tape test: 1mm on the surface of the coating film with a knife.
Cross-cut 100 squares by inserting 11 parallel lines vertically and horizontally at intervals, attach cellophane adhesive tape on top of it, peel off the tape, and select the squares that will not peel out of the 100 squares. I checked the number of

4 Durability Test The adhesion and scratch resistance of the coating film after Ihr immersion in boiling water was investigated.

Table 1 The (old) component of the coating composition (B) of Comparative Example 1 was the same as Examples 1 to 3, except that 19 g of the compound of formula (b4) below was used instead of the compound of formula (b1). The prepared composition was used.

CsF I 1c21+4sI (OCIlsl, l
(b4) Example 4~! 1 Comparative Example 2 Actual/Flow Side 1 to 3 ■ In the preparation of coating composition (B), the polyfluoroalkylene group-containing bissilane compound as the (old) component was replaced with γ-glyside as the (b1) and (B2) components. Xyprobyltrimethoxysilane is combined with the above formulas (b1) and (b4) to form the following formula (b2):
, (b3) , [b5) , (b6) (Ctls
O) 5SiC*ll4(CFa) 5czl14Si
(OCIIs) s (b2) film was formed.

In this way, the characteristics of the low-reflection transparent molded bodies provided with the coating films made of the coating compositions (A) and (B) were evaluated in the same manner as in Examples 1 to 3.

The results are shown in Table 3.

Table 2 It was prepared in the same manner as in Examples 1 to 3 using the compound C11, Si (OCII3) - (b61) and using the solvent, acetic acid aqueous solution, catalyst, etc. in the amounts shown in Table 2.

Separately, a coating film of the coating composition (A) was formed on a CR-39 plate as a base material in the same manner as in Example 2, and then this was dipped in the above coating composition (Bl).
Coated in the same manner as in Example 2) diacetone alcohol* bottle) Aluminum acetylacetonate Table 3 Examples 12 to 17 Comparative Examples 3 to 6 ■ Preparation of high refractive index base material 2.2-Bis[4-(2 -allyloxycarbonyloxy)ethoxy-3-5-dibromophenyl]propane 7
To a mixed composition of 0 parts by weight, 30 parts by weight of diallyl isophthalate, and 5 parts by weight of benzyl allyl carbonate, 1.5 parts by weight of diisopropyl peroxydicarbonate as a radical polymerization initiator was added and mixed.

Next, this mixed solution was cast-polymerized using a gasket. Polymerization was started by increasing the temperature from 40°C to 90°C, and then maintained at 90°C for 2 hours.

After the polymerization was completed, the substrate was taken out and annealed at 110° C. for 2 hours.

In this way, a transparent base material with a refractive index of 1.585 was obtained.

■Preparation of coating composition (A) Same as Examples 1-3.

■ Preparation of coating composition +8) In place of γ-glycidoxyprobyltrimethoxysilane as component (B2) in Examples 1 to 3, the compounds and amounts shown in Table 4 were used, and in addition, 1% acetic acid aqueous solution or diacetone was used. Example 1~ except that the amount of alcohol was as shown in Table 7
It was prepared in the same manner as 3.

■Formation of coating film on the base material IOcmX lOcmX of the transparent base material obtained in the above (■)
A 2 mm plate was immersed in the coating composition (^) prepared in the proportions shown in Table 5 in the same manner as in Examples 1 to 3,
A cured coating film was formed by heat treatment, and then immersed in the coating composition (B) prepared in the above ①, followed by heat treatment to form a cured coating film.

In this way, the characteristics of the low-reflection transparent molded bodies provided with the coating films made of coating composition (A) and coating composition tB) were evaluated in the same manner as in Examples 1 to 3. The results are shown in Table 5.

Table 4 Table 5 \/ Examples 18 to 19 In the preparation of (A) for the coating composition in Example 2, the (at) compound of component (A1) was converted to the following formula (a2
), (a31 Table 6 (Weight average molecular weight 4.000) (Weight average molecular weight 35,000) Except for replacing it with a compound having a repeating unit represented by
A coating film of coating composition (A) was formed on a CR-39 plate as a base material in the same manner as in Example 2, and then a coating film of coating composition (B) was formed in the same manner as in Example 2. was formed.

In this way, the properties of the low-reflection transparent molded bodies provided with the coating films of coating composition (A) and coating composition (B) were evaluated in the same manner as in Examples 1 to 3. The results are shown in Table 6.

Examples 20 to 25 Comparative Examples 7 to 9 ■ In the preparation of the coating composition (A) in Example 2 (A2)
The components γ-glycidoxypropyltrimethoxysilane were replaced with the compounds and amounts shown in Table 7, and the 1% aqueous acetic acid solution was replaced with water and the amount of diacetone alcohol was shown in Table 7. A coating composition (A) was prepared in the same manner as in Example 2, and a coating composition (A) was prepared in the same manner as in Example 2.
A coating film of the coating composition (Al) was formed on the R-39 plate, and then a coating film of the coating composition (B) was formed thereon in the same manner as in Example 2.

In this way, the characteristics of the low-reflection transparent molded articles provided with the coating films of coating compositions (A) and (B) were evaluated in the same manner as in Examples I to 3. The results are shown in Table 8.

Table 7) Diacetone alcohol (old) of coating compositions (B) of Comparative Examples 7 to 9
The components were the same as in Example 2, except that 25 g of the compound of the following formula (b5) was used instead of the compound (b1) in Example 2.

CIl, ClCl1. DC,11,si (OCIIs
), +b5)\. / Examples 26-29 (A) of the coating composition (A) in Examples 1-3
Eight types of coating compositions (A) were prepared in which the mixing ratios of 11^-old (1) component and HA-02 (A2) were varied as shown in Table 9. A CR-39 plate as a base material is immersed in one of these, and pulled at a speed of 30
cm/min, then heat treated at 80°C for 30 minutes to form a first coating film, which was then immersed in another coating composition (A) at a pulling rate of 6 cm. After pulling up at a speed of 1/min, heat treatment was performed at 80° C. for 30 minutes to form a second coating film.

Furthermore, the CR-39 plate on which the coating film of coating composition (A) was formed was immersed in the coating composition (B) prepared in Examples 1 to 3 and pulled up at a pulling speed of 6 cm/min. A coating film was formed by heat treatment at 120° C. for 120 minutes.

In this way, the characteristics of four types of low-reflection transparent molded bodies provided with coatings consisting of two layers of the coating composition (Al 2 and coating composition (B)) were evaluated in the same manner as in Examples 1 to 3. The results are shown in Table IO.

Table 9 Table Examples 30-34 Coating compositions prepared in Examples 1-3 (A
IIA-01, which is the (^1) component of ), and IIA-01 (A2)
A CR-39 plate was immersed in a composition prepared by mixing component 11A-02 in the ratio shown in Table 11 or IIA-02 alone, and then in the coating composition (B) in the order shown in Table 11, and the heat treatment was repeated. A three-layer coating film was formed. The pulling speed associated with immersion at this time was 6 cm/min.
Further, the heat treatment was performed at 120°C for 60 minutes.

The characteristics of the low-reflection transparent molded product thus obtained are shown in Examples 1 to 1.
Evaluation was made in the same manner as in 3. The results are shown in Table 12.

Table 11 Table 12 [Effects of the Invention] The low-reflection transparent molded article of the present invention has an excellent effect of maintaining a balance between light reflection prevention performance and transmittance,
In addition, it has excellent adhesion and scratch resistance, and in particular, it has excellent properties that do not change at all even after a durability test.

Claims (3)

[Claims] (1) At least one layer of a coating film of the following component (A) or a coating composition consisting of the component (A1) and the component (A2) on the surface of a transparent plastic base material and the following (B1):
1. A low-reflection transparent molded article comprising at least one coating film of a coating composition comprising the component (B1) and the component (B2). (A1) At least one compound having a repeating unit represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼
seed. (However, in the formula, X^1 and X^2 each represent a halogen other than fluorine, a methyl group, an ethyl group, or a methoxy group, and may be the same or different, and a and b each represent an integer of 0 to 4. (A2) At least one organosilicon compound represented by the general formula R^1_cR^2_dSiY^1_4_-_c_-d or a partial hydrolyzate thereof. (However, in the formula, R^1 and R^2 each have 1 to 16 carbon atoms.
represents an organic group, which may be the same or different, Y^
1 is a hydrolyzable functional organic group, c and d are each 0
Indicates an integer of ~3 and satisfies 0≦c+d≦3. ) (B1) At least one type of fluorine-containing compound or its partial hydrolyzate represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼. (However, in the formula, R^3 and R^4 are hydrogen or carbon atoms 1 to 6.
represents an organic group, which may be the same or different,
3 represents a hydrolyzable group, Rf represents a perfluoro group-containing organic group, and e and f represent integers of 1 to 3. ) (B2) General formula R^5_iR^6_jS_iY^2_4_-_i_-_
At least one organosilicon compound represented by j or a partial hydrolyzate thereof. (However, in the formula, R^5 and R^6 each have 1 to 16 carbon atoms.
represents an organic group, which may be the same or different, Y^
2 is a hydrolyzable functional organic group, i and j are each 0
Indicates an integer of ~3 and satisfies 0≦i+j≦3. ) (2) At least one of the coating films of the coating composition consisting of the component (B1) or the component (B1) and the component (B2).
2. The low-reflection transparent molded article according to claim 1, wherein the layer is provided through a coating film of a coating composition comprising component (A1) or component (A1) and component (A2). (3) The coating film of the coating composition consisting of the component (B1) or the component (B1) and the component (B2) is the coating composition consisting of the component (A1) or the component (A1) and the component (A2). 2. The low-reflection transparent molded article according to claim 1, wherein the low-reflection transparent molded article is provided as the outermost layer with a coating film interposed therebetween.