JP3017595B2 - Anti-reflective article and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-reflective article and a method for manufacturing the same, and more particularly, to an anti-reflective article using thin film light interference and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, it has been proposed to reduce the reflection of light on the surface of a base material, improve the transmitted light, or protect the surface of an optical component such as glass or plastic by utilizing light interference of a thin film. The main purpose is to provide an anti-reflection coating on the surface of a substrate.

[0003] Many of these antireflection coatings are formed by vacuum evaporation or sputtering.
From the viewpoint of the mechanism of the apparatus and the cost, the articles to which these methods can be applied are limited to relatively small parts, and are not suitable for continuous production. On the other hand, a method of applying a solution or dispersion of an anti-reflection processing agent has also been proposed. However, this method generally requires a high temperature for drying or curing, increases the energy cost, and increases the plastic base material. In the case of (1), there was a disadvantage that thermal deformation was unavoidable.

As a light reflection preventing agent which can solve these disadvantages, a low refractive index polymer having a fluorinated aliphatic ring structure has recently been proposed (Japanese Patent Laid-Open No. 2-0).
19801), however, in this case, the adhesion to the lower layer is insufficient, so that the adhesion or abrasion resistance such as damage or delamination due to a cleaning operation for dirt or the like is obtained.
It is not satisfactory in solvent resistance and durability.

[0005]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies in order to solve the above-mentioned conventional disadvantages.
By providing a silicone-based primer layer comprising a special acrylic copolymer and a cross-linking agent under the low-refractive-index polymer thin film having a fluorinated aliphatic ring structure, it is possible to obtain extremely good results. Heading, the present invention has been reached.

Accordingly, a first object of the present invention is to provide a polymer film having a low refractive index having a fluorine-containing aliphatic ring structure, which has good adhesion, excellent abrasion resistance and solvent resistance, and has a long-term ( An object of the present invention is to provide a (light) antireflective article capable of maintaining (light) antireflective property. A second object of the present invention is to provide a method for producing an antireflection article, in which a low refractive index polymer thin film having a fluorinated aliphatic ring structure is firmly adhered.

[0007]

SUMMARY OF THE INVENTION The above objects of the present invention are attained in an antireflective article having a low refractive index layer comprising a thin film of a polymer having a fluorine-containing aliphatic ring structure. The lower layer has a cured film obtained by curing an acrylic copolymer obtained by polymerizing a polymerizable silane represented by Chemical Formula 8 described below and another radical polymerizable monomer together with a crosslinking agent described later. The present invention has been achieved by an anti-reflective article and a method for producing the same.

The polymer having a fluorinated aliphatic ring structure used in the present invention may be a polymer obtained by polymerizing a monomer having a fluorinated ring structure, or a polymer having at least two polymerizable double bonds. Polymers having a ring structure in the main chain, such as those obtained by cyclopolymerization of a fluorine monomer, are preferred.
In addition, from the viewpoint of transparency and mechanical properties, the
% Is preferable.

A polymer having a ring structure in the main chain obtained by polymerizing a monomer having a fluorinated ring structure is a fluorinated ring such as perfluoro (2,2-dimethyl-1,3-dioxole). It can be obtained by homopolymerizing a monomer having a structure or copolymerizing with a radical polymerizable monomer such as tetrafluoroethylene (JP-B-63-189).
64 etc.).

[0010] Further, such as obtained by cyclopolymerization of a fluorine-containing monomer having at least two polymerizable double bonds,
The polymer having a ring structure in the main chain is formed by cyclization polymerization of a monomer such as perfluoro (allyl vinyl ether) or perfluoro (butenyl vinyl ether) or copolymerization with a radical polymerizable monomer such as tetrafluoroethylene. (For example, JP-A-63-238111 and JP-A-63-238115).

Further, perfluoro (2,2-dimethyl-
A monomer having a fluorinated ring structure such as 1,3-dioxole) and a fluorinated monomer having at least two polymerizable double bonds such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether) It is also possible to use a polymer obtained by copolymerizing a polymer. In the case of a polymer having a fluorinated aliphatic ring structure produced using an organic peroxide-based polymerization initiator as described above, the terminal has a carbonyl group derived from the initiator at its terminal.

In the present invention, it is presumed that the carbonyl group thus produced gives a good result in adhesion to a primer (primer) described later. Therefore, in order to positively introduce a carbonyl group into the polymer, a small amount of CF ₂ ＣＦCFOCF ₂ CF ₂ CF ₂ —CO
A monomer such as OCH ₃ may be copolymerized. In the present invention, the thickness of the polymer thin film having a fluorinated aliphatic ring structure does not need to be particularly limited, and the thickness can be arbitrarily selected depending on the desired optical effect.

The acrylic copolymer used in the present invention is:
It is a copolymer obtained by polymerizing a polymerizable silane represented by the following formula 8 and another radical polymerizable monomer.

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Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an unsubstituted or substituted divalent hydrocarbon group such as a methylene group or trimethylene group, and R ³ is a methyl group, an ethyl group, a phenyl group, a vinyl group. An alkyl group having 1 to 8 carbon atoms such as a group, an alkenyl group, an aryl group, an aralkyl group, and R ⁴ represents an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, an alkenyl group, a ketoxime group, or an acyl group; 0 to
Indicates an integer of 2. Specific examples of R ⁴ include a methyl group, an ethyl group, an isopropyl group, an isopropenyl group, a vinyl group, a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group, a methylethylketoxime group, and an acetyl group.

As a specific example of Chemical formula 8, CH ₂ ＣＨCH—C
_{OOC 3 H 6 Si (OCH 3} ) 3, CH 2 = CH-CO
_{OC 3 H 6 Si (OC 2} H 5) 3, CH 2 = CH-CO
OC ₃ H ₆ Si (OC (CH ₃ ) H = CH ₂ ) ₃ , CH
_{2 = CH-COOC 3 H 6} Si (ON = C (CH 3)
_{(C 2 H 5)) 3} , CH 2 = CH-COOC 3 H 6 Si
_{(OC 2 H 4 OCH 3)} 3, CH 2 = C (CH 3) -C
OOC ₃ H ₆ Si (OCH ₃ ) ₃ , CH ₂ ＣC (C
_{H 3) -COOC 3 H 6 Si} (OC 2 H 5) 3, CH 2
ＣC (CH ₃ ) —COOC ₃ H ₆ Si (OC (CH ₃ )
_{H = CH 2) 3, CH} 2 = C (CH 3) -COOC 3 H
₆ Si (ON = C (CH ₃ ) (C ₂ H ₅ )) ₃ , CH ₂
ＣC (CH ₃ ) —COOC ₃ H ₆ Si (OC ₂ H ₄ OC
_{H 3) 3, CH 2 =} C (CH 3) -COOC 3 H 6 Si
_{(CH 3) (OCH 3)} 2, CH 2 = C (CH 3) -C
OOC ₃ H ₆ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CH ₂
ＣC (CH ₃ ) —COOC ₃ H ₆ Si (CH ₃ ) (OC
(CH ₃ ) H ＝ CH ₂ ) _{2 and the} like.

Examples of the radical polymerizable monomer copolymerizable with the polymerizable silane represented by Chemical formula 8 include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Functional group-containing (meth) acrylates such as alkyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and N-methylol acrylamide, acrylic acid, methacrylic acid,
Examples thereof include organic acids such as maleic anhydride and acetates such as vinyl acetate and allyl acetate. From the viewpoint of the hardness of the cured film described later, methyl methacrylate and ethyl (meth) acrylate are frequently used.

Further, glycidyl (meth) acrylate or 2-hydroxyethyl methacrylate may be copolymerized for the purpose of improving the adhesion to the plastic substrate. Radical polymerization initiators for copolymerizing the polymerizable silane represented by Formula 8 and the above polymerizable monomers are industrially widely used, such as azobisisobutyronitrile and benzoyl peroxide. It can be appropriately selected from those.

The obtained acrylic copolymer is preferably used by dissolving it in an organic solvent in consideration of coatability on a plastic substrate. Examples of the organic solvent used in this case include alcohols such as methanol, ethanol, isopropanol, butanol, diacetone alcohol, methyl cellosolve, ethyl cellosolve, and butyl cellosolve, aromatic compounds such as benzene, toluene, and xylene, ethyl acetate, and butyl acetate. Examples thereof include acetates such as isobutyl acetate, ketones such as methyl isobutyl ketone, cyclohexanone, and methyl ethyl ketone.
It is not preferable to use a solvent alone that can roughen the surface of a substrate such as plastic.

Particularly, from an industrial viewpoint, it is preferable to use ethyl cellosolve, isopropyl alcohol, or the like. As a cross-linking agent for the acrylic copolymer,
The compounds shown in Chemical formulas 2 and 17 are applied. These can be used in accordance with working conditions, such as a condensation reaction due to moisture in the air and a condensation reaction due to heating.

[0020]

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Wherein R ³ and R ⁴ in Chemical formulas 9 to 12 are the same as in Chemical formula 8, R ⁵ and R ⁶ are unsubstituted or substituted monovalent or divalent hydrocarbon groups, and b is 0 to It is an integer of 2.
Specific examples of R ⁵ and R ⁶ are hydrogen, methyl group ,, an ethyl group, butyl group, vinyl group, phenyl group, and groups represented by the following formula 13 Formula 17.

[0022]

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Embedded image R ³ _c Si (OR ⁴ ) _4-c

The reduction ^{R 3} and ^{R 4} in 17 are the same people husband and ^{R 3} and ^{R 4} in Chemical Formula 8, c is 1 or 2. Formula 17
Are CH ₃ Si (OCH ₃ ) ₃ and CH ₃
Si (OC ₂ H ₅ ) ₃ , CH ₃ Si (OC (CH ₃ ) H
= CH ₂ ) ₃ , CH ₃ Si (ON = C (CH ₃ ) (C _{2
H 5)) 3, CH 3} Si (O (OC) CH 3) 3, CH
₂ ＣＨCHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (OC
_{2 H 5) 3, CH 2} = CHSi (OC (CH 3) H = C
_{H 2) 3, CH 2 =} CHSi (ON = C (CH 3) (C
_{2 H 5)) 3, CH} 2 = CHSi (O (OC) CH 3)
₃ , C ₆ H ₅ Si (OC (CH ₃ ) H = CH ₂ ) ₃ , C
_{6 H 5 Si (ON = C} (CH 3) (C 2 H 5)) 3, C
_{6 H 5 Si (O (OC} ) CH 3) 3 and the like.

The cross-linking agent represented by Chemical formulas 9 to 12 and 17 reacts with the functional group-containing silyl group of the acrylic copolymer to form a cured film, and a base material and the cured film It also contributes to the adhesion to the fluorine-containing polymer to be overcoated. The amount of the crosslinking agent to be added is not particularly limited as long as the functional group of Chemical formula 8 is crosslinked.

In the present invention, a small amount of an organic titanate, an organic tin compound, an aminosilane coupling agent or the like may be added for the purpose of accelerating the curing of the acrylic copolymer and the crosslinking agent. Further, a fluorine-based leveling agent or a silicone-modified polyether-based leveling agent can be added for the purpose of improving the leveling property at the time of coating. For the purpose of improving the weather resistance, a benzophenone-based, benzotriazole-based, or cyanoacrylate-based ultraviolet absorber may be added in such an amount that the appearance is not impaired.

Further, in order to adjust the refractive index to a predetermined value, various organic materials, organic-inorganic compounds (or complexes) and the like can be added to the undercoating agent of the present invention. In the present invention, the coating thickness of the undercoating agent does not need to be particularly limited, and can be arbitrarily selected depending on the desired optical effect. If there is no need to have an optical effect on the primer, usually preferably set to less 50 n m, in particular 3
It is preferably not more than 0 n m.

The antireflective article of the present invention is obtained by applying the above-mentioned undercoating agent to the surface of a substrate, drying it, and optionally heating it as needed to cure the coating film. Applying a coating liquid containing a low refractive index polymer having a ring structure
It can be easily obtained by drying. The coating method in this case can be appropriately selected from known methods such as dipping and spraying.

The substrate used in the present invention is appropriately selected from known ones, and examples thereof include, for example, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polyethylene terephthalate, and polybutylene. Terephthalate, polystyrene, polyolefin and diethylene glycol bisallyl carbonate
And plastic materials such as a polymer (trade name: CR-39) and inorganic materials such as glass.

[0029]

As described in detail above, in the plastic optical article having the anti-reflection ability of the present invention, the adhesion between the base material and the cured film of the low refractive index fluoropolymer is extremely good. And the durability of the antireflection ability is extremely good. Further, in the manufacturing method of the present invention, since no vapor deposition or sputtering is required, the productivity is extremely excellent and the continuous production is easy.

[0030]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Synthesis Example 1 35 g of perfluoro ( butenyl vinyl ether ) , trichlorotrifluoroethane (hereinafter abbreviated as R113) 5
g, 150 g of ion-exchanged water , and 90 mg of ((CH ₃ ) ₂ CHOCOO) ₂ as a polymerization initiator in an inner volume of 20 g .
Put in a pressure-resistant glass autoclave of 0ml, the inside of the system 3
After purging with nitrogen twice, suspension polymerization was carried out at 40 ° C. for 22 hours to obtain 28 g of a polymer.

The intrinsic viscosity [η] of this polymer is 0.50 in perfluoro (2-butyl-tetrahydrofuran) at 30 ° C., the glass transition point is 108 ° C., and at room temperature, it is a tough and transparent glass. It is a polymer. Further, the 10% thermal decomposition temperature is 465 ° C. and visible light (wavelength 400 to 700).
nm) was as high as 95% or more. The above polymer was mixed with perfluoro (2
-Butyl-tetrahydrofuran) to prepare Topcoat Solution 1.

Synthesis Example 2 82 parts of methyl methacrylate, γ
-Methacryloxypropyltrimethoxysilane 25 parts,
A mixture of 7 parts of ethyl acrylate, 7 parts of vinyl acetate, 9 parts of glycidyl methacrylate and 1 part of benzoyl peroxide was added to a mixed solution of 500 parts of methyl isobutyl ketone, 400 parts of isopropyl alcohol and 400 parts of ethyl cellosolve, and 80 to 90 An acrylic copolymer (A) was synthesized by a polymerization reaction at 8 ° C. for 8 hours (nonvolatile content: 10%).

Next, to 100 parts by weight of the acrylic copolymer (A), 10 parts by weight of an ethanol solution (active ingredient 25%) of a mixture of the following chemical formulas 18 and 19 and 1,000 parts by weight of methyl isobutyl ketone were added. And primer solution 1
Was prepared.

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Further, CH ₂ ＣＨCHSi (OCH (CH ₃ ) ＝ CH ₂ ) _{3 was} added to 100 parts by weight of the acrylic polymer (A).
Primer solution 2 was prepared by adding 3 parts and 1,000 parts by weight of isobutyl acetate. Further, 100 parts of the above primer solution 2 was added to a polystyrene resin (Styrone G82).
59: trade name, refractive index: 1.5, manufactured by Asahi Kasei Corporation
The primer solution 3 was prepared by dissolving 4 parts of 9).

Embodiment 1 The primer solution 1 was applied to a plate of polycarbonate (abbreviated as PC: the same applies hereinafter) by a dipping method, air-dried for 10 minutes, and then the top coat solution 1 was applied by a dipping method to obtain a sample. 6 at 110 ° C
After a final cure of 0 minutes, the items in Table 1
Table 2 shows the results of the initial evaluation.
Table 3 shows the evaluation results after storage in a 5% environment for 500 hours.

Embodiment 2 FIG. Polymethyl methacrylate (P
A primer solution 2 was applied to a flat plate of MMA (hereinafter abbreviated to the same) by dipping, air-dried for 10 minutes, and then a topcoat solution 1 was applied by dipping to obtain a sample. 6
After performing a final cure at 5 ° C. for 120 minutes, the same evaluation as in Example 1 was performed.

Embodiment 3 FIG. A sample was obtained in exactly the same manner as in Example 2 except that the primer solution 3 was used in place of the primer solution 2 used in Example 2, and the same evaluation as in Example 1 was performed.

Comparative Example A top coat solution 1 was applied to a plate of PMMA without primer treatment, and cured at 65 ° C. for 120 minutes to obtain a sample. The same evaluation as in Example 1 was performed.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kou Aosaki 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside the Central Research Laboratory Asahi Glass Co., Ltd. (56) References JP-A-2-19801 (JP, A) JP-A-1-149878 (JP, A) JP-A-1-149879 (JP, A) (58) Fields surveyed ( Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C09J 5/00 G02B 1/10-1/12

Claims (3)

(57) [Claims] 1. An antireflection article having a low refractive index layer comprising a thin film of a polymer having a fluorinated aliphatic ring structure, wherein a polymerizable silane represented by the following formula 1 is provided below the low refractive index layer. And an acrylic copolymer obtained by polymerizing the polymer with another radical polymerizable monomer are represented by the following chemical formulas (2), (3), (4) and (5).
And selected from the group consisting of compounds represented by Formula 6
Antireflective article characterized by having a cured film was allowed to cure with at least one crosslinking agent; provided, R ¹ in-expression is a hydrogen atom or a methyl group, R ² is an unsubstituted or substituted divalent hydrocarbon R ³ represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an aryl group or an aralkyl group;
⁴ is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, an alkenyl group, a ketoxime group or an acyl group , R ⁵ and
And R ⁶ are a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon
And R ⁵ and R ⁶ together form a divalent hydrocarbon group
May be. a is an integer of 0 to 2 , b is an integer of 0 to 2, c is
Represents an integer of 1 or 2. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image R ³ _C Si (OR ⁴ ) _4-C 2. The method according to claim 1, wherein the acrylic copolymer and the crosslinking agent are moist
2. The anti-reflection device according to claim 1, wherein the resin is cured by heating.
Antistatic article. 3. The silicone plastic according to claim 1.
Fluorine-containing aliphatic ring structure
Coating and curing a low refractive index polymer
For producing an anti-reflective article .