JPH05341105A - Coating resin composite - Google Patents

Abstract

PURPOSE:To provide an optical glass coating composite having a high refractive index and excellent durability. CONSTITUTION:A coating resin composite contains (1) 20-40wt% of N-vinyl carbazole or its derivative (component A); (2) 35-79wt% of an aromatic compound (component B) containing one reactable functional group; and (3) 1-25wt% of a compound (component C) having at least two reactable functional groups, and has a refractive index of at least 1.58 after hardening.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating resin composition, and more particularly to a curable composition for coating the surface of an optical component such as optical glass. More specifically, the present invention relates to a coating resin composition having excellent refractive index matching properties and adhesiveness with an optical component and giving excellent moisture resistance and optical properties to an optical component to which this composition is adhered.

[0002]

2. Description of the Related Art As a method for repairing surface irregularities of optical parts,
There is known a method of filling a surface unevenness with a coating agent having a refractive index similar to that of an optical component.

As a coating composition for repairing surface irregularities of a high refractive index optical component, for example, glycerol-modified bisphenol A di (meth) acrylate and glycerol-modified fluorine-containing bisphenol A di (meth) acrylate are essential components. A coating composition is known, and the refractive index can be adjusted in the range of 1.45 to 1.59 by adjusting the composition ratio of the two. Further, at least one compound selected from the group consisting of N-vinylcarbazole and its substitution product, and N-vinylpyrrolidone and its substitution product, and acrylamide N substitution product are selected. A coating agent containing at least one compound and having a refractive index after curing of 1.60 or more is known (JP-A-3-15).
7471).

[0004]

Many optical glasses have the following problems.
Contains alkali metal ions such as sodium and potassium to suppress light scattering due to inhomogeneous glass. Under high humidity, alkali metal ions inside the glass are easily eluted on the glass surface using water as a medium. The elution of alkali metal ions adversely affects the adhesion of the glass / coating resin and deteriorates the optical performance. The conventional coating resin composition has a high refractive index and excellent initial performance, but has a problem in durability. An object of the present invention is to provide a coating composition for optical glass which has a high refractive index and is excellent in durability.

[0005]

The present inventors have completed the present invention as a result of earnest researches aimed at improving such problems of conventional resins.

That is, the present invention provides (1) 20 to 40% by weight of N-vinylcarbazole or its derivative (component A), and (2) an aromatic compound (component B) having one reactive functional group. 35 to 79% by weight, and (3) 1 compound (C component) having at least two reactive functional groups
The coating resin composition is characterized in that each of the coating resin composition contains 25 to 25% by weight and the refractive index after curing is at least 1.58.

The present invention will be described in detail below.

The component A used in the present invention is N-
Examples thereof include vinylcarbazole, 3-nitro-N-vinylcarbazole, 3-amino-N-vinylcarbazole, 3-methylamino-N-vinylcarbazole, and 3,6-dibromo-N-vinylcarbazole. N-vinylcarbazole has a refractive index of 1.69, and this derivative has a refractive index of 1.66 to 1.68, which has a refractive index close to that of the glass of the optical component to be coated. It is a solid component for making it. The component A is a component for increasing the refractive index, and its content is 20 to 40% by weight, and if it is less than 20% by weight, the refractive index of the coating resin composition becomes 1.58 or more necessary for repairing the surface irregularities of the optical glass. It is difficult to raise the amount, and conversely, when it exceeds 40% by weight, it becomes insoluble in the solvent described later, which is not preferable.

The component B used in the present invention is an aromatic compound having one functional group capable of undergoing polymerization reaction such as an acryloyl group, a methacryloyl group, a vinyl group or an allyl group in the molecule, excluding the component A. It is an ingredient. For example, phenylcarbitol acrylate, nonylphenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acryloyloxyethyl phthalate, phenyl acrylate, phenoxyethyl acrylate, tribromophenoxyethyl acrylate, benzyl acrylate, p-bromobenzyl acrylate, etc. Acrylates; and methacrylates corresponding to these acrylates; vinyl compounds such as styrene, p-chlorostyrene and vinylnaphthalene; allyl compounds such as allyl benzoate. Of these, those having a hydroxy group are preferred because they enhance adhesion.

Component B is a solvent component that dissolves component A, which is a solid component, and has a relatively high refractive index when polymerized alone, for example, a refractive index of 1.53 to 1.59. Further, the B component reduces undesired residual stress generated in the coating film by the C component described later. It is easy for the copolymer of the component A and the component B to obtain a refractive index of at least 1.58, and even 1.60 or more. For example, with respect to 1 part by weight of phenoxyethyl acrylate, N
When 0.7 parts by weight or more of vinylcarbazole is dissolved at room temperature, the refractive index of the copolymer reaches 1.63 or more.

The content of the component B is 35 to 79% by weight, and if it is less than 35% by weight, the residual stress generated in the coating film by the component C cannot be reduced and it is not sufficient to dissolve the component A. On the other hand, if it exceeds 79% by weight, the coating film is likely to be attacked by the solvent and the chemical resistance is lowered, and the amounts of the A component and the C component are relatively small so that the refractive index cannot be increased. In addition, alkali is eluted from the glass surface of the optical component, which is not preferable.

The C component used in the present invention is a component that forms a crosslinked structure inside the coating film to improve the heat resistance of the coating film and to prevent the elution of alkali from the glass surface of the optical component. The content of the C component is 1 to 25% by weight. If it is less than 1% by weight, the heat resistance, chemical resistance and alkaline component elution prevention performance of the coating are insufficient, and if it exceeds 25% by weight, it is accompanied by curing shrinkage. The residual stress in the coating film becomes large, peeling of the coating film easily occurs, and the deterioration of optical characteristics becomes large, which is not preferable.

The component C used in the present invention contains two or more polymerizable groups such as an acryloyl group, a methacryloyl group, a vinyl group and an allyl group in the molecule. For example,
2,2'-bis (4-acryloxyethoxyphenyl) propane, 2,2'-bis (4-acryloxyethoxyphenyl) propane, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, 2 , 2'-bis (4-acryloxy-3,5-dibromophenyl) propane, 2,
2'-bis (4-acryloxyethoxy-3,5-dibromophenyl) propane, 2,2'-bis (4-acryloxyphenyl) sulfone, 2,2'-bis (4-acryloxyethoxyphenyl) sulfone , 2,2'-bis (4-acryloxyethoxy-3,5-dibromophenyl) sulfone, bis (4-acryloxyphenyl) sulfide, bis (4-acryloxyphenyl) sulfide, bis (4
-Acryloxyethoxy-3,5-dibromophenyl)
Aromatic acrylates having two or more acryloyl groups such as sulfides and methacrylates corresponding to these acrylates; ethylene glycol diacrylate, tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1 Acrylate as an aliphatic alcohol derivative having two or more acryloyl groups such as 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate and trimethylolpropane triacrylate, and these acrylates Methacrylates; vinyl compounds such as divinylbenzene;
Aromatic allyl compounds having two or more allyl groups such as diallyl terephthalate, diallyl isophthalate, triallyl trimellitic acid, tetraallyl pyromellitic acid and diallyl diphenate; allyl groups such as diethylene glycol bisallyl carbonate Examples thereof include an aliphatic allyl compound having two or more.

In order to further enhance the adhesive strength or the solubility of the B component, a polymerizable compound having a hydro group, such as 2-hydroxyethyl, in addition to the above A, B and C components. Acrylate, N-vinylpyrrolidone and the like may be added in an amount of 1 to 30% by weight based on the total of A, B and C components.

The method for polymerizing the resin composition of the present invention is not particularly limited, and known polymerization methods can be adopted. A polymerization initiator may be added to the coating agent of the present invention, and the coating agent may be cured by irradiation with ultraviolet rays or heating.

When the coating film of the resin composition of the present invention is cured by ultraviolet rays or other light, benzophenone, benzyl, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoin ethyl ether, etc. are used as the initiator. Examples thereof include, but are not limited to, diethoxyacetophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone. The initiator is usually 0.0 with respect to the resin composition.
Add 1 to 5% by weight.

Examples of the polymerization initiator used for heat curing include 2,2'-azobis (2-cyclopropylpropionitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). , 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4,4-trimethylpentane), dimethyl 2,2'-azobis (2-methylpropionate) Azo compounds such as or peroxy compounds such as t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxy (2-ethylhexanoate), t-butylperoxyisopropyl carbonate Esters, peroxydicarbonates such as diisopropyl peroxydicarbonate, benzoyl peroxide, diacyl peroxides such as 3,3,5-triethylhexanoyl peroxide , Dialkyl peroxides such as dicumyl peroxide, hydroperoxides such as t-butyl hydroperoxide, peroxyketals such as 1,1, -bis (t-butylperoxy) cyclohexane, cyclohexanone peroxide, And the like, and other peroxides.

The amount of the polymerization initiator is usually 0.001 to 10% by weight, preferably 0.1% by weight based on the coating composition.
It is from 01 to 5% by weight.

As a method for smoothing the surface of the coated film, a coating agent is applied to the optical glass surface by a dipping method, a spray method, a brush coating method or the like, and then a film of polyester or the like is applied if necessary. A mirror surface can be easily obtained by placing it on top.

The surface roughness of the optical glass to be coated with the coating resin composition of the present invention has an average surface roughness of 0.1 to 0.1.
It preferably has a rough surface of 10 μm.

When an optical glass is coated with the coating resin composition of the present invention, the adhesion can be improved by treating the glass surface to be coated with a silane coupling agent in advance. Further, the adhesiveness can be improved by adding a silane coupling agent to the coating composition instead of treating the glass surface. The amount of silane coupling agent added is
It is 0.1 to 10% by weight with respect to the coating composition.
As the silane coupling agent, one having an organic functional group such as an acryloyl group, a methacryloyl group, an amino group, a vinyl group is suitable.

[0022]

Adhesive surface is rough optical glass Cote _Lee packaging resin composition of the present invention according to the present invention shows excellent optical properties, a moisture resistance.

[0023]

EXAMPLES Examples of the present invention will now be described, but the present invention is not limited to these. The test method for each property was as follows.

The refractive index was measured by an Abbe refractometer.

The optical performance was measured by MTF. MTF
The value is a CCD image sensor receiving an image of a rectangular wave grating pattern using a gradient index glass lens array as a sample,
The response function MTF is calculated from the light amount level by the following equation.

MTF (W) = 100 × [i (W) max−i (W) min] / [i (W) max + i (W) min] where i (W) max and i (W) min are Spatial frequency W (lp / m
It is the maximum value and the minimum value of the rectangular wave response in m). MT
The F value is a value at a spatial frequency of 4 lp / mm. The higher the MTF value, the better the resolving power of the lens.

The humidity resistance test was carried out at 60 ° C. and 90% RH for a gradient index glass lens array coated with the resin composition of the present invention.
The sample was kept for 1000 hours under the conditions described above, and the moisture resistance was evaluated by comparing the initial MTF value with the MTF value after the test.

Example 1 The following compounds were prepared to give a composition 1. Composition 1 has no precipitation of vinylcarbazole even after 1 month at 25 ° C. after preparation, indicating that it can be stored for a long time.

Composition 1 N-vinylcarbazole (A component) 25 parts by weight 2-hydroxy-3-phenoxypropyl acrylate (B component) 48 parts by weight 2-hydroxyethyl acrylate 3 parts by weight 2,2′-bis (4- Acryloxyethoxy phenyl) propane (C component) 24 parts by weight As a photoinitiator 2-hydroxy-2-methylpropiophenone 3 parts by weight As a silane coupling agent 3-methacryloxypropyltrimethoxysilane 3 parts by weight Average surface unevenness 3 μm With a rough surface of 1.61-1.64
Gradient index type glass lens array with self-refractive index "SELFOC lens array" (trade name, Nippon Sheet Glass Co., Ltd.)
Composition 1 was applied on the surface of the product (1) to a film thickness of about 20 μm, and then a polyester film was placed thereon and irradiated with ultraviolet light to be sufficiently cured. After curing, the polyester film was removed. The refractive index of the coating after curing was 1.583.

A humidity resistance test was conducted on the gradient index glass lens array thus produced. As a result, as shown in Table 1, both the initial MTF value and the moisture resistance (retention rate of [post-test MTF value / initial MTF value] in percentage) were excellent.

Example 2 The following compounds were prepared to give a composition 2. Composition 2 is 2
No vinylcarbazole was deposited at 5 ° C. for 1 month.

Composition 2 N-vinylcarbazole 30 parts by weight 2-hydroxy-3-phenoxypropyl acrylate 25 parts by weight phenoxyethyl acrylate 40 parts by weight 2,2′-bis (4-acryloxyethoxyphenyl) propane 5 parts by weight light 2-Hydroxy-2-methylpropiophenone 3 parts by weight as an initiator 3-methacryloxypropyltrimethoxysilane 3 parts by weight as a silane coupling agent The composition 2 was applied and cured in the same manner as in Example 1, and a moisture resistance test was conducted. Carried out. The results are shown in Table 1.

[Table 1] Table 1 ------------------ Example 1 Example 2 ---------- −−−−−−−−−−−−−−−−− Refractive index after curing 1.590 1.605 Initial MTF value 78.9 81.8 MTF value after test 76.9 79.2 Retention rate (%) 97.5 96.9 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Composition 3 is 2
No vinylcarbazole was deposited at 5 ° C. for 1 month.

Composition 3 N-vinylcarbazole 35 parts by weight 2-hydroxy-3-phenoxypropyl acrylate 40 parts by weight N-vinylpyrrolidone 20 parts by weight 2,2′-bis (4-acryloxyethoxyphenyl) propane 5 parts by weight 2-Hydroxy-2-methylpropiophenone 3 parts by weight as photoinitiator 3-methacryloxypropyltrimethoxysilane 3 parts by weight as silane coupling agent Composition 3 was applied and cured in the same manner as in Example 1, and a moisture resistance test was performed. Was carried out. The results are shown in Table 2.

Example 4 The following compound was prepared to give a composition 4. Composition 4 is 2
No vinylcarbazole was deposited at 5 ° C. for 1 month.

Composition 4 N-vinylcarbazole 27 parts by weight 2-hydroxy-3-phenoxypropyl acrylate 36 parts by weight Phenoxyethyl acrylate 27 parts by weight Nonaethylene glycol diacrylate 10 parts by weight 2-hydroxy-2-methyl as photoinitiator Propiophenone 3 parts by weight 3-methacryloxypropyltrimethoxysilane 3 parts by weight as a silane coupling agent Composition 4 was applied and cured in the same manner as in Example 1 and a moisture resistance test was carried out. The results are shown in Table 2.

[Table 2] Table 2 ------------- Example 3 Example 4 Example 4 ---------- −−−−−−−−−−−−−−−−− Refractive index after curing 1.603 1.588 Initial MTF value 82.0 80.0 MTF value after test 74.5 78.2 Retention rate (%) 97.9 97.8 −−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 The following compound was prepared to give a composition 3.

Composition 5 N-vinylcarbazole 30 parts by weight phenoxyethyl acrylate 21 parts by weight 2-hydroxyethyl acrylate 7 parts by weight 2,2′-bis (4-acryloxyethoxyphenyl) propane 42 parts by weight Photoinitiator 2- Hydroxy-2-methylpropiophenone 3 parts by weight Silane coupling agent 3-methacryloxypropyltrimethoxysilane 3 parts by weight Composition 5 was cured in the same manner as in Example 1 and a moisture resistance test was conducted. The results are shown in Table 3.

Comparative Example 2 The following compound was prepared to obtain a composition 6.

Composition 6 Bisphenol A glycerol modified diacrylate 100 parts Photoinitiator 2-hydroxy-2-methylpropiophenone 3 parts by weight Composition 6 was cured in the same manner as in Example 1 and a moisture resistance test was carried out. The results are shown in Table 3.

Comparative Example 3 Composition 7 was prepared by mixing the following compounds.

Composition 7 N-vinylcarbazole 40 parts by weight N-vinylpyrrolidone 20 parts by weight Phenoxyethyl acrylate 40 parts by weight As a photoinitiator 2-hydroxy-2-methylpropiophenone 3 parts by weight As a silane coupling agent 3- Methacryloxypropyltrimethoxysilane 3 parts by weight Composition 7 was cured in the same manner as in Example 1 and subjected to a moisture resistance test. The results are shown in Table 3.

Table 3 Table 3 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 Comparative Example 2 Comparative Example 3 ----- −−−−−−−−−−−−−−−−−−−−−−−−−−− Refractive index after curing 1.603 1.580 1.615 Initial MTF value 75.7 77.0 79 .2 MTF value after the test 28.0 Film peeling 52.7 Retention rate (%) 37.0 0 66.6 ----------------------------------- −−−−−−−

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Takigawa 3-5-11 Doshumachi, Chuo-ku, Osaka City Japan Sheet Glass Co., Ltd. (72) Manabu Takami 3-5-11 Doshumachi, Chuo-ku, Osaka Inside Nippon Sheet Glass Co., Ltd. (72) Inventor Hiroyuki Nakazaki 3-5-11 Doshomachi, Chuo-ku, Osaka City Inside Nippon Sheet Glass Co., Ltd.

Claims (1)

[Claims] (1) 20 to 40% by weight of N-vinylcarbazole or its derivative (component A), and (2) 35 aromatic compounds (component B) having one reactive functional group.
To 79% by weight, and (3) 1 to 25% by weight of a compound (component C) having at least two reactive functional groups, respectively, and having a refractive index after curing of at least 1.58. And a coating resin composition.