JPS6034084B2 - striped filter - Google Patents

Description

[Detailed description of the invention] The present invention relates to a stripe filter.

Stripe filters used in color television cameras, etc. are made by layering a thin film (hereinafter referred to as gelatin layer) of a water-soluble resin such as gelatin, gris, casein, or PVA on the surface of an optically transparent substrate such as glass. It is generally formed into a shape.

However, although these water-removable resin films have excellent adhesion and dyeability, they have a problem that they are somewhat insufficient in hardness and are easily affected by water and humidity, so some kind of protective coating ( It was common to apply an overcoat. The present invention consists of a thin film formed of a material that does not need to be coated with such an overcoat,
Therefore, the object is to provide a striped filter without an overcoat. In other words, we have simplified the manufacturing process for striped filters, and at the same time, we have created striped filters that are essentially hard, free from scratches and scratches, and have excellent water resistance, oil resistance, and chemical resistance. The purpose is to provide. That is, the present invention provides an organosilicon compound represented by the general formula RaIRb2Si(OR3)4-(a+b) and/or its hydrolyzate (hereinafter referred to as component A) and a curing catalyst (hereinafter referred to as component B).
The present invention relates to a striped filter characterized in that a coating obtained from a coating composition consisting of the following is used as a colored layer.

"Here, RI is an organic group containing an epoxy group. R2 is an organic group consisting of an alkyl group, a halogenated alkyl group, or an allyl group, each of which has a carbon-silicon bond of S
The group R3 bonded to j is an alkyl group having 4 or less carbon atoms,
Alkoxyalkyl group or acyl group a is 1 or 2,
b is 0 or 1 and a+b is 1 or 2.

Examples of the compound A component used in the present invention include y-glycidoxypropyltrimethoxysilane and y-glycidoxyf.

Lopyltriethoxysilane, y-glycidoxyethoxypropyltrimethoxysilane, y-glycidoxypropyltri8(-ethoxy)ethoxysilane, y-glycidoxypropyltriacetoxysilane, y-glycidoxypropylmethyldimethoxysilane , y-glycidoxypropylmethyldiethoxysilane, 8-(3,4-epoxycyclohexyl)ethyltrimentoxysilane, 8-
(3,4-epoxycyclohexyl)ethyltriethoxysilane or a hydrolyzate thereof. The hydrolyzate referred to here refers to, for example, those obtained by hydrolyzing the above-mentioned compounds with water or an acidic aqueous solution such as hydrochloric acid, sulfuric acid, or organic acid, and includes those containing silanol resulting from hydrolysis, as well as partial condensates thereof. (oligomers, etc.) can also be included in this. The hydrolysis of the compound can also be carried out without using a solvent, using only the alcohol or carboxylic acid produced during the reaction of the compound with water. It is also possible to add or replace other solvents. In order to hydrolyze two or more of the above compounds, it is possible to hydrolyze each compound separately and then mix them, but there is also a method of co-hydrolyzing the mixed compounds, or a method of hydrolyzing one compound and then adding the other compound. In addition to this, a sequential hydrolysis method in which hydrolysis is continued can also be applied.

The above compound is used as it is, but whether it is used after hydrolysis depends on the required curing conditions and the stability of the coating material.

When the above-mentioned compound is used without being hydrolyzed, the temperature required for curing becomes high, but the stability of the coating material is high. The coating layer of the present invention is formed by adding a curing catalyst to these compounds and/or their hydrolysis, applying the mixture onto a substrate, and heating and curing it.

The curing catalyst used here, that is, component B, is an organic acid known as a curing agent for ordinary epoxy resins or anhydrides thereof, various amines, nitrogen compounds such as amides, and metal complexes (for example, Resins'', McGraw-Hill, 19
For the purposes of the present invention, aluminum alkoxides and/or aluminum chelate compounds represented by the general formula N.Xn.Y3-n are particularly preferably used. "Here, x is a lower alkoxy group having 4 or less carbon atoms, Y is M, COCH2
Ligands (M,,M2,M3) originating from compounds selected from the group consisting of COM2 and M3COCH2COOM4
and M4 is a lower alkyl group having 4 or less carbon atoms), n is 0
, 1, 2 or 3.

Specific examples of these include aluminum tri-i-propoxide, aluminum -n-propoxide, aluminum -n-butoxide, and aluminum di-propoxide.

Ropoxide monomethyl acetoacetate, aluminum di-n-butoxide ethyl acetoacetate, aluminum mono-p. Examples include oxide diacetylacetonate, aluminum acetylacetonate, aluminum methyl acetate bis acetylacetonate, aluminum ethyl acetoacetate bis acetylacetonate, aluminum bismethyl acetoacetate acetylacetonate, aluminum pis ethyl acetoacetate acetylacetonate, and the like. Regarding the coating composition for forming the coating layer, an organosilicon compound (component A) and a curing catalyst (component B) are essential components, but it is also necessary to improve various physical properties such as improved hardness, improved dyeability, and moisture resistance. Various formulations can be used for. Among these formulations, the following three components are particularly preferred. [a- Epoxy resin or polyfunctional epoxy compound.

{b} A compound represented by the general formula R (OR6)4-(c1d) or a hydrolyzate thereof.

"Here, R4 and R5 are C, to C, o alkyl, aryl, halogenated alkyl, halogenated aryl, alkenyl, or a compound having a (meth)acryloxy group, ami/group, mercapto group, or cyano group. is bonded to Si with a carbon-silicon bond, and R
6 is a C, -C6 alkyl group, alkoxyalkyl group or acyl group, c and d are 0, 1 or 2, and c and d are 1 or 2.

{c- Silica fine particles with a particle size of 10m
Epoxy resins or polyfunctional epoxy compounds are widely used as coating materials and molding materials.

These compounds are preferably polyglycidyl ether or polyglycidyl ester. Porglycidyl ethers are reaction products of polyfunctional phenols and epichlorohydrin, and reaction products of aliphatic or alicyclic polyhydric alcohols and epichlorohydrin, with a molecular weight of 1,000.
0 or less is preferable, and examples of polyfunctional phenols used for this include 2,2-di(p-hydroxyphenyl)propane (bisphenol A), di(p-hydroxyphenyl)methane (pisphenol F) ), and other polyhydric phenols such as ethylene oxide and propylene oxide are also included in this category. The aliphatic or alicyclic polyhydric alcohol used therein is preferably an alcohol having 40 or less carbon atoms.

These alcohols include (poly)ethylene glycol, (poly)propylene glycol, neobentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, sorbitol, 1,4-dihydroxymethylcyclohexane, and hydrogenated bisphenol A. , glycerol, and polyhydric alcohols (excluding (poly)ethylene glycol and (poly)propylene glycol) modified with ethylene oxide or propylene oxide. As polyglycidyl esters, reaction products of aliphatic, cycloaliphatic and aromatic polybasic acids having 8 or less carbon atoms and epichlorohydrin are preferable, and as polybasic acids used in these reactions, Examples include succinic acid, glutaric acid, adipic acid, hexahydroterephthalic acid, phthalic acid, isophthalic acid, and terephthalic acid.

Examples of compounds {b} include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and vinyltrimethoxysilane. , vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, phenyltriacetoxysilane, y-chloropropyltrimethoxysilane, y-chlorobro Pyrtriethoxysilane, y-chloropropyltriacetoxysilane, 3.3.3-trifluoropropyltrimethoxysilane, y-methacryloxypropyltrimethoxysilane, y-aminof.

Lopyltriethoxysilane, y-mercaptopropylmethoxysilane, y-mercuff. Tolylalkoxy or triacyloxysilanes such as topropyltriethoxysilane, N-8(aminoethyl)-y-aminopropyltrimethoxysilane, 8-cyanoethyltriethoxysilane, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldimethoxysilane Ethoxysilane, phenylmethyldiethoxysilane, y-chloropropylmethyldimethoxysilane, dimethylacetoxysilane, y-
methacryloxypropylmethyldiethoxysilane, y
-Mercaptopropylmethyldimethoxysilane, y-mercuff. Toph. Lopylmethyldiethoxysilane, y-aminof. Examples include dialkoxysilanes or diacyloxysilanes such as lopyldimethoxysilane, y-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane.
An effective example of the above {c} is silica sol.

Silica sols are colloidal dispersions of high molecular weight silicic anhydride in organic solvents such as water and/or alcoholic solvents. For purposes of this invention, diameters of about 5 to 3 meters are particularly preferred. Furthermore, silica fine particles treated or coated with various organic substances for the purpose of improving dispersibility can also be included.

If the particle size is larger than the value described here (1 to 100 nm), the transparency of the thin film may decrease, cracks may occur, etc.

It is of course possible to use each of the above components alone or in combination of two or more. The amount of these components a and B used is 10% of the organosilicon compound A in the coating composition.
It can be used in amounts up to 100 parts by weight relative to 0 parts by weight.

Component C can be used in an amount of up to 20 parts by weight per 10 parts by weight of organosilicon compound A in the coating composition, but in order to achieve the desired effect, preferably 1 part by weight is used.
It is used in a range of 180 parts by weight.

The curing catalyst B component in the coating composition is 0.1 to 2 parts by weight, preferably 0. .5 to 1 part by weight is used.

If the amount is too small, curing will be insufficient, and if it is too large, there will be a decrease in dyeability and durability. In order to apply the coating composition of the present invention, water and/or various organic solvents can be used to adjust the concentration, viscosity, etc. to desired values.

Furthermore, it is possible to add various additives or various resins that can be mixed without substantially losing transparency.

For example, various surfactants are effective for controlling the fluidity of the coating film at the coating stage, increasing the surface smoothness, and reducing the coefficient of friction of the surface. Furthermore, ultraviolet absorbers, anti-foam absorbers, anti-foaming agents, viscosity modifiers, etc. can be used as needed.
Examples of resins that can be mixed include copolymers of acrylic acid or methacrylic acid esters containing hydroxyl groups and/or carboxylic acids, cellulose derivatives such as hydroxyethyl cellulose, alcohol-soluble cellulose butyrate, and alkyl melamine or urea. Examples include so-called amino resins which are methylol derivatives. The procedure for manufacturing the striped filter of the present invention is, for example, as follows: [1] The coating composition is applied to a substrate, and a coating layer is formed by drying and curing.

At this time, before applying the coating composition to a substrate such as glass, the surface of the substrate may be physically or chemically treated or coated to improve adhesion. Preferred examples of these include alkali treatment, plasma etching, use of a silane coupling agent, and use of thermoplastic or thermosetting acrylic copolymer resin. In addition, after applying the coating composition, the temperature at which it is heated and cured is 50~
300 pm o Preferably 60 to 250°C is used. If the temperature is lower than this, curing will be insufficient, and if the temperature is higher than this, problems such as cracks and decomposition of the film will occur. In applying each coating composition, conventionally known coating methods can be applied.

For example, bond painting, spin painting, roll painting, curtain flow painting, spray painting, etc. can be applied. The amount of the coating composition applied to the substrate depends on, for example, the required performance and usage conditions, and cannot be uniformly determined.In order to obtain a coating with good durable adhesion and beamability or a good balance of physical properties, the coating composition must be Preferably, the coating is applied to a thickness of about 0.5 to 2 cm.

The substrate used in the present invention is an optically transparent material such as glass, quartz, or film, or in some cases, a semiconductor such as a solid-state image sensor.

(2) Next, a beam barrier layer made of, for example, photoresist is formed on the surface of the coating layer in a predetermined pattern, and the coating layer not covered by the beam barrier layer is dyed into a fine cotton-like or mosaic pattern.

In dyeing the coating layer, cationic dyes, anionic dyes, acid dyes, basic dyes and disperse dyes can be used, but disperse dyes give particularly preferable results.

Rigidity Next, the beam-proofing layer is removed, and a new beam-proofing layer is created as an intermediate layer.

(4) A striped filter is manufactured by repeating the steps m~[3} or m~{2) on this intermediate layer.

As described above, the stripe filter of the present invention has the greatest feature in the dyed coating layer.

That is, since the coating layer has both the advantages of an epoxy resin and a silicone resin, there is no need for a conventional overcoat. All the objectives of the invention are thereby advantageously achieved. Furthermore, in order to prevent peeling between the intermediate layer and the like and the coating layer, it is also possible to use a method of, for example, slightly roughening the surface of the coating layer.
For example, when the coating layer is exposed to a high-frequency electric field under reduced pressure, oxygen and fluorine radials are applied to the coating layer, resulting in the formation of minute irregularities on the surface.

Hereinafter, the present invention will be explained in more detail with reference to Examples and drawings.

Note that FIGS. 1 to 8 are sectional views showing the stripe filter of the present invention, and FIGS. 9 to 10 are plan views thereof. These are all conceptual diagrams. Example 1 ○ - Preparation of paint In a reactor equipped with a takazusa machine, 100 glycidoxypropylmethyljethoxysilane and methanol silica sol (average particle size of silica: 130 lnm) with a solid content concentration of 30% were added.
333 portions were mixed, and further 5 portions of acetylacetone were added to dissolve the Takaazusa at room temperature.

Add about 1/2 volume of zeolite to this mixture and
I was dehydrated during the night. The moisture content of each coating liquid after dehydration was measured using a near-infrared method, and as a result, it was all 0.4% or less. This composition was applied by a spinner method onto a glass substrate 1 that had been pretreated with a silane coupling agent. 160q after drying
o for 45 minutes to obtain a first layer 2 having a thickness of about 2 mm.
FIG. 2 shows a stage in which a photoresist 3 such as OMR83 (manufactured by Tokyo Ohka Products) is applied and dried on the surface of the first layer 2. As shown in FIG.

Next, ultraviolet rays (arrows) are irradiated as shown in Figure 3 through a mask 5 in which transparent parts 4 and light shielding parts with a width of about 20 m are perforated alternately in parallel, and only the parts exposed to the ultraviolet rays are cured. I let it happen. The lower hardened portion is dissolved away with OMR83 developer and the beam barrier layer 3A is formed on the surface of the first layer 2 in a predetermined pattern.
As shown in the figure. This was followed by a red disperse dye (0.5% of Nippon Kayaku's Karon Polyester Light Red BLSE).
Aqueous solution) was used to carry out immersion dyeing at 90 qo for 20 minutes to form red bands R in the portions of the first layer where there was no resist dyeing layer 3A.

The beam barrier layer 3A was removed using an organic solvent having a swelling effect, such as Torquelene (FIG. 5). Furthermore, the above-mentioned photoresist is applied to this surface, and the entire surface is cured with ultraviolet rays.
An intermediate layer 6 that does not transmit the disperse dye was formed.

This stage is shown in FIG. The above operation is repeated once again, and the disperse dye (Mitsui Toatsu Chemical Co., Ltd.
The second layer 8 with green stripes G was formed using a 0.5% aqueous solution containing 2 parts of Miketon Polyester Fluor MQ and 3 parts of Daito Chemical's TD Yellow DGLFcon. Figure).

Furthermore, the same operation was performed on the surface, and a third layer 9 having blue stripes B was formed using a disperse dye (0.5% aqueous solution of Miketon Polyester Blue MQ) between both strips R and G. , the state in which the stripe filter manufacturing is completed is 8th to 9th.
It is a diagram.

Example 2 FIG. 10 shows an example of a cross-type stripe filter consisting of a second layer, in which the same material as in the previous example was used except for the disperse dye, and a cyan band C and a yellow band Y were formed.

A 0.5% aqueous solution of Sumikalon Turquis Blue S-GL (manufactured by Sumitomo Chemical ■), a disperse dye for C (cyan).

Disperse dye for Y (yellow) Sumikalon Yellow SE-Sen L (manufactured by Sumitomo Chemical ■) 0.
5% Aqueous Solution Example 3 The same operations as in Example 1 were carried out, except that glass was treated with a silane coupling agent, then the following thermosetting acrylic paint was applied, and then cured for 16,000 to 20 minutes. I created a stripe filter.

This product had good adhesion under humid conditions. The thermosetting acrylic paint used here is a solution with a solid content of 25% made with the following formulation.

140 Weight part ■ CYM old L-3
03 (Melamine resin manufactured by American Cyanamid)
30 parts by weight'3} Epicort 1001
(epoxy resin manufactured by Shell Chemical) solution (solid content 50%)
) 20 parts by weight '41 Ethyl cellosolve 250 parts by weight Example 4y-glycidoxif.

While stirring 248 minutes of pyrmethyldiethoxysilane at 100 degrees, 36 hours of an aqueous solution of 0.0% hydrochloric acid was added dropwise. This was added to 30% solids methanol silica sol (average particle size 13
±lnm) After 580 minutes, add 8.7 hours of aluminum acetylacetonate and dissolve. A striped filter was obtained by performing the same operation as in Example 1.

The curing conditions for this composition were 9:0 and 2 hours. Example 5 y-glycidoxypropylmethyldiethoxysilane 19
On the evening of 7.3, epoxy resin (Denacol EX-931 Nagase Sangyo ■Polypropylene glycol diglycidyl ether) 34.8 evening, 30% solid content methanol silica sol (average particle size 13 ± lnm) 709.22 was mixed with this. Add and dissolve 19.3 tons of aluminum acetylacetonate.

Furthermore, 38.7 parts of acetylacetone and 0.6 parts of polyanhydrous sodium acetate are added to obtain a mixed solution. Example 3 using this
A striped filter was obtained by performing the same operation as above.
In the stripe filter obtained as described above, not only the stripes of each color exhibit predetermined spectral characteristics, but also the outermost layer a exposed on the surface has both the properties of silicone resin and epoxy resin.

Therefore, its hardness reached 4 days on the Empi hardness scale, and it was extremely hard compared to the conventional product, which had a hardness of HB ~, so it was hardly scratched even by abrasion with steel wool.

[Brief explanation of drawings]

The drawings are conceptual diagrams showing one embodiment of the present invention.
The figure is a cross-sectional view of the manufacturing process, and Figure 8 is a cross-sectional view of the product.
FIG. 9 is also a plan view. 1... Substrate, 2, 8, 9... Thin film layer, 6, 7... Intermediate layer, R, G, B...
Colored bands. Figure 1 Multiple Figures 2 Figures Multiple Figures Multiple Figures Multiple Figures 5 Figures 6 Multiple Figures Multiple Figures 8 Figures Multiple Figures 9

Claims (1)

[Claims] 1 General formula R^1_aR^2_bSi(OR_3)_4
A striped filter characterized in that a coating film obtained from a coating composition comprising an organosilicon compound represented by ____(_a_+_b_) and/or its hydrolyzate and a curing catalyst is used as a colored layer. "Here, R_1 is an organic group containing an epoxy group. R_2 is an alkyl group. R_3 is an organic group consisting of a halogenated alkyl group or an allyl group, each of which is bonded to Si through a carbon-silicon bond. Alkyl group, alkoxyalkyl group or acyl group a is 1 or 2, b is 0 or 1, and a+b is 1 or 2.