JPH0559311A - Resin composition for light-resistant colored thin film - Google Patents

Abstract

PURPOSE:To provide a resin composition for thin film, composed of a photo- stabilizer coated with a photo-decomposable polymer resin, a film-forming polymer resin, a colorant and a separation agent, having excellent long-term light- resistance, dispersibility of the colorant and tackiness and useful for color filter. CONSTITUTION:The objective resin composition for a light-resistant colored thin film and useful for color filter contains (A) (A1) a photo-stabilizer consisting of at least one component selected from a quencher (e.g. nickel complex), a hindered amine compound and an antioxidant (e.g. triphenyl phosphite) coated with (A2) at least one photo-decomposable polymer resin selected from a polymer having ketone structure (e.g. ethylene/carbon monoxide copolymer), a polymer having unsaturated bond (e.g. 1,2-polybutadiene) and a polymer susceptible to photo-oxidation (e.g. polyisobutylene oxide), (B) a polymer resin capable of forming a thin film (e.g. acrylic resin), (C) a colorant and (D) an ionic and/or nonionic surfactant as a dispersing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for light-resistant colored thin film. In particular, the present invention relates to a composition useful as a color filter used for a multicolor display body such as a color liquid crystal display device and a color facsimile and an optical device.

[0002]

2. Description of the Related Art As a method for producing a colored thin film constituting a color filter, there are a dyeing method and a stock solution coloring method. The staining method is gelatin, casein, glue or
A mordant layer made of a hydrophilic resin such as polyvinyl alcohol is provided, and the mordant layer is dyed with a dye to form a colored layer. The stock solution coloring method is a method in which an ink prepared by mixing a resin with a coloring agent is directly printed on the substrate surface by offset printing, or a photosensitive material in which a dye or an organic pigment is dispersed on a patterned conductive film on the substrate. There is a photolithography method in which a desired shape / arrangement is formed by applying a resin composition on a substrate and exposing and developing it. The color fastness of the resulting color filter is widely used because the stock solution coloring method in which the pigment is dispersed is superior to the dyeing method, and the process is simple and suitable for mass production.

Further, in order to improve the light resistance of coloring,
For example, a method of adding a light stabilizer such as a benzoate type, benzophenone type, benzotriazole type, piperidine type is used. Further, it is known that a combination of a light stabilizer and an antioxidant or a combination of an ultraviolet absorber and a hindered amine light stabilizer has a relatively high light resistance effect [Chemical Industry, Vol. P. 72 (1985)].

[0004]

The light resistance imparting method by adding the light stabilizer described above uses a large amount of the light stabilizer in order to suppress the fading reaction and improve the light resistance of the thin film. However, there are problems such as suppressing the curing reaction of (1), whitening of the film, and deterioration of adhesion.

[0005]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention is a light-resistant coloring comprising a photodegradable polymer resin, a light stabilizer, a thin film forming polymer resin, a colorant and a dispersant. A resin composition for a thin film, wherein the light stabilizer is coated with a photodegradable polymer resin, and the resin composition for a light resistant colored thin film is provided.

The photodegradable polymer resin used in the present invention is a polymer having a ketone structure: for example, ethylene-carbon monoxide copolymer, vinyl ketone-vinyl monomer copolymer, and styrene-phenyl vinyl ketone copolymer. A polymer having an unsaturated bond: for example, thermoplastic 1,2-polybutadiene (for example, manufactured by Nippon Synthetic Rubber Co., Ltd.);
In addition, there are polymers that are easily photooxidized: for example, polyisobutylene oxide (manufactured by Daicel Chemical Industries, Ltd.) and the like, which can be used alone or as a mixture.

Examples of the thin film-forming polymer resin used in the present invention include acrylic resin, polyester resin, epoxy resin and polyamide resin, which can be used alone or as a mixture.

The light stabilizer used in the present invention includes a quencher, a hindered amine compound and an antioxidant, and at least one of them is used.

The quencher which is one of the light stabilizers used in the present invention includes, for example, nickel complexes, carotenes, amines, phenols, sulfides, and the like. For example, Ni-bis (dithiobenzyl) [ The following is abbreviated as NB
DB], Ni-dialkyldithiocarbamate [hereinafter,
Abbreviation NBC], Ni-bisdiacetyl [abbreviation NBDA], nickel bis (octylphenyl) sulfide, 2,2′-thiobis (4-tert-octylphenolate) n-butylamine nickel (II), 2,
2'-thiobis (4-tert-octylphenolate) -2-ethylhexylamine nickel (II), 2,
2'-thiobis (4-tert-octylphenolate) triethanolamine nickel (II), etc.,
It is preferable to use one type or two or more types.

In this case, 0.001 to 1 part by weight is suitable for 100 parts by weight of the colorant, and the addition amount is 0.0.
When the amount is less than 01 parts by weight, the effect of improving the light resistance is hardly obtained, and when the amount is more than 1 part by weight, the adhesion of the film is deteriorated, which is not preferable. One of the light stabilizers used in this invention
Examples of the hindered amine compound (HALS) include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and sebacic acid-bis (2,2,6,6-).
Tetramethyl-4-piperidyl) sebacic acid-bis (N
-Methyl-2,2,6,6-tetramethyl-4-piperidyl), and other oligomer type and polymer type having a cyclic hindered amine structure can be used. In this case, the amount of addition is 10
0.001 to 5 parts by weight is suitable for 0 parts by weight, and if it is less than 0.001 parts by weight, there is almost no effect as an improvement in light resistance, and if it exceeds 5 parts by weight, whitening or adhesion occurs. It is not preferable because it causes deterioration of the sex.

An antioxidant which is one of the light stabilizers used in the present invention is, for example, 2,6-di-t-butyl-4-.
Methylphenol, tetrakis- [methylene-3-
It is possible to use hindered phenol derivatives such as (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propyneauto] methane and phosphite derivatives such as trinonylphenylphosphite and triphenylphosphite. it can. In this case, the addition amount is suitably 0.01 to 5 parts by weight with respect to 100 parts by weight of the thin film-forming polymer resin, and if less than 0.01 parts by weight, there is almost no effect of improving light resistance. When it exceeds the weight part, it is not preferable because it causes whitening and deterioration of adhesion.

The colorant used in the present invention includes organic pigments and inorganic pigments. Examples of organic pigments include azo lake type, insoluble azo type, phthalocyanine type, quinacridone type, dioxazine type, isoindolinone type, berynone type, anthraquinone type, perylene type and the like, and mixtures thereof. Examples of inorganic pigments include milori blue, cobalt-based, manganese-based, ultramarine blue, cobalt blue, cerulean blue, viridian, emerald green, cobalt green, and mixtures thereof. The blending amount of this colorant is suitably 5/1 to 1/10 (solid content weight ratio) with respect to the above-mentioned thin film forming polymer resin, and if it is less than 1/10, desired spectral characteristics cannot be obtained. 5,
If it exceeds / 1, the adhesiveness is remarkably reduced, which is not preferable.

In the present invention, a surfactant is used as a dispersant, which is for dispersing a colorant and a light stabilizer coated with a photodegradable polymer, and is an ionic surfactant and / or Alternatively, a nonionic surfactant is used.

As the ionic surfactant, a cationic surfactant and an anionic surfactant can be appropriately used. Examples of the cationic surfactant include amine acetate, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkylpyridinium halogenide, and alkyldimethylbenzylammonium chloride. Examples of the anionic surfactant include sodium alkylsulfate, sodium amidosulfate, sodium secondary alkylsulfate, sodium glycol ether sulfate, sodium alkylsulfonate, sodium amidosulfonate, sodium dialkylsulfosuccinate, sodium alkylallylsulfonate, and alkyl. Examples include sodium naphthalene sulfonate. As the nonionic surfactant, polyoxyethylene alkylphenol, polyoxyethylene fatty alcohol,
There are polyoxyethylene fatty acid, polyoxyethylene acid amide, polyoxyethylene fatty amine, polyoxyethylene styrene ether, and the like, and as the nonionic surfactant, those having HLB in the range of 10 to 18 can be preferably used. ..

The following are specific examples. (A) Nonionic dispersant: Asahi Denka Kogyo Co., Ltd., Adecanol NK-15, HLB = 15, Kao Atlas Co., Span 40, HLB = 7, Daiichi Kogyo Seiyaku Co., Neugen ET / 90, HLB = 19 ( b) Cationic dispersant: Toho Chemical Industry Co., Ltd., Catinal HTB (c) Anionic dispersant: Toho Chemical Industry Co., Ltd., Toho Salt A-5

The above HLB is calculated by the Griffin equation (MC Griffin J. et al.
Soc. Cosmet. Chemists, 5,249
It is calculated by (1954)), but when it is less than 10, the colorant is not dispersed, and when it exceeds 18, foaming tends to occur when a colored thin film is formed, which is not preferable. Further, these ionic surfactants and / or nonionic surfactants are suitable in an amount of 0.5 to 10% by weight, and less than 0.5% by weight, based on the total solid content of the colored thin film composition. However, there is no dispersion effect, and if it exceeds 10% by weight, a large amount of pyrolysis gas is generated in a high temperature region, and voids are observed in the formed thin film, which is not preferable.

The composition of the present invention is characterized by using a light stabilizer coated with a photodegradable polymer resin, and the coating can be carried out by a known method.
Examples of this coating method include a low temperature encapsulation method (low temperature dry mixing method), a submerged curing coating method (orifice method), a complex coacervation method, and a submerged drying method.
It is appropriately selected depending on the types of the photodegradable polymer resin and the light stabilizer used, the type and application of the colored thin film to be formed, and the like.

The composition of the present invention can be prepared by a conventional method for producing a light stabilizer coated with the above-mentioned photodegradable polymer resin, a thin film-forming polymer resin, a colorant and a dispersant.

A colored thin film can be prepared by using the composition of the present invention.
It is manufactured as follows. First, to the composition of the present invention consisting of a light stabilizer coated with a photodegradable polymer resin, a thin film forming polymer resin, a colorant and a dispersant, an organic solvent is added, if necessary, and mixed by stirring. Then, if necessary, a photocrosslinking agent or a thermal crosslinking agent is added, and then mixed and stirred again to prepare a thin film forming liquid.

An organic solvent may be added to the composition of the present invention for the purpose of i) obtaining a smooth coating film, ii) improving solution stability, and iii) facilitating dispersion. Such organic solvents include ethyl, butyl, cellosolves such as methyl cellosolve, alcohols such as isopropanol and butanol, glycols, hydrophilic solvents such as carbitols can be mainly used, but in some cases, xylol, triol, mineral tar. Hydrophobic solvents such as Ben can also be used. Examples of auxiliaries that can be used include a leveling agent that improves the smoothness of the coating film and an antifoaming agent that stops the foaming of the bath.

A curing agent is optionally added to cure the thin film-forming polymer resin. As the curing agent, a photocrosslinking type imparting photosensitivity or a thermal crosslinking type imparting thermosetting property is used. Any of the types, for example, in the case of photocrosslinking type, diazo compounds, azide compounds, photopolymerization initiators, etc.,
If necessary, a reactive diluent monomer, a sensitizer, and a thermal polymerization inhibitor are added. In the case of the heat-crosslinking type, isocyanate, hexamethylenetetramine, peroxide, diallylphthalate, diethylenetriamine and the like are added.

A light-resistant colored thin film is produced using the above-mentioned colored thin film forming liquid, and as a typical example, a case of producing a color filter by a photolithography method and an electrodeposition method will be described. However, the thin film is not limited to these methods, and other methods can be used.

(Photolithography Method) The above-mentioned thin film forming liquid is coated on the entire surface of a glass substrate as a medium for forming a color filter by using a spinner or a roll coater. Pre-baking may be performed at this stage if necessary. Next, the photomask having a desired pattern is fixed at a predetermined position on the substrate. Irradiate light on the photomask,
The coating film of the colored thin film composition which is not covered with the photomask is cured. Next, the unexposed portion of the colored thin film forming liquid is washed. If necessary, baking is performed at a predetermined temperature to fix the coating film of the exposed portion on the substrate. As a result, the color filter of the first color is formed, and the remaining 2
With respect to color, a color filter composed of three primary colors can be obtained by the same steps as described above.

(Electrodeposition method) A transparent electrode pattern having conductivity such as indium oxide or tin oxide is formed on a glass substrate as a medium for forming a color filter, and platinum or platinum is added to a diluted colored thin film forming solution. The counter electrode made of stainless steel or the like and the glass substrate provided with the transparent pattern are immersed. About 6 to 10 between the transparent electrode pattern to be colored and the counter electrode.
A DC voltage of 0V is applied. By this voltage application, the resin ions and the colorant in the electrodeposition liquid migrate only on the pattern to which the voltage is applied, and after deposition on the glass substrate as a coating film,
The glass substrate is taken out from the electrodeposition bath, thoroughly washed with deionized water, and then heated to cure the coating film. In this way, a colored transparent electrode pattern of one color is produced. As described above, a color filter composed of three primary colors is obtained by the same steps as described above.

[0025]

The colored thin film prepared by using the composition of the present invention has a property that the photodegradable polymer resin coating the light stabilizer is gradually decomposed with the passage of time and the light stabilizer is exposed. Since the deterioration of the discoloration is suppressed, the light resistance of coloring is maintained for a long period of time. Next, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0026]

【Example】

(Raw materials) Raw materials used in the examples are as follows. (I) Photodegradable polymer resin (a) Thermoplastic 1,2-polybutadiene (manufactured by Japan Synthetic Rubber Co., Ltd.) (b) Polyisobutylene oxide (manufactured by Daicel Chemical Industries, Ltd.) (c) Styrene-phenyl vinyl Ketone Copolymer Incidentally, the resin (c) was produced as follows. That is, the polymerization reaction was equipped with a glass stopper and a valve.
It was carried out in a 00 ml flask. After charging the monomer, the catalyst and 20 ml of ethyl acetate solvent, nitrogen was introduced into the flask and heated at a temperature of 60 ° C. for 36 hours. Next, the content was cooled, poured into 1000 ml of methanol, filtration and washing with methanol were repeated several times, and dried in a circulating air oven to obtain a copolymer.

(Ii) Light stabilizer (a) Quencher ... Ni-bisdiacetyl (b) Hindered amine compound ... 4-Benzoyloxy-2,2,6,6-tetramethylpiperidine (c) Antioxidant ...... 2,6-di-t-butyl-4-methylphenol Further, a photodegradable polymer resin, for example, an average particle size of 0.05μ.
m or less styrene-phenyl vinyl ketone copolymer 10
0 g and 8 g of a light stabilizer (quenching agent, hindered amine compound, antioxidant) having an average particle diameter of 0.1 μm or less are added to Hosokawa Micron Co., Ltd. Mechanofusion System AM-
If it is treated with 15F, the light stabilizer can be easily coated. Other photodegradable polymer resins (a) and (b) can be coated with the light stabilizer in the same manner.

(Iii) Polymer resin for forming a thin film (a) For photolithography A 500 ml round bottom separable flask is charged with 50 parts of 2-hydroxyethyl methacrylate, 40 parts of dimethylaminopropyl methacrylate, and 10 parts of methacrylamide. Then, 0.5 part of azobisisobutyl nitrile as a polymerization initiator and 200 parts of methyl cellosolve as a solvent are charged, nitrogen gas is injected, and the mixture is stirred at 40 ° C. and uniformly dissolved. Then, the temperature was raised to 70 ° C. and the mixture was stirred for 5 hours to copolymerize the monomer having the above composition. Next, the copolymerization mixture was put into cyclohexane to obtain a copolymer. The obtained copolymer was dissolved in a mixed solvent of 7 parts of acetic acid and 95 parts of ion-exchanged water to prepare a 15% by weight copolymer solution. (B) Electrodeposition Nippon Oil & Fat Co., Ltd. Aqua 6000, containing a curing agent (iv) Diazo compound Shinko Giken Co., Ltd. diazo resin D013 (v) Colorant Sanyo Dye Co., Ltd. Phthalocyanine Bull, Phthalocyanine Green, Azo Metal salt red pigment (vi) Dispersant Nonionic dispersant: Span 40 manufactured by Kao Atlas Co., Ltd.
HLB = 7

(Production of Colored Thin Film) First, using the above-mentioned Mechanofusion System AM-15F, the light stabilizer of each of Examples 1 to 11 shown in Table 1 was mixed with each photodegradable resin (part by weight). ). Then, the light stabilizer coated with the photodegradable resin of Examples 1 to 8, the thin film-forming polymer resin I, the dispersant, the diazo compound and the colorant (all are parts by weight) are mixed, and A composition used for preparing a thin film for photolithography of No. 8 was prepared.

Next, the compositions of Examples 1 to 8 described above were applied uniformly to a film thickness of about 2 μm on eight substrates (Examples 1 to 8) having a predetermined ITO patterning, Then, pre-baking is performed at 70 ° C. for 10 minutes to form a colored thin film, the colored thin film is exposed for 60 seconds by an exposure device using a predetermined mask pattern, and developed with water to develop a colored thin film for photolithography. A pattern was formed.

A light stabilizer coated with a photodegradable resin of Examples 9 to 11, a thin film forming polymer resin II, a dispersant and a colorant (all are parts by weight) were mixed, and a solid content concentration of 1 was added.
Deionized water was added so as to be 5% by weight to prepare a coating solution used for preparing a thin film for electrodeposition.

Next, a substrate (anode) on which a predetermined ITO pattern was applied and a stainless steel plate (cathode) as a counter electrode were immersed in the electrodeposition coating liquid of Examples 9 to 11 and 60 V was applied between both electrodes. Was applied for 10 seconds for electrodeposition coating. After energizing,
The electrodeposition-coated substrate was thoroughly washed with water, dried, and baked in an oven at 180 ° C. for 30 minutes to prepare a colored thin film.

[0033]

[Table 1]

(Evaluation of Colored Thin Film) The colored thin film compositions, coating films and thin films in the examples of the present invention were evaluated as follows.・ Dispersibility: After mixing and stirring, the mixture was allowed to stand for 7 days and the separated state of the pigment and the resin was observed. ◎ …… No separation, × …… Separation ・ Light resistance …… Made CF to 10 with metal halide lamp
Irradiation was carried out for 0 hours, and the spectral endurance before and after irradiation was measured with a color microanalyzer MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the color difference (ΔE) was obtained and evaluated. ◎ …… △ E ≦ 2, △ …… 2 <△ E ≦ 4, × …… △ E> 4 ・ Adhesion ・ ・ ・ Conforms to JIS K 5400-79. (Method) With a cutter knife blade, draw 11 films at 1 mm intervals at a right angle to make 100 goggles, and observe the traces of film removal. Further, the adhesive tape is pressure-bonded, and after peeling off the tape, the peeling condition of the eyelet is observed. (Evaluation) The results are shown in Table 2 below.

[0035]

[Table 2]

Tag property: The cured coating film was touched with a finger at 25 ° C. and evaluated in 5 levels according to the following criteria. 5-Does not feel any tag 4-Slightly feels a tag but does not leave behind the finger at all on the coating film 3-Slightly leaves behind the finger on the coating film 2-Remains clearly behind the finger on the coating film 1- The coating composition adheres to the finger. Spectral characteristics ... The spectral characteristics of the produced CF are measured by the color microanalyzer MCPD-1000 (Otsuka Electronics Co., Ltd.).
Manufactured), and the color difference (Δ
E) was obtained and evaluated. ◎ …… ΔE ≦ 2, △ …… 2 <ΔE ≦ 4, × …… ΔE> 4

Resin compositions for colored thin films of Examples 1 to 11,
When the colored thin film and the colored thin film were evaluated by the above-mentioned method, as shown in Table 3, any of the colored thin film compositions had good dispersibility, excellent resolution of the coating film, and excellent light resistance. We were able to.

[0038]

[Table 3]

[0039]

According to the present invention, excellent long-term light resistance,
Further, it is possible to provide a resin composition for a colored thin film, which is capable of producing a colored thin film excellent in dispersibility and tag property of a colorant. Further, the resin composition for a colored thin film can be applied to color filters of various multicolored displays and optical devices, and particularly when used for a liquid crystal display, it realizes high display quality and reliability. is there.

Claims (3)

[Claims] 1. A resin composition for a light-resistant colored thin film comprising a photodegradable polymer resin, a light stabilizer, a thin film-forming polymer resin, a colorant and a dispersant, wherein the light stabilizer has a high photodegradability. A resin composition for a light-resistant colored thin film, which is coated with a molecular resin. 2. The composition according to claim 1, wherein the photodegradable polymer resin comprises at least one of a polymer having a ketone structure, a polymer having an unsaturated bond and a polymer which is easily photooxidized. 3. The composition according to claim 1, wherein the light stabilizer comprises at least one of a quencher, a hindered amine compound and an antioxidant.