JP3130334B2 - Resin composition for light-resistant colored thin film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for a light-resistant colored thin film. In particular, the present invention relates to a composition useful as a color filter used in a multi-color display such as a color liquid crystal display device and a color facsimile, an optical device, and the like.

[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
This is performed by providing a mordant layer made of a hydrophilic resin such as polyvinyl alcohol, and dyeing the mordant layer with a dye to form a colored layer. The stock solution coloring method is a method in which an ink made by blending a colorant with a resin is directly printed on the substrate surface by offset printing or the like, and 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 resin composition is applied onto a substrate, exposed and developed to form a desired shape and arrangement. The color fastness of the resulting color filter is superior to that of the stock solution in which the pigment is dispersed, compared to the dyeing method, and the method is widely used because 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 benzoate-based, benzophenone-based, benzotriazole-based, or piperidine-based light stabilizer is used. It is also 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. 72 (1985)].

[0004]

In the above method for imparting light resistance by adding a light stabilizer, a large amount of light stabilizer is used to suppress the fading reaction and improve the light resistance of the thin film. However, there are problems such as suppression of the curing reaction, whitening of the film and reduction in adhesion.

[0005]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a light-resistant colorant 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 photodegradable polymer resin is
Polymer with ketone structure, polymer with unsaturated bond
And from at least one polymer which is susceptible to photooxidation
The present invention provides a resin composition for a light-resistant colored thin film , wherein a light stabilizer is coated with a photodegradable polymer resin.

The photodegradable polymer resin used in the present invention includes polymers 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, polymers that are easily oxidized by photooxidation include, for example, polyisobutylene oxide (for example, manufactured by Daicel Chemical Industries, Ltd.), which can be used alone or as a mixture.

As the thin film-forming polymer resin used in the present invention, there are acrylic resin, polyester resin, epoxy resin, polyamide resin and the like, and they 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.

Quenchers which are one of the light stabilizers used in the present invention include, 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, referred to as
NBC], Ni-bisdiacetyl [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) and the like,
It is preferable to use one or more of these.

[0010] In this case, the addition amount is suitably 0.001 to 1 part by weight with respect to 100 parts by weight of the coloring agent.
If the amount is less than 01 parts by weight, there is almost no effect of improving light resistance, and if it exceeds 1 part by weight, the adhesion of the film is undesirably reduced. One of the light stabilizers used in the present invention
One of the hindered amine compounds (HALS) is, for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis-sebacate (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate-bis (N
-Methyl-2,2,6,6-tetramethyl-4-piperidyl), and other oligomers and polymers having a cyclic hindered amine structure. In this case, the amount of addition should be
0.001 to 5 parts by weight is suitable for 0 part by weight. When the amount is less than 0.001 part by weight, there is almost no effect of improving light resistance. When the amount exceeds 5 parts by weight, whitening or adhesion occurs. This leads to a decrease in the properties, which is not preferred.

The antioxidant which is one of the light stabilizers used in the present invention is, for example, 2,6-di-tert-butyl-4-.
Methylphenol, tetrakis- [methylene-3-
Hindered phenol derivatives such as (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propineato] methane, and phosphite derivatives such as trinonylphenyl phosphite and triphenyl phosphite can be used. it can. In this case, the amount of addition is suitably from 0.01 to 5 parts by weight based on 100 parts by weight of the thin film-forming polymer resin. Exceeding the weight part is not preferable because it causes whitening and a decrease in adhesion.

The coloring agents used in the present invention include organic pigments and inorganic pigments. Examples of the organic pigment include an azo lake type, an insoluble azo type, a phthalocyanine type, a quinacridone type, a dioxazine type, an isoindolinone type, a verinone type, an anthraquinone type, a perylene type, and a mixture thereof. Examples of inorganic pigments include Miroli blue, cobalt-based, manganese-based, ultramarine, cobalt blue, cerulean blue, viridian, emerald green, cobalt green, and mixtures thereof. The compounding amount of the coloring agent is suitably from 5/1 to 1/10 (weight ratio of solid content) to the above-mentioned thin film-forming polymer resin, and if it is less than 1/10, desired spectral characteristics cannot be obtained. , 5
When the ratio exceeds / 1, the adhesion is remarkably reduced, which is not preferable.

In the present invention, a surfactant is used as a dispersant. The surfactant is used for dispersing a colorant and a light stabilizer coated with a photodegradable polymer. 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 alkyl sulfate, sodium amido sulfate, sodium dialkyl sulfate, sodium glycol ether sulfate, sodium alkyl sulfonate, sodium amido sulfonate, sodium dialkyl sulfosuccinate, sodium alkyl allyl sulfonate, and alkyl. And sodium naphthalene sulfonate. As nonionic surfactants, polyoxyethylene alkylphenol, polyoxyethylene fatty alcohol,
There are polyoxyethylene fatty acid, polyoxyethylene amide, polyoxyethylene fatty amine, polyoxyethylene styrene ether, and the like. Among nonionic surfactants, those having an HLB in the range of 10 to 18 can be suitably used. .

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

The above HLB is calculated by the Griffin formula (MC Griffin J. et al.) Based on the weight fraction of the hydrophilic part.
Soc. Cosmet. Chemists, 5,249
(1954)), but if it is less than 10, the colorant will not be dispersed, and if it exceeds 18, it is not preferable because foaming is likely to occur when a colored thin film is formed. In addition, these ionic surfactants and / or nonionic surfactants are suitably used in an amount of 0.5 to 10% by weight based on the total solid content of the composition for a colored thin film. When the content exceeds 10% by weight, a large amount of pyrolysis gas is generated in a high temperature range, and voids are seen 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.
As the coating method, there are a low-temperature encapsulation method (low-temperature dry mixing method), a curing-in-liquid coating method (orifice method), a complex coacervation method, a submerged drying method, and the like.
It is appropriately selected depending on the type of the photodegradable polymer resin and the light stabilizer used, and the type and use of the colored thin film to be formed.

In the composition of the present invention, a light stabilizer, a thin film-forming polymer resin, a colorant and a dispersant coated with the above-mentioned photodegradable polymer resin can be produced by a usual method.

The colored thin film is formed by using the composition of the present invention.
It is manufactured as follows. First, an organic solvent is added 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, if necessary, followed by stirring and mixing. Next, if necessary, a photo-crosslinking agent or a thermal cross-linking agent is added, followed by mixing and stirring 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, and, in some cases, xylol, triol, and mineral terolate. Hydrophobic solvents such as ben can also be used. Examples of the auxiliary agent that can be used include a leveling agent for improving the smoothness of the coating film and an antifoaming agent for stopping foaming in the bath.

In order to cure the thin film-forming polymer resin, a curing agent is added as necessary. The curing agent may be a photocrosslinkable type having photosensitivity or a thermocrosslinking type having thermosetting property. Any of the types, for example, in the case of a photocrosslinking type, a diazo compound, an azide compound, a photopolymerization initiator, etc.
If necessary, a reactive diluting monomer, a sensitizer, and a thermal polymerization inhibitor are added. In the case of the thermal crosslinking type, isocyanate, hexamethylenetetramine, peroxide, diallyl phthalate, diethylene triamine and the like are added.

A light-resistant colored thin film is manufactured by using the above-mentioned colored thin film forming liquid. A typical example is a case where a color filter is manufactured by a photolithography method and an electrodeposition method. However, other methods can be used for the thin film without being limited to these methods.

(Photolithography Method) The above thin film forming liquid is applied to the entire surface of a glass substrate as a medium for forming a color filter by using a spinner or a roll coater. At this stage, preliminary firing may be performed if necessary. Next, a photomask on which a desired pattern is formed is fixed at a predetermined position on the substrate. Irradiate light onto the photomask,
A part of the colored thin film composition which is not covered with the photomask is cured. Next, the unexposed portions of the colored thin film forming liquid are washed. By baking at a predetermined temperature as necessary, the coating film of the exposed portion is fixed on the substrate. As a result, a first color filter is formed, and then the remaining 2 color filter is formed.
As for the color, a color filter composed of three primary colors is 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 on which a color filter is to be formed, and platinum or platinum is added to the diluted colored thin film forming liquid. A counter electrode made of stainless steel or the like and the glass substrate provided with the transparent pattern are immersed. Approximately 6 to 10 between the transparent electrode pattern to be colored and the counter electrode.
A DC voltage of 0 V 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 was applied, and after being deposited on the glass substrate as a coating film,
The glass substrate is removed from the electrodeposition bath, washed thoroughly with deionized water, and then heated to cure the coating. 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]

In the colored thin film produced by using the composition of the present invention, as time passes, the photodegradable polymer resin coating the light stabilizer gradually decomposes, and the light stabilizer is exposed to light. , And the color fastness 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) The raw materials used in the examples are as follows. (I) Photodegradable polymer resin (a) Thermoplastic 1,2-polybutadiene (manufactured by Nippon Synthetic Rubber Co., Ltd.) (b) Polyisobutylene oxide (manufactured by Daicel Chemical Industries, Ltd.) (c) Styrene-phenylvinyl Ketone copolymer The resin (c) was produced as follows. That is, the polymerization reaction was carried out by adding a glass stopper and a bulb.
Performed in a 00 ml flask. After charging the monomer, catalyst and 20 ml of ethyl acetate solvent, nitrogen was introduced into the flask and heated at 60 ° C. for 36 hours. Next, the content was cooled, poured into 1000 ml of methanol, and 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-based compound ... 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (c) Antioxidant ... 2,6-di-t-butyl-4-methylphenol A photodegradable polymer resin, for example, having an average particle size of 0.05 μm.
m or less styrene-phenyl vinyl ketone copolymer 10
0 g and 8 g of a light stabilizer (quencher, hindered amine compound, antioxidant) having an average particle diameter of 0.1 μm or less were added to Mechanofusion System AM- manufactured by Hosokawa Micron Corporation.
If treated with 15F, the light stabilizer can be easily coated. The other photodegradable polymer resins (a) and (b) can be similarly coated with a light stabilizer.

(Iii) Thin film-forming polymer resin (a) For photolithography In a 500 ml round bottom separable flask, 50 parts of 2-hydroxyethyl methacrylate, 40 parts of dimethylaminopropyl methacrylate and 10 parts of methacrylamide Then, 0.5 parts of azobisisobutylnitrile as a polymerization initiator and 200 parts of methylcellosolve as a solvent are added, nitrogen gas is injected, and the mixture is stirred at 40 ° C. to be uniformly dissolved. Thereafter, 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 copolymer mixture was introduced 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 Yushi Co., Ltd. Aqua 6000, containing a curing agent (iv) Diazo compound Shinko Giken Co., Ltd. diazo resin D013 (v) Colorant Sanyo Pigment Co., Ltd. Metal salt red pigment (vi) Dispersant Nonionic dispersant: Span 40 manufactured by Kao Atlas Co., Ltd.
HLB = 7

(Production of Colored Thin Film) First, each of the light stabilizers of Examples 1 to 11 shown in Table 1 was replaced with each of the photodegradable resins (all by weight) using the aforementioned Mechanofusion System AM-15F. ). Next, 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 coloring agent (all by weight) were mixed. Composition No. 8 was prepared for use in the preparation of a thin film for photolithography.

Next, the compositions of Examples 1 to 8 were uniformly applied to eight substrates (Examples 1 to 8) on which predetermined ITO patterning was performed to a thickness of about 2 μm using a spin coater. Thereafter, pre-baking is performed at 70 ° C. for 10 minutes to form a colored thin film. The colored thin film is exposed to light for 60 seconds by an exposing machine using a predetermined mask pattern, developed with water, and colored for photolithography. A pattern was formed.

The light stabilizer coated with the photodegradable resin of Examples 9 to 11, the thin film-forming polymer resin II, the dispersant and the colorant (all by weight) were mixed, and the solid content was adjusted to 1 part.
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 predetermined ITO patterning has been performed and a stainless steel plate (cathode) as a counter electrode are immersed in the electrodeposition coating liquids of Examples 9 to 11, and a voltage of 60 V is applied between the two electrodes. Was applied for 10 seconds to perform electrodeposition coating. After energizing,
The electrodeposited substrate was sufficiently washed with water, dried, and baked in an oven at 180 ° C. for 30 minutes to produce a colored thin film.

[0033]

[Table 1]

(Evaluation of Colored Thin Film) The colored thin film composition, coating film and thin film in 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 state of separation between the pigment and the resin was observed. ◎ …… No separation, × …… Separation ・ Light resistance ...
Irradiation was carried out for 0 hour, and the spectral persistence before and after the irradiation was measured with a color microanalyzer MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). ◎: △ E ≦ 2, △: 2 <△ E ≦ 4, ×: △ E> 4 ・ Adhesion: JIS K 5400-79. (Method) With a cutter knife blade, the coating film is drawn at right angles at intervals of 1 mm at 11 mm intervals to form 100 goban eyes, and the trace of the peeling of the coating film is observed. Furthermore, it is pressure-bonded to an adhesive tape, and the peeling state of the gobang after peeling off the tape 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 on a 5-point scale based on the following criteria. 5- No tag felt 4- Little tag felt but no trail behind finger 3- Paint slightly behind finger 2- Paint clearly behind finger 1- The coating composition adheres to the finger.-Spectral characteristics: The spectral characteristics of the prepared CF are measured using a color microanalyzer MCPD-1000 (Otsuka Electronics Co., Ltd.)
), And the color difference (Δ
E) was determined and evaluated. ◎: ΔE ≦ 2, △: 2 <ΔE ≦ 4, x: ΔE> 4

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

[0038]

[Table 3]

[0039]

According to the present invention, excellent long-term light resistance,
In addition, it is possible to provide a colored thin film resin composition capable of producing a colored thin film having excellent colorant dispersibility and tag properties. In addition, the resin composition for colored thin films can be applied to color filters of various multicolor displays and optical devices, and achieves high display quality and reliability, particularly when used for liquid crystal displays. is there.

Claims (2)

(57) [Claims] 1. A light-resistant colored thin film resin composition comprising a photodegradable polymer resin, a light stabilizer, a thin film-forming polymer resin, a colorant and a dispersant, wherein the photodegradable polymer resin is a resin.
Ton-structured polymers, polymers with unsaturated bonds,
And at least one polymer that is susceptible to photo-oxidation.
A light-resistant colored thin film resin composition , wherein the light stabilizer is coated with a photodegradable polymer resin. 2. The composition according to claim 1, wherein the light stabilizer comprises at least one of a quencher, a hindered amine compound and an antioxidant.