KR20010066841A - Compositions for Forming Light Scattering Films and Light Scattering Films - Google Patents

Abstract

PURPOSE: A composition for forming light diffusion film is provided to efficiently diffuse reflected light, to attain uniform surface lighting with high frontal brightness and to obtain excellent flattening property, heat and chemical resistance by incorporating a copolymer of unsaturated carboxylic acids, epoxy group containing unsaturated compounds and specific olefinic unsaturated compounds and a light diffusion substance. CONSTITUTION: The resinous composition for a light diffusion film contains a copolymer of unsaturated carboxylic acids and/or unsaturated carboxylic acid anhydrides, epoxy group containing unsaturated compounds and olefinic unsaturated compounds other than monomers a light diffusion substance. The composition further comprises multifunctional monomers, polymerization initiators, epoxy compounds, and acid-generating agent. The copolymer is obtained by copolymerizing unsaturated carboxylic acids and/or unsaturated carboxylic acid anhydrides, epoxy group containing unsaturated compounds and olefinic unsaturated compounds other than monomers. The light diffusion substance has a function to diffuse reflected light and to heighten the frontal brightness of a liquid crystal display panel.

Description

Composition for forming light scattering film and light scattering film {Compositions for Forming Light Scattering Films and Light Scattering Films}

This invention relates to the curable composition for light-scattering films used for a liquid crystal display etc., and the light-scattering film formed from this.

Since liquid crystal displays require surface illumination with uniform and high front brightness, conventionally, a backlight unit has been provided. However, in recent years, the adoption of transflective and reflective liquid crystal displays has been increasing in view of power saving due to the spread of portable terminals.

Semi-transmissive and reflective liquid crystal displays are provided with reflecting plates, such as aluminum plates, under the liquid crystal panel to obtain brightness by reflecting light from the upper panel. However, according to this method, since the reflecting plate is planar, when the incident direction of the incident light from the upper part of the panel is oblique, the direction of the reflected light is shifted from the front direction of the panel, and sufficient front luminance is not obtained.

In order to improve the above drawbacks in the reflective liquid crystal display, a technique using a so-called light diffuser plate has been proposed. This method spreads the direction of the reflected light by giving a fine concavo-convex shape to the reflecting plate surface to obtain front luminance.

However, since this method needs to complicate the shape of the light diffusion plate, the process is complicated and disadvantageous both in terms of process and cost.

In order to solve the problem, Japanese Patent Laid-Open Nos. 7-261164 and 7-98452 have proposed a technique using a light scattering film. These publications provide a film obtained from a composition in which light scattering materials such as calcium fluoride, titanium oxide, and polytetrafluoroethylene are dispersed on the upper part of the color filter to scatter incident light and reflected light, thereby realizing high front luminance. It is disclosed that it can.

However, in the film obtained from the composition, as the light scattering material is present, physical properties such as flatness, heat resistance, chemical resistance, and adhesion to a transparent electrode (ITO film), which are inherent to be provided as a protective film, are reduced, and thus are still in practical use. I can't say that.

In a display manufacturing process, the position is set by detecting the alignment mark on a glass plate at the time of glass plate bonding. However, when bonding the glass plate which used the film | membrane obtained from the said composition as a protective film, there exists a problem that it is difficult to position correctly because of the scattering property of a protective film.

This invention is made | formed in view of the said situation.

SUMMARY OF THE INVENTION An object of the present invention is to realize surface illumination with uniform and high front luminance by efficiently scattering reflected light in a transflective and reflective liquid crystal display, and at the same time, having excellent flatness, heat resistance and chemical resistance, and high adhesion to ITO film. It is providing the curable composition for light-scattering film formation which can provide a light-scattering film.

Another object of the present invention is to provide a curable composition having radiation sensitivity that eliminates scattering of alignment mark portions in an exposure and development process and enables precise positioning.

Another object of the present invention is to provide a light scattering film formed from the curable composition for forming a light scattering film of the present invention.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the objects and advantages of the present invention, first,

(A) at least one carboxylic acid compound selected from the group consisting of (a1) unsaturated carboxylic acids and unsaturated carboxylic anhydrides,

(a2) unsaturated compounds containing an epoxy group, and

(a3) copolymers of olefinically unsaturated compounds other than the compounds (a1) and (a2), and

(B) light scattering material

It is achieved by the curable composition for light-scattering film formation (hereinafter, referred to as "first invention") characterized by containing.

The above objects and advantages of the present invention are secondly achieved by a light scattering film (hereinafter referred to as "second invention") formed from the curable composition for forming a light scattering film of the present invention.

In addition, the term "radiation" in the present invention is used in the concept including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular rays, gamma rays, synchrotron radiation, proton beam rays and the like.

Hereinafter, each component of the radiation sensitive composition for light scattering films of 1st invention is demonstrated.

Copolymer (A)

Copolymer (A) is a copolymer of compounds (al), (a2) and (a3). Compound (al) is unsaturated carboxylic acid or unsaturated carboxylic anhydride.

Examples of the compound (a1) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these unsaturated dicarboxylic acids. Of these, acrylic acid, methacrylic acid and maleic anhydride are preferably used in view of copolymerization reactivity, solubility in aqueous alkali solution and easy availability. These compounds (a1) are used individually or in mixture of 2 or more types.

The copolymer (A) preferably contains 1 to 50% by weight, particularly preferably 5 to 40% by weight of structural units derived from compound (a1). In this range, the copolymer (A) exhibits optimum performance in planarization, adhesion, coatability and heat resistance.

The compound (a2) is an epoxy group-containing unsaturated compound.

Examples of the compound (a2) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, glycidyl (alpha) -ethyl acrylate, glycidyl (alpha)-propyl acrylate, glycidyl (alpha)-propyl acrylate (Meth) acrylic acid glycidyl esters such as dill and derivatives thereof; And

Unsaturated such as (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl Epoxy compounds are mentioned as an example.

Among these, glycidyl (meth) acrylate and 2-methylglycidyl (meth) acrylate are preferably used in view of copolymerization reactivity, planarity, and the like. These compounds (a2) are used individually or in mixture of 2 or more types.

The copolymer (A) preferably contains 5 to 80% by weight, particularly preferably 7 to 70% by weight of structural units derived from compound (a2). In this range, the copolymer (A) shows optimum performance in planarization, heat resistance and adhesion.

Compound (a3) is an olefinically unsaturated compound different from compounds (a1) and (a2).

As the compound (a3), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) Tricyclo [5.2.1.O ^2,6 ] decane-8-yl acrylate (common names in the art are (meth) acrylic acid dicyclopentanyl), (meth) acrylic acid dicyclopentanyloxyethyl, (meth) acrylic acid (Meth) acrylic acid esters such as isoboroyl;

Vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene and vinylnaphthalene;

Indene derivatives such as indene and 1-methylindene;

Phenylmaleimide, benzyl maleimide, cyclohexyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide capro Dicarbonylimide derivatives such as ate, N-succinimidyl-3-maleimidepropionate, N- (9-acridyl) maleimide; And

Examples include conjugated dienes such as butadiene and isoprene.

Of these, (meth) acrylic acid esters and dicarbonylimide derivatives are preferably used in terms of adhesion, flattening properties, and the like. These compounds (a3) are used individually or in mixture of 2 or more types.

The copolymer (A) preferably contains 1 to 40% by weight, particularly preferably 2 to 35% by weight of structural units derived from compound (a3). In this range, the copolymer (A) exhibits optimum performance in adhesion, planarization, and the like.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A) is preferably in the range of 3,000 to 300,000, more preferably 3,000 to 100,000, particularly preferably 3,000 to 50,000.

By setting the copolymer (A) to Mw in this range, a balance excellent in various performances such as flattening, transparency, storage stability, adhesion, light scattering property, and developability of the film after curing is exhibited.

(B) light scattering material

(B) The light scattering material is a material which scatters the reflected light and increases the front luminance of the liquid crystal display panel.

Examples of the light scattering material (B) include inorganic oxide particles, organic particles, mineral particles, and metal particles.

Examples of the inorganic oxide particles include silica, titania and alumina.

As organic particle | grains, Styrene type organic particle | grains, such as a polystyrene, a styrene / isoprene copolymer, and a styrene / divinylbenzene copolymer;

Acrylic organic particles such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, ethyl polyacrylate, butyl polyacrylate, and methyl methacrylate / butyl methacrylate copolymer;

Acrylonitrile-based organic particles such as polyacrylonitrile and acrylonitrile / vinylidene chloride copolymer;

Benzoguanamine type or melamine type organic particle | grains, such as a benzoguanamine polymer, a melamine polymer, and a benzoguanamine / melamine copolymer;

Polyolefin organic particles such as polyethylene, polypropylene, and polybutene;

Ethylene such as ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer Acrylic organic particles;

Fluorine-based organic particles such as polytetrafluoroethylene;

Polyurethane-based organic particles;

Nylon organic particles;

Natural organic type particle | grains, such as cellulose, cellulose acetate, chitosan, and calcium alginate, etc. are mentioned.

Examples of the mineral particles include mica. Examples of the metal particles include metal powders of metals such as aluminum, tin, and gold.

Among these, inorganic oxide particles are preferred in that the refractive index is significantly different from that of the component (A), and the light scattering effect is large. Silica is particularly preferably used as the inorganic oxide particles.

In addition, since the organic particles can obtain a large scattering intensity in a range where the scattering angle is relatively small, the organic particles exhibit excellent scattering effects in the transflective or reflective liquid crystal display, thereby increasing the front luminance. Among them, styrenic organic particles and acrylic organic particles can be preferably used in that large scattering strength can be obtained.

(B) Although the shape of a light-scattering substance can be used as long as it has light scattering property, spherical shape and substantially spherical shape are preferable. As particle size, 0.01-20 micrometers is preferable, Especially preferably, it is 0.3-10 micrometers. By using the light scattering material of such shape and size, the panel front luminance can be effectively improved.

Commercially available products of such (B) light scattering materials, and inorganic oxide particles such as silica include Nip seal SS-10, SS-15, SS-10A, SS-20, SS-30S, SS-30P, SS-30A, SS -40, SS-50, SS-70, SS-72F, SS-115, SS-l70X, E-75, E-150, E-200A, E-220A, K-300 (above, Nippon Silica High School (Note) Manufactured), Sirius 250, 250N, 256, 256N, 310, 320, 350, 358, 430, 431, 440, 450, 470, 435, 445, 436, 446, 456, 530, 540, 550, 730, 740,770 (above, product made by Fuji-Sirisia Kagaku Co., Ltd.), micropearl (made by Sekisui Fine Chemical Co., Ltd.), tos perl 105, 120, 130, 145, 3120, 240 (more than Toshiba Silicone Co., Ltd. product) ), AEROSIL 130, 200, 200V, 200CF, 200FAD, 300, 300CF, 380, R972, R974, RX200, RY200, R202, R805, R812, OX50, TT600, MOX170, COK84 (above, Nippon Aerosil Co., Ltd.);

As a commercial item of these organic particles,

As styrene type organic particle | grains, PB200H, 200P (above, Gao Corporation make), the tech polymer SBX series, SBP series (above, Sekisui Kasei Hing Kogyo Co., Ltd. make), SGP series (Soku Kagaku Co., Ltd. make) ), STADEX series, CLINTEX series (above, JSR Corporation make), Nipole series (Nippon Xeon Corporation make), Nippon Microgel S-5001, S-5004, P-5001, P-3101 (more, Nippon Paint Co., Ltd., SGP-3G (made by Sogaku Kagaku Co., Ltd.), PB 200C, 200D (above, Gao Co., Ltd.), Micropearl series (made by Sekisui Fine Chemical Co., Ltd.), etc .;

As acrylic organic particle, tech polymer MB series, MBX series, MBP series, EMA series, BMX series (above, Sekisui Kasei Hinggo Kogyo Co., Ltd.), MR series, MP series (made by Sok Kagaku Co., Ltd.), Nippon microgel S-5002, S-5003, S-5005, S-5 101, S-5102, P-5002, P1101 (above, Nippon Paint Co., Ltd.), Jurima MB series (Nippon Junyaku Co., Ltd.) ) Made in Japan), Matsumoto micro spare M series (Matsumoto Yushi Seiyaku Co., Ltd.), Akozel series (Mitsui Saianamit Co., Ltd.), Eposa MA1001, MA1002, MA1004, MA1006, MA1010, MA1013, Epocal MA series (above, Nippon Shokuba Co., Ltd.) etc. can be illustrated, respectively.

Examples of minerals such as mica include natural mica and synthetic mica pearl pigments, Artica SA-100, SB-100, YB-100, and BB-100 (above, manufactured by Nippon Kogyo Kogyo Co., Ltd.).

The addition amount of the (B) light scattering product is preferably 1 to 100 parts by weight, more preferably 3 to 80 parts by weight, per 100 parts by weight of the copolymer (A). The light scattering plate which is excellent in the balance of transparency and light scattering property in this range can be provided.

Moreover, a dispersing agent can be used together in order to disperse | distribute (B) light scattering material effectively to a copolymer (A). Examples of such dispersants include silane coupling agents, urethane dispersants, polyethyleneimine dispersants, ethers of polyoxyethylene, and esters of polyethylene glycol. Among these, silane coupling agents and urethane dispersants are preferably used.

Examples of the silane coupling agent include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. Specifically, trimethoxysilylbenzoic acid, γ-methacrylooxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) 3-amino Propylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Methyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane , γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

As the urethane-based dispersant, a reaction product of aromatic diisocyanates with polylactones having a hydroxyl group at one end and / or polylactones having a hydroxyl group at the sock end is preferable, and in particular, tolylene diisocyanates and a hydroxyl group at one end are preferable. Preferred are reaction products with polycaprolactone present and / or polycaprolactone having a hydroxyl group at the sock end. Specific examples of these urethane-based dispersants include trade names EFKA (manufactured by Efka Chemicals, Inc.), Disperbyk (manufactured by BYK Corporation), Disparon (manufactured by Kusumoto Kasei Co., Ltd.), and the like.

When using the said dispersing agent, the usage-amount is 100 weight part or less with respect to 100 weight part of (B) light scattering substances, More preferably, it is 0.01-70 weight part.

When the amount in this range is used, the (B) light scattering substance is effectively dispersed in the component (A), and furthermore, the physical properties such as transparency, heat resistance, and planarity of the light scattering film after formation are not impaired.

(C) polyfunctional monomer and (D) polymerization initiator can be contained in the composition for light-scattering film formation of this invention further. By doing in this way, the composition suitable for the method of using radical polymerization in a light-scattering film formation process can be provided.

(C) component and (D) component are explained in full detail below.

The polyfunctional monomer as the component (C) has two or more polymerizable ethylenically unsaturated bonds and monomers which can be polymerized by radical species generated upon irradiation with light and / or heating to the polymerization initiator (D) described later. It consists of.

Such polyfunctional monomers include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; Diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and dicarboxylic acid modified substances thereof; Oligoacrylates or oligomethacrylates such as polyesters, urethane resins, alkyd resins, silicone resins, and spiran resins; Diacrylates or dimethacrylates of sock end hydroxylated polymers such as sock end hydroxypoly-1,3-butadiene, sock end hydroxypolyisoprene, sock end hydroxypolycaprolactone; And trisacryloyloxyethyl phosphate and trismethacryloyloxyethyl phosphate.

Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols are preferable, and trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and penta are specifically preferred. Erythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythrate Lithol hexamethacrylate, succinic acid modified pentaerythritol triacrylate, and succinic acid modified pentaerythritol trimethacrylate. Particularly, trimethylolpropane triacrylate, pentaerythritol triacrylate, poly (meth) acrylate, dipentaerythritol pentaacrylate and dipentaeryte of the compound represented by the following general formula (Bisphenol A dipentaerythritol) Ritol hexaacrylate is preferred.

Commercially available products of these include Alonics M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, TO-1450, M-1600 , M-1960, M-8100, M-8530, M-8560, M-9050, TO-1450 (above, product made by Toa Kosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA- 60, DPCA-120, MAX-3510 (above, made by Nippon Kayaku Co., Ltd.), biscot 295, 300, 360, GPT, 3PA, 400 (above, made by Osaka Yuki Kagaku Kogyo Co., Ltd.) as an example Can be.

In this invention, (C) polyfunctional monomer can be used individually or in mixture of 2 or more types.

The usage-amount of (C) component is 100 weight part of components (A), Preferably it is 10-200 weight part, More preferably, it is 20-150 weight part. When using the amounts in this range, a light scattering film excellent in high heat resistance, high leveling property, high transmittance, adhesion and chemical resistance is provided.

The said (D) component is a compound which has the ability to generate | occur | produce a radical by heat and / or light, and to start superposition | polymerization of the said (C) component. Among these compounds, thermal radical polymerization initiators include biimidazole compounds, benzoin compounds, triazine compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, and azo compounds. Examples are compounds. Among these, a biimidazole type compound, a triazine type compound, an acetophenone type compound, and an azo type compound are preferable.

As said biimidazole compound

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is mentioned.

Preferred compounds among these biimidazole compounds

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

Particularly preferred compounds are

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole.

In addition, specific examples of the triazine-based compound

2,4,6-tris (trichloromethyl) -s-triazine,

2-methyl-4,6-bis (trichloromethyl) -s-triazine,

2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine,

And triazine-based compounds having a halomethyl group such as 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is preferable.

These triazine type compounds can be used individually or in mixture of 2 or more types.

Specific examples of the acetophenone-based compound

2-hydroxy-2-methyl-1-phenylpropan-1-one,

2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,

2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,

1-hydroxy-cyclohexyl-phenyl-ketone,

And 2,2-dimethoxy-1,2-diphenylethan-1-one.

Among these acetophenone compounds, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 is particularly preferable.

The acetophenone compounds may be used alone or in combination of two or more thereof.

Specific examples of the azo compound include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (4-dimethylvaleronitrile), 2, 2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 4,4 '-Azobis (4-cyanovaleric acid) and 1,1'-azobis (1-acetoxy-1-phenylethane) are mentioned.

Among these azo compounds, in particular, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (4-dimethylvaleronitrile), 2,2 ' -Azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) can be preferably used. .

The amount of the thermal radical polymerization initiator mentioned above is preferably 0.01 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, particularly preferably 1 to 20 parts by weight based on 100 parts by weight of the (C) polyfunctional monomer.

Moreover, as a radiation sensitive radical polymerization initiator in (D) component, they are alpha-diketones, such as benzyl and diacetyl; Acyloins such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzo Benzophenones such as phenone; Acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacylchloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-triazine; 2,4,6-trimethylbenzoyldiphenylphosphineoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphineoxide, bis (2,4,6-trimethylbenzoyl) phenyl Acylphosphine oxides such as phosphine oxide; And peroxides such as di-t-butylperoxide.

Commercially available products of these radiation-sensitive radical polymerization initiators include IRGACURE-184, 369, 500, 651, 907, 1700, 819, 124, 1000, 2959, 149, 1800, 1850, Darocur-1173, 1116, 2959, 1664, 4043 ( Above, product made in Chiba specialty chemicals company), KAYACURE-DETX, MBP, DMBI, EPA, OA (above, product made by Nippon Kayaku Co., Ltd.), LUCIRIN TPO (product made by BASF Co. LTD), VICURE-10, 55 ( More than, STAUFFER Co. LTD), TRIGONALP1 (manufactured by AKZO Co. LTD), SANDORAY 1000 (manufactured by SANDOZ Co. LTD), DEAP (manufactured by APJOHN Co. LTD), QUANTACURE-PDO, ITX, EPD (above, WARD BLEKINSOP Co LTD.

Moreover, it is also possible to obtain the highly sensitive radiation sensitive resin composition with little inactivation by oxygen by using these radiation sensitive radical polymerization initiators and a radiation sensitive sensitizer together.

The use amount of the radiation sensitive radical polymerization initiator is preferably 0.01 to 60 parts by weight, more preferably 0.5 to 50 parts by weight, still more preferably 1 to 40 parts by weight based on 100 parts by weight of the (C) polyfunctional monomer. .

The curable composition consisting of the component (A) and the component (B) of the present invention may further contain an epoxy compound (E) and an acid generator (F). By doing in this way, the composition suitable for using the hardening reaction by the acid of an epoxy compound in a light-scattering film formation process can be provided.

(E) component and (F) component are explained in full detail below.

The epoxy compound (E) is a component which causes a polymerization or crosslinking reaction with an acid generated by the acid generator (F) described later to cause a curing reaction of the composition coating film.

As said (E) epoxy compound

Bisphenol A type epoxy resin, Hydrogenated bisphenol A type epoxy resin, Bisphenol F type epoxy resin, Hydrogenated bisphenol F type epoxy resin, Bisphenol S type epoxy resin, Hydrogenated bisphenol S type epoxy resin, Bisphenol AD type epoxy resin, Hydrogenated bisphenol AD type epoxy Epoxy resins such as resins, novolac type epoxy resins, cyclic aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxidized oils, epoxy novolac resins and bromide thereof;

Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, Bisphenol AD diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, Hydrogenated bisphenol S diglycidyl ether, Hydrogenated bisphenol AD diglycidyl ether, Brominated bisphenol A diglycidyl ether, Brominated bisphenol F diglycidyl ether, Brominated bisphenol S diglycidyl ether, Brominated bisphenol AD diglycidyl ether Aromatic epoxy compounds, such as cyl ether, are mentioned.

Among these epoxy compounds, epoxy resins are preferred in terms of high hardness of the light-scattering film after curing and less adverse effects on other film properties, particularly bisphenol A-based epoxy resins, novolac-type epoxy resins, and cyclic aliphatic epoxy resins. Epoxy resins having 2 to 100 of the same epoxy group are preferably used.

As a commercial item of these epoxy resins, As bisphenol-A epoxy resin, Epicoat 828, 834, 1001, 1002, 1003, 1004, 1007, 1009, 1010, 157SS65 (above, manufactured by Yuka Shell Epoxy Co., Ltd.); As bisphenol F-type epoxy resin, Epicoat 806, 806L, 807 (above, Yuka Shell Epoxy Co., Ltd. product); As a novolak-type epoxy resin, Epicoat 152, 154 (more, product made by Yuka Shell Epoxy Co., Ltd.), EPPN201, 202 (more, product made by Nippon Kayaku Co., Ltd.), EOCN-102, EOCN-103S, EOCN-104S , EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.); As a polyfunctional epoxy resin, Epicoat 1032H60 (made by Yuka Shell Epoxy Co., Ltd.); As cyclic aliphatic epoxy resin, CY175, CY177, CY179 (more than CIBA-GEIGY AG company made), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (more than UCC company make), Shodine 509 (Showa Denko) Co., Ltd.), Araldite CY-182, CY-192, CY-184 (more than, made by CIBA-GEIGY AG company), epicron 200, 400 (more, product made by Dainippon Ink Industries, Ltd.), Epicoat 871, 872 (above, manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, ED-5662 (above, manufactured by Celanese Co., Ltd.), and the like.

The addition amount of the component (E) is preferably 1 to 250 parts by weight, more preferably 3 to 200 parts by weight, per 100 parts by weight of the component (A). When using the quantity in this range, the composition for light-scattering film formation excellent in planarization, adhesiveness, applicability | paintability, and heat resistance is provided.

The said (F) component is a photo acid generator or a thermal acid generator which generate | occur | produces an acid by light or heat, and is a compound which performs hardening reaction of the said (E) component. Examples of the photoacid generator include diaryl iodonium salts and triarylsulfonium salts, and these can be preferably used. Examples of the thermal acid generator include sulfonium salts (except the triarylsulfonium salts mentioned above), benzothiazonium salts, ammonium salts, and phosphonium salts. Of these, sulfonium salts (excluding the triarylsulfonium salts mentioned above) and benzothiazonium salts are preferably used.

Examples of the diaryl iodonium salts include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoro arsenate, diphenyl iodonium trifluoromethanesulfonate, Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluenesulfonate, 4-methoxyphenylphenyl iodonium tetrafluoroborate, 4-methoxyphenylphenyl iodonium hexafluorophosphonate, 4- Methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodiumdetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodine Num triple Oro may be mentioned methane sulfonate, bis (4-t- butylphenyl) iodonium trifluoroacetate, bis (4-t- butylphenyl) iodonium -p- toluenesulfonate as an example. Of these, diphenyl iodonium hexafluorophosphonate is preferably used.

Examples of the triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, Triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumtetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxy Phenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsene Bit, 4-thiophenyl-diphenyl-tree may deulsu the methanesulfonate, 4-thiophenyl-diphenyl-trifluoroacetate, 4-thiophenyl-diphenyl -p- toluenesulfonate example fluoro. Among them, triphenylsulfonium trifluoromethanesulfonate is preferably used.

Specific examples of the sulfonium salt (excluding the above-described triarylsulfonium salt) include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, and dimethyl-4. -(Benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoro Alkylsulfonium salts such as arsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl- 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Benzylsulfonium salts such as hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl 4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5- dibenzylsulfonium salts such as t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro And substituted benzylsulfonium salts such as antimonate and o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

Among them, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate and 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate are preferably used.

Examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl ) Benzylbenzothianes such as benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate and 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Zonium salt is mentioned as an example.

Of these, 3-benzylbenzothiazonium hexafluoroantimonate is preferably used.

The usage-amount of these (F) components is preferably 1-40 weight part, More preferably, it is 5-30 weight part per 100 weight part of (E) epoxy compounds. In this range of use, good curing properties can be obtained and the various properties of the light scattering film after curing are not impaired.

OTHER ADDITIVES

The light scattering film formation composition of this invention can be made to contain additives other than the above as needed.

For example, in order to improve the applicability | paintability of a composition, surfactant can be mix | blended. As surfactant, a fluorochemical surfactant, silicone type surfactant, etc. can be used preferably.

As the fluorine-based surfactant, a compound having at least one fluoroalkyl or fluoroalkylene group can be preferably used. Specific examples thereof include 1,2,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,2,2,2-tetrafluorohexyl ether and octaethylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycoldi (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycoldi (1,1, 2.2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3.3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8 , 9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane.

In addition, sodium fluoroalkylbenzenesulfonic acid, fluoroalkyloxyethylene ethers, diglycerin tetrakis fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanols, perfluoroalkylalkoxylates, fluorine alkyls Ester can also be used preferably.

Commercially available products of these fluorine-based surfactants include BM-1000, BM-1100 (above, manufactured by BM Chemie), F-Top EF30l, 303, 352 (above, manufactured by Shinsei Kasei Co., Ltd.), Megapack Fl42D, F171, 172, 173, F183, F178, F191, F471 (above, Dai Nippon Ink Co., Ltd.), Flowride FC430, 431, 170C, FC171, FC430, FC431 (above, Sumitomo 3M Co., Ltd.), Asahi Guard AG710 And Supron S-382, SC-101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.).

As the silicone surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid (co) polymer polyflow Nos. 57, 95 (above, Kyoeisha Chemical Co., Ltd.) Corporation), DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, FS-1265-300 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF Commercially available products of -4446, TSF-4460, and TSF-4452 (above, Toshiba Silicone Co., Ltd.) are mentioned.

In addition to the above-described fluorine-based surfactants and silicone-based surfactants, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, poly Polyethylene ethylene ether, such as oxyethylene nonyl phenyl ether, polyethylene glycol dialkyl ester, such as polyethyleneglycol dilaurate and polyethyleneglycol distearate, can also be used preferably.

These surfactant can be used individually or in combination of 2 or more types.

Although the use ratio of these surfactant changes with the kind and ratio of each component which comprises the kind and hardening | curing agent composition, Preferably it is 0-10 weight part with respect to 100 weight part of component (A), More preferably, it is 0.0001- It is the range of 5 weight part.

Moreover, the adhesion | attachment adjuvant for improving adhesiveness with a board | substrate or an underlayer can be mix | blended with the composition of this invention. A storage stabilizer, an antifoamer, etc. can also be mix | blended with the composition of this invention as needed.

solvent

The curable composition for light scattering films of this invention is manufactured in the state disperse | distributed uniformly to the solvent so that solid content concentration may become 10 to 60 weight% preferably.

As a solvent used at this time, Alcohol, such as diacetone alcohol and propylene glycol; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosorb acetate and ethyl cellosorb acetate; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy Ethyl-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropio Esters such as nate, 3-methyl-3-methoxybutylbutyrate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, 3-methoxypropionate, ethyl 3-methoxypropionate, and butyl 3-methoxypropionate Etc. can be used. These solvents can be used individually or in mixture.

If necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, capronic acid, caprylic acid, 1- Such as octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosorbate acetate, carbitol acetate A high boiling point solvent can also be added.

Formation method of light scattering film

Next, the method of forming the light-scattering film of 2nd invention using the composition for light-scattering film formation of said 1st invention is demonstrated.

The light scattering film of the second invention may be formed as a second film on the planarizing film formed on the substrate, or the light scattering function may be provided to the planarizing film by using the light scattering film-forming composition of the first invention in the planarizing film forming composition. have.

In order to form the light-scattering film of 2nd invention, the composition for light-scattering film formation of 1st invention is first apply | coated to a board | substrate surface, and preliminary baking removes a solvent and forms the coating film of a curable composition.

At this time, in the case of using the light scattering film-forming composition containing the component (C) and the component (D), or in the case of using the light scattering film-forming composition containing the photoacid generator as the component (F), After hardening a coating film surface by irradiating light further after that, main baking can be performed and the light-scattering film of 2nd invention can be formed.

In addition, when using the composition for light-scattering film formation containing a thermal acid generator as (F) component, it can be set as the light-scattering film of 2nd invention by performing this baking, without performing a subsequent light irradiation process. have.

In addition, in order to remove unnecessary parts, such as an alignment mark, using the composition containing (C) component and the radical photopolymerization initiator as (D) component, radiation is carried out through the mask of a predetermined pattern after performing preliminary baking as mentioned above. Is irradiated and then developed with a developer to remove unnecessary portions such as alignment mark portions.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as triethylamine, methyldiethylamine and N-methylpyrrolidone; Alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline; Alkali which consists of alkalis which are cyclic amines, such as a pyrrole, a piperidine, 1,8- diazabicyclo [5.4.0] -7-undecene, and a 1, 5- diazabicyclo [4.3.0] -5-nonane An aqueous solution etc. can be used.

Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. to the said alkali aqueous solution can also be used as a developing solution.

The developing time is preferably 30 to 180 seconds. The developing method may be any of the liquid immersion method and the dipping method. After the development, washing with running water for 30 to 90 seconds, drying with compressed air and compressed nitrogen to remove moisture on the substrate, forms a patterned film.

Thereafter, the main baking is performed to form the light scattering film of the second invention.

As a coating method of the composition for light-scattering film formation of 1st invention above, it does not specifically limit but a suitable method, such as a spray method, a roll coating method, and a spin coating method, can be chosen.

The conditions of the preliminary firing vary depending on the type of each component in the composition solution, the use ratio and the like, but are preferably about 30 seconds to 20 minutes at 60 to 120 ° C.

As conditions for this baking, 30 minutes-about 2 hours are preferable at 150-250 degreeC.

In addition, each preliminary baking and this baking can be performed in one step or divided into two or more processes.

The curable composition for light scattering film formation of this invention can form a light scattering film by a simple process as mentioned above.

In addition, as indicated in the following examples, the light scattering film of the present invention has high transparency, has the property of efficiently scattering light, and is also excellent in various physical properties as a planarizing film or a protective film.

<Example>

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 Synthesis of Copolymer (A1)

20 parts by weight of acrylic acid as the component (a1), 45 parts by weight of glycidyl methacrylate as the component (a2), 20 parts by weight of styrene as the component (a3) and 15 parts by weight of dicyclopentanyl methacrylate as diethylene glycol ethylmethyl ether. The mixture was added to 200 parts by weight, and 4 parts by weight of azobisvaleronitrile (ADVN) was added, followed by polymerization at 70 ° C. for 5 hours to obtain a polymer solution having a copolymer (A1) concentration of 33% by weight.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A1) was 6,000.

Synthesis Example 2 (Synthesis of Copolymer (A2))

20 parts by weight of methacrylic acid as component (a1), 45 parts by weight of methacrylic acid 2-methylglycidyl as component (a2), 20 parts by weight of styrene and 15 parts by weight of phenylmaleimide as components (a3) The mixture was added to 200 parts by weight of methyl ether, and 4 parts by weight of azobisvaleronitrile (ADVN) was added, followed by polymerization at 70 ° C. for 5 hours to obtain a polymer solution having a copolymer (A1) concentration of 33% by weight.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A1) was 8,000.

<Example 1>

After adding propylene glycol monomethyl ether acetate to a solution containing the copolymer (A1) synthesized in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer (A1), the total amount was made into a solution of 350 parts by weight. 10 parts by weight of γ-glycidoxypropyldiethoxysilane as a silane coupling agent, 20 parts by weight of Tospearl 120 (manufactured by Toshiba Silicone Co., Ltd.) as component (B), and dipentaerythritol hexaacrylate as component (C). (Toago Kosei Co., Ltd. product) 60 weight part, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one (irugacure 369; Chiba) as a component (D) 25 parts by weight of Specialty Chemicals Co., Ltd., 0.04 parts by weight of SH28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) and sufficiently stirred, followed by filtration using a filter made of polypron having a pore size of 10 μm and curable composition (S1) Got.

Formation of Light Scattering Film

The above-mentioned light scattering film-forming composition (S1) was applied onto a glass substrate using a spin coater so as to have a film thickness of 6 μm, and prebaked at 80 ° C. for 5 minutes using a hot plate to form a coating film. The ultraviolet-ray whose intensity | strength is 10 mW / cm <2> was irradiated for 30 second at 365 nm using the mask of a predetermined pattern to the coating film obtained above. Ultraviolet irradiation at this time was performed in oxygen atmosphere (in air). Subsequently, it was developed for 1 minute at 25 degreeC in 0.14 weight% of tetramethylammonium hydroxide aqueous solution, and then it wash | cleaned for 1 minute with distilled water. This operation eliminated unnecessary parts. Thereafter, the substrate on which the coating film was formed was main-fired in a clean oven at 230 ° C. for 30 minutes to obtain a light scattering film.

Evaluation of Light Scattering Membranes

<Adhesiveness>

In the adhesion test of JIS K-5400 (1900) 8.5, 100 checkerboards were formed with the cutter knife in the light-scattering film | membrane formed above in accordance with the 8.5 * 2 checker scale tape method, and the adhesion test was done. At this time, the number of remaining checkerboard eyes is shown in Table 1.

<Transparency and haze measurement>

The Haze gard plas apparatus <Product No. Cat. No. 4725> (manufactured by BYK Gardner Co., Ltd.) to measure transparency (accumulated transmittance) and haze. The results are shown in Table 1.

<Flat Mars>

About the light-scattering film formed above, surface smoothness was measured by the contact type film thickness measuring apparatus (alpha) -step (made by Tencol Japan Corporation). Table 1 shows the difference between the maximum value and the minimum value when the film thickness was measured at a measurement length of 2 mm.

<Heat resistance>

About the light-scattering film | membrane formed above, the film thickness was measured by the contact type film thickness measuring apparatus (alpha) -step (made by Tencol Japan Co., Ltd.), and 250 degreeC and the further baking for 60 minutes were performed in the clean oven. After further baking, the film thickness was again measured to calculate the film residual ratio before and after the additional baking. The results are shown in Table 1.

<Formation of ITO Film>

On the light scattering film formed in the same manner as above, a sputtering apparatus was used to form an ITO film of about 3,000 kPa (the substrate having the light scattering film and the ITO film thereon on the glass substrate thus formed was then an ITO sputter substrate). I say).

Drug resistance evaluation of ITO membrane

<Alkali resistance>

The adhesiveness of the ITO film | membrane was evaluated similarly to the adhesion test of the said light scattering film | membrane with respect to the board | substrate immersed for 30 minutes at 60 degreeC in the ITO sputter | substrate board | substrate formed as mentioned above in 5% NaOH aqueous solution. The results are shown in Table 1.

<Acid resistance>

The adhesion test of the light scattering film was performed on the substrate in which the ITO sputtered substrate thus formed was immersed in HCl / FeCl ₂ · 6H ₂ O / H ₂ O = 2: 2: 1 (weight ratio) for 15 minutes at 45 ° C. Similarly, the adhesion of the ITO membrane was evaluated. The results are shown in Table 1.

<N-methylpyrrolidone (NMP) resistance>

The ITO sputter substrate thus formed was immersed in N-methylpyrrolidone (NMP) for 30 minutes at 40 ° C., and the adhesion of the ITO film was evaluated similarly to the adhesion test of the light scattering film. The results are shown in Table 1.

Moisture Resistance

The adhesiveness of the ITO film | membrane was evaluated similarly to the adhesion test of the said light scattering film | membrane with respect to the board | substrate which left the above-mentioned ITO sputter | substrate board | substrate left to stand for 24 hours in 60 degreeC and 90% humidity constant temperature bath. The results are shown in Table 1.

<Example 2>

Instead of the solution containing copolymer (A1) in Example 1, using a solution containing copolymer (A2) synthesized in Synthesis Example 2 (corresponding to 100 parts by weight (solid content) of copolymer (A2)) Was carried out in the same manner as in Example 1, except that, instead of dipentaerythritol hexaacrylate, component (C) was used, an optical scattering film-forming composition (S2) was obtained.

Using (S2) instead of (S1), a light scattering film and an ITO sputter substrate were formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 3>

After adding propylene glycol monomethyl ether acetate to a solution containing the copolymer (A1) synthesized in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer (A1), the total amount was made into a solution of 350 parts by weight. , 10 parts by weight of γ-glycidoxypropyldiethoxysilane as the silane coupling agent, 45 parts by weight of Tospearl 120 (manufactured by Toshiba Silicone Co., Ltd.) as the component (B), and dipentaerythritol hexaacrylate as the component (C). (Toago Kosei Co., Ltd.) 60 weight part, 2-methyl-1 [4- (methylthio) phenyl] -2- morpholino propane- 1-one (irugacure 907; Chiba) as a component (D) Specialty Chemicals Co., Ltd.) 30 parts by weight and 5 parts by weight of 2,4-diethyl thioxanthone were added and sufficiently stirred, and then filtered using a polypron filter having a pore diameter of 10 µm to obtain a curable composition (S3). .

A light scattering film and an ITO sputter substrate were formed and evaluated in the same manner as in Example 1 using (S3) instead of (S1). The results are shown in Table 1.

<Example 4>

Instead of using 20 parts by weight of Tospearl 120 as the light scattering particles in Example 1, except that 20 parts by weight of acrylic particles "Tech Polymer MB20X-5" (trade name, manufactured by Sekisui Kasei Co., Ltd.) was used. It carried out similarly to Example 1, and obtained the composition for light-scattering film formation (S4).

A light scattering film and an ITO sputter substrate were formed and evaluated in the same manner as in Example 1 using (S4) instead of (S1). The results are shown in Table 1.

Example 5

Instead of using 20 parts by weight of Tospearl 120 as the light scattering particles in Example 1, except that 20 parts by weight of styrene-based particle "tech polymer SBX-6" (trade name, manufactured by Sekisui Kasei Co., Ltd.) was used, In the same manner as in Example 1, a light scattering film-forming composition (S5) was obtained.

A light scattering film and an ITO sputter substrate were formed and evaluated in the same manner as in Example 1 using (S5) instead of (S1). The results are shown in Table 1.

Example 1 Example 2 Example 3 Example 4 Example 5 Light Scattering Film Adhesion 100/100 100/100 100/100 100/100 100/100 Transmittance (%) 93.7 93.7 93.9 93.4 92.4 Haze (%) 68.5 68.7 81.0 53.5 61.8 Heat resistant film remaining rate (%) 97.0 98.5 98.1 97.3 97.9 Planarization (nm) 80 100 150 180 280 Film thickness (㎛) 5.80 5.75 5.45 6.23 6.41 ITO Sputter Board Alkali resistance 100/100 100/100 100/100 100/100 100/100 Acid resistance 100/100 100/100 100/100 100/100 100/100 NMP resistance 100/100 100/100 100/100 100/100 100/100 Moisture resistance 100/100 100/100 100/100 100/100 100/100

As is clear from the above embodiment, the light scattering film of the present invention has high transparency and haze, and exhibits desirable performance as a light scattering film disposed in a cell of a transflective and reflective liquid crystal display, and also has performance as a flattening film and a protective film. It can be seen that.

According to the present invention, it is possible to efficiently scatter reflected light in semi-transmissive and reflective liquid crystal displays to realize surface illumination with uniform and high front brightness, and at the same time, light having excellent flatness, heat resistance and chemical resistance, and high adhesion to ITO film. A composition is provided that can provide a scattering film. This composition is a radiation-sensitive curable composition which removes the scattering film of the alignment mark part by an exposure and image development process, and enables accurate positioning.

In addition, a light scattering film having good efficiency is formed from the composition.

<Example 6>

Preparation of light scattering film forming composition

After diluting the solution containing the copolymer (A1) synthesized in Synthesis Example 1 (corresponding to 100 parts by weight of the copolymer (A1) (solid content)) with 250 parts by weight of propylene glycol monomethyl ether acetate, a silane coupling agent was used. 10 parts by weight of γ-glycidoxypropyl diethoxysilane, 20 parts by weight of Tospearl 120 (manufactured by Toshiba Silicone Co., Ltd.) as the component (B), and dipentaerythritol hexaacrylate as the component (C) (Doa Kosei Co., Ltd.) (Manufactured) 60 parts by weight, 2 parts by weight of 1,1'-azobis (cyclohexane-1-carbonitrile) (thermal radical generator, manufactured by Wako Pure Chemical Industries, Ltd.) as a component (D), SH28PA (Toray Dow) Corning Silicone Co., Ltd. product) 0.04 weight part was added and fully stirred, and it filtered using the polypron filter of 10 micrometers of pore diameters, and obtained curable composition (S6).

Formation of Light Scattering Film

The light scattering film-forming composition (S6) was applied onto a glass substrate using a spin coater so as to have a film thickness of 6 μm, and prebaked under a condition of 80 ° C. for 3 minutes using a hot plate to form a coating film. I was. Then, the substrate on which the coating film was formed was main-fired in the clean oven on 230 degreeC and the conditions of 1 hour, and the light-scattering film was obtained.

Evaluation of the light scattering film, formation of the ITO film, and evaluation of the chemical resistance of the ITO film were performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 7>

Preparation of light scattering film forming composition

Instead of the solution containing copolymer (A1) in Example 6, a solution containing copolymer (A2) synthesized in Synthesis Example 2 was used (corresponding to 100 parts by weight (solid content) of copolymer (A2)) Was carried out in the same manner as in Example 6, except that, instead of dipentaerythritol hexaacrylate, component (C) was used, an optical scattering film-forming composition (S7) was obtained.

A light scattering film and an ITO sputter substrate were formed and evaluated in the same manner as in Example 6 using (S7) instead of (S6). The results are shown in Table 2.

<Example 8>

Preparation of light scattering film forming composition

After diluting the solution containing the copolymer (A1) synthesized in Synthesis Example 1 (corresponding to 100 parts by weight of the copolymer (A1) (solid content)) to 250 parts by weight of propylene glycol monomethyl ether acetate, the silane coupling agent was used. 10 parts by weight of γ-glycidoxypropyldiethoxysilane, 20 parts by weight of Nipsil SS-20 (manufactured by Nippon Silica Kogyo Co., Ltd.) as component (B), and epicoat 1032H60 (bisphenol A-based polyfunctional) as component (E). After adding 100L (sulfonium salt type acid generator and Sanshin Chemical Co., Ltd. product) to Sun-Aid as an epoxy resin, Yuka Shell Epoxy Co., Ltd., and a component (F), it fully stirred, and then polypron of 100 micrometers of pore diameters. It filtered using the agent filter and obtained curable composition (S8).

A light scattering film and an ITO sputter substrate were formed and evaluated in the same manner as in Example 6 using (S8) instead of (S6). The results are shown in Table 2.

Example 9

Preparation of light scattering film forming composition

Instead of the solution containing the copolymer (A1) in Example 8, using a solution containing the copolymer (A2) synthesized in Synthesis Example 2 (corresponding to 100 parts by weight (solid content) of the copolymer (A2)) In the same manner as in Example 9, except that Tospearl 120 was used instead of NEP Seal SS-20 as the component (B), to thereby obtain a light scattering film-forming composition (S9).

A light scattering film and an ITO sputter substrate were formed and evaluated in the same manner as in Example 6 using (S9) instead of (S6). The results are shown in Table 2.

Example 6 Example 7 Example 8 Example 9 Light Scattering Film Adhesion 100/100 100/100 100/100 100/100 Transmittance (%) 93.9 94.0 93.8 94.0 Haze (%) 68.3 68.5 65.2 64.2 Heat resistant film remaining rate (%) 97.1 98.7 98.3 99.5 Planarization (nm) 85 125 345 290 Film thickness (㎛) 5.78 5.69 5.38 5.52 ITO Sputter Board Alkali resistance 100/100 100/100 100/100 100/100 Acid resistance 100/100 100/100 100/100 100/100 NMP resistance 100/100 100/100 100/100 100/100 Moisture resistance 100/100 100/100 100/100 100/100

<Example 10>

Preparation of light scattering film forming composition

After adding propylene glycol monomethyl ether acetate to a solution containing the copolymer (A1) synthesized in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer (A1), the total amount was made into a solution of 350 parts by weight. , 10 parts by weight of γ-glycidoxypropyldiethoxysilane as the silane coupling agent, 20 parts by weight of the acrylic particle "Tech Polymer MB20X-5" (trade name, manufactured by Sekisui Kasei Co., Ltd.) as the component (B), component 60 parts by weight of dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.) as (C) and 1,1'-azobis (cyclohexane-carbonitrile) as a component (D) (thermal radical generator, 0.04 part by weight of Wako Junyaku Co., Ltd.) and SH28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.), and the mixture is sufficiently stirred, and filtered using a polypron filter having a pore diameter of 10 µm, and the curable composition (S10) is Got it.

Formation and evaluation of the light scattering film, formation of the ITO film and evaluation of chemical resistance were performed in the same manner as in Example 6. The results are shown in Table 3.

<Example 11>

Preparation of light scattering film forming composition

Instead of using 20 parts by weight of the tech polymer MB20X-5 as component (B) in Example 10, 20 parts by weight of the styrene-based fine particles "tech polymer SBX-6" (trade name, manufactured by Sekisui Kasei Co., Ltd.) Others were carried out similarly to Example 10, and obtained the composition for light-scattering film formation (S11).

The light scattering film and the ITO sputtering substrate were formed and evaluated in the same manner as in Example 10 using (S11) instead of (S10). The results are shown in Table 3.

Example 10 Example 11 Light Scattering Film Adhesion 100/100 100/100 Transmittance (%) 93.6 92.6 Haze (%) 53.2 61.5 Heat resistant film remaining rate (%) 97.3 98.1 Planarization (nm) 210 320 Film thickness (㎛) 6.12 6.31 ITO Sputter Board Alkali resistance 100/100 100/100 Acid resistance 100/100 100/100 NMP resistance 100/100 100/100 Moisture resistance 100/100 100/100

According to the present invention, it is possible to efficiently scatter reflected light in semi-transmissive and reflective liquid crystal displays to realize surface illumination with uniform and high front brightness, and at the same time, light having excellent flatness, heat resistance and chemical resistance, and high adhesion to ITO film. A composition is provided that can provide a scattering film. This composition is a radiation-sensitive curable composition which removes the scattering film of the alignment mark part by an exposure and image development process, and enables accurate positioning.

In addition, a light scattering film having good efficiency is formed from the composition.

Claims (10)

(A) at least one carboxylic acid compound selected from the group consisting of (a1) unsaturated carboxylic acids and unsaturated carboxylic anhydrides, (a2) unsaturated compounds containing an epoxy group, and (a3) copolymers of olefinically unsaturated compounds other than the compounds (al) and (a2), and (B) light scattering material Curable composition for forming a light-scattering film, characterized in that it contains. The composition according to claim 1, wherein the copolymer (A) is derived from 1 to 50% by weight of the structural unit derived from the carboxylic acid compound (a1) and the epoxy group-containing unsaturated compound (a2) based on the copolymer (a1). Curable composition containing 5 to 80 weight% of units and 1 to 40 weight% of structural units derived from an olefinic unsaturated compound (a3). The curable composition according to claim 1, wherein the light scattering material (B) is an inorganic oxide particle, an organic particle, or a mineral particle. The curable composition according to claim 1, further comprising a polyfunctional monomer (C) and a polymerization initiator (D). The curable composition according to claim 4, wherein the polyfunctional monomer (C) is a bifunctional or higher (meth) acrylate. The curable composition of claim 1, wherein the polymerization initiator (D) has the ability to generate radicals by heat and / or light to initiate polymerization of the polyfunctional monomer (C). The curable composition according to claim 1, further comprising an epoxy compound (E) and an acid generator (F). The curable composition according to claim 7, wherein the epoxy compound (E) is a bisphenol A epoxy resin, a novolac epoxy resin or a cyclic aliphatic epoxy resin. The curable composition according to claim 7, wherein the acid generator (F) is a photo acid generator or a thermal acid generator. A light scattering film formed from the curable composition according to claim 1.