KR19980080195A - Thermosetting coloring composition for color filter formation - Google Patents

Abstract

The present invention relates to a thermosetting coloring composition for forming a color filter, which can be used to form a color filter by laser transfer, comprising forming a color filter comprising 5-50% by weight of solids and a residual amount of solvent based on the total amount In the coloring composition for the solid, the solid content is 20-60% by weight of the bonding resin represented by the formula (1), 10-40% by weight of the crosslinking agent, 0.1-10% by weight of the polymerization initiator, 30-60% by weight of the coloring material And 0-10% by weight of other additives.

Wherein R 1 is hydrogen or methyl, R 2 is an alkyl group having 1-12 carbon atoms, a hydroxyalkyl group having 2-10 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group having 3-10 carbon atoms, or a benzyl group, R 3 is an alkyl group having 1-12 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group or benzyl group having 3-10 carbon atoms, X is hydrogen, a vinyl group or an epoxy group, and 0.1 ≦ a ≦ 0.65, 0.3 ≦ b ≦ 0.8 and 0 ≦ c ≦ 0.2 (where a, b and c are mole fractions, where a + b + c = 1). The thermosetting coloring composition for a color filter according to the present invention is a composition which can be used when forming a color filter by a laser transfer method which is easier to process and has better yield than a conventional method. The color composition for color filters according to the present invention is a composition which can be used when forming a color filter by a laser transfer method which is easier to process and has better yield than a conventional method.

Description

Thermosetting coloring composition for color filter formation

The present invention relates to a thermosetting coloring composition. More specifically, the present invention relates to thermosetting coloring compositions that can be used for the production of color filters using laser transfer methods.

The color filter is essential to realize the multi-color of the liquid crystal display device. In general, the items required for the color filter should have spectral characteristics close to those of the color television, and the chromaticity characteristics will not be changed even when exposed to light for a long time. It should be excellent in light resistance, smooth surface of color filter and no foreign protrusions, excellent heat resistance, so that the spectral characteristics will not change in the subsequent heat treatment process, and the pixel accuracy of the color filter should be consistent with the transparent electrode. And good chemical resistance, good compatibility with seal adhesive, no pin hole or color unevenness.

Moreover, in accordance with the trend toward thinner and larger liquid crystal display devices, in addition to the various requirements mentioned above, color filters are not only flawless and large, but also low cost, yield improvement, and process shortening are required.

Such a color filter is usually applied to a glass substrate by applying a photosensitive coloring composition obtained by dispersing a coloring material such as a pigment in a mixture of a thermoplastic copolymerizable compound and a photosensitive compound to a glass substrate, and then performing a series of processes of developing with an alkaline solution after ultraviolet exposure. It is obtained by forming a blue color filter pattern.

However, this method has a problem that the manufacturing process is long and complicated and the yield is low, and thus, a method of manufacturing a kali filter using a laser transfer method has been proposed as an improvement.

Laser transfer has been mainly used in fields such as printing, typesetting, photography, and the like, and accepts a material (glass or polymer) in a desired pattern from a donor film including a layer to which a material to be transferred (such as a dye or a pigment) is applied. This method uses the principle of transferring onto a film, which has the advantage that the desired pattern can be transferred to the correct position. Recently, a method of applying to forming a black matrix, a spacer, a color filter, etc. in the manufacture of a liquid crystal display device is examined. It is becoming.

The structure of the donor film commonly used in such a laser transfer method may vary depending on the physicochemical properties of the material to be transferred and the energy source used for the transfer. On the base film serving as a support, light is transferred to the base film by absorbing light. It has a structure consisting of a propulsion layer containing aluminum, carbon, IR dyes, etc., which are converted into energy, and a transfer layer containing the material to be transferred.

In particular, the transfer layer may vary depending on the kind of the transfer body formed by the transfer, for example, when the formed transfer body is a spacer, the transfer layer includes a material for forming a spacer.

Moreover, when the transfer body formed is a color filter, the donor film by which the coloring composition for color filter formation was apply | coated on the said propulsion layer is used. The present invention relates to a color composition for forming a color filter which can be used in the production of a color filter by laser transfer.

The technical problem to be achieved by the present invention is to provide a thermosetting coloring composition for forming a color filter which can be used when manufacturing a color filter by a laser transfer method which is simpler than a conventional pigment dispersion method and exhibits high yield.

The problem of the present invention is a coloring composition for forming a color filter comprising 5-50% by weight of solids and a residual amount of solvent, based on the total amount, wherein the solids are represented by the following Chemical Formula 1 of 20-60% by weight: Forming a color filter comprising a binding resin, 10-40% by weight of a crosslinking agent, 0.1-10% by weight of a polymerization initiator, 30-60% by weight of a coloring material and 0-10% by weight of other additives It is made of a coloring composition for.

Formula 1

Wherein R 1 is hydrogen or a methyl group,

R2 is an alkyl group having 1-12 carbon atoms, a hydroxyalkyl group having 2-10 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group having 3-10 carbon atoms, or a benzyl group,

R3 is an alkyl group having 1-12 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group having 3-10 carbon atoms, or a benzyl group,

X is hydrogen, a vinyl group or an epoxy group,

0.1 ≦ a ≦ 0.65, 0.3 ≦ b ≦ 0.8 and 0 ≦ c ≦ 0.2 (where a, b and c are mole fractions, where a + b + c = 1).

In the thermosetting coloring composition for forming a color filter according to the present invention, first, the bonding resin of the formula is an acrylic resin obtained by polymerizing an unsaturated organic acid containing an hydroxyl group, an unsaturated organic acid ester and an unsaturated organic acid ester containing an epoxy or vinyl group.

At this time, as the unsaturated organic acid containing a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, N-methylol acrylamide or Allyl alcohol may be used. ,

Unsaturated organic acid esters include aliphatic alkyl (meth) acrylates; Or phenyl (meth) acrylate, 2- or 4-chlorophenyl (meth) acrylate, 2- or 4-nitrophenylamino (meth) acrylate, benzyl (meth) acrylate, 2- or 4-chlorobenzyl ( Aromatic alkyl (meth) acrylates such as meta) acrylate, 2- or 4-nitrobenzyl (meth) acrylate or 2- or 4-dimethylaminophenyl (meth) acrylate; and the like.

Further, examples of the unsaturated organic acid ester containing the epoxy or vinyl group include allyl (meth) acrylate, butylglycidyl (meth) acrylate or glycidyl (meth) acrylate.

The compound represented by Chemical Formula 1 preferably has a glass transition temperature of 30-120 ° C. and a weight average molecular weight of 1000-100,000. If the glass transition temperature is less than 30 ° C, heat resistance is poor, and if the glass transition temperature is higher than 120 ° C, a problem occurs that the accuracy of the color filter pattern after transfer falls. In addition, when the weight average molecular weight is out of the above range, it is not preferable because the heat resistance and transfer characteristics are poor.

Meanwhile, in the coloring composition for forming a color filter according to the present invention, the crosslinking agent is a polyfunctional compound and an oligomer thereof, and specific examples thereof include polyfunctional alcohols such as ethylene glycol, propylene glycol, polyalcohol, polyglycol, and oligomers thereof; Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-cyclohexanedi (meth) acrylate, trimethylol tri (meth) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, Polyfunctional acrylates such as sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, tetramethylene glycol di (meth) acrylate and the like; Epoxy group-containing polyfunctional compounds such as bisphenol A diglycidyl ether, glycidyl ether of boric acid, allyl glycidyl ether, polyalcohol-polyglycol type epoxy resins, glycerin triglycidyl ether resins, and oligomers thereof have.

In addition, benzoyl peroxide, t-butyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, or the like may be used as the polymerization initiator.

As a coloring agent, CI yellow pigment 20, 24, 83, 86, 93, 109, 110, 117, 125, 137, 138, 139, 147, 153, 166,168; CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; CI blue pigment 15, 15: 1, 15: 3, 15: 4, 15: 6, 15: 9, 22, 60 64; CI green pigment 7,36; Or a mixture of at least two pigments selected from the group consisting of CI violet pigments 19, 23, 29, 30, 37, 40 and 50. Preferably, from the mixture of CI red pigment 177 and CI yellow pigment 83 as a red pigment, from the mixture of CI green pigment 36 and CI violet pigment 23 as a green pigment, and CI blue pigment 15 as a blue pigment: 6 and CI violet pigment 23, respectively.

In general, various dispersion means such as a three-bone roll mill, a double-roll mill, a sand mill, and a bead mill may be used for dispersing the coloring material, and an appropriate dispersing aid may be added to improve the dispersion. Derivatives such as various surfactants, pigments, and the like may be used as the dispersing aid, and these may prevent re-agglomeration of the pigment after dispersion, thereby forming a color filter having excellent transparency.

Moreover, the said solvent can disperse | distribute pigment | dye materials, such as a pigment fully, For example, cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, and cyclohexa. Nol, ethyl cellosolve and propylene glycol monomethyl ether acetate may be used alone or in combination of two or more.

In addition, the coloring composition for forming a color filter according to the present invention may further include a slip agent, a leveling agent, a sagging agent or an antifoaming agent. Increasing the coatability makes it possible to obtain a good color filter pattern.

Conventional methods for forming a color filter by laser transfer using the color composition for color filter formation according to the present invention are as follows:

First, in preparing a donor film, a polyethylene terephthalate film, a polycarbonate, etc. may be used as the base film. Upon absorbing light, a black layer (propulsion layer) is formed on the base film to release nitrogen or hydrogen gas or release heat to provide transfer energy, and then an intermediate layer and a color filter-forming composition are formed on the black layer. This coated color layer is formed sequentially. The intermediate layer may be omitted but is preferably formed to prevent subsequent color layers from being contaminated by the black layer and to improve the smoothness of the color filters formed.

The color layer is formed by applying a composition for forming a color filter to a thickness of about 1 to 2 μm, and may be used as a gravure printing method, a die coating method or a bar coating method (bar). coating) and the like, and preferably, a bar coating method is used.

Subsequently, a color filter is formed by placing a donor film at a predetermined distance from the transparent substrate on which the black matrix is formed and irradiating a laser. The pattern is optionally formed in the order of red, green, and blue, and the color filter is thermally cured. To form.

Transfer method The color composition for color filter manufacturing maintains a uniform composition during the transfer process and can be obtained a color filter pattern with a high accuracy in good surface state should not be deformed or evaporated by heat generated in the propelling layer. In the present invention, an acrylic resin of Chemical Formula 1 is used as the binder resin, and at least one crosslinking agent having excellent compatibility is added thereto to prepare a coloring composition. At this time, it is preferable that the acid value of binder resin is 70-130 mgKOH in consideration of adhesiveness with glass.

The color filter thus formed is reduced in price due to the shortening of the manufacturing process compared to the color filter formed by a conventional method, and is excellent in high precision, high color purity, chemical resistance and heat resistance.

Hereinafter, a method of manufacturing a color filter according to an embodiment of the present invention will be described in more detail.

Polymerization of Acrylic Resin

Methacrylic acid, butyl methacrylate and glycidyl acrylate (40:50:10 molar ratio) are dissolved in propylene glycol monomethyl ether acetate and solution-polymerized at 60 ° C. using azobisisobutyronitrile as a polymerization initiator to acryl Copolymer resin was prepared. At this time, the weight average molecular weight of the produced copolymer resin was 30,000 and the glass transition temperature was 80 ℃.

Production of coloring material

After dispersing the CI red pigment 177 and the CI yellow pigment 83 with a bead mill using a dispersant to a particle size of about 0.1㎛, these dispersions were mixed to prepare a red pigment material according to the NTSC standard. In a similar manner, the green coloring material was prepared using a mixture of CI green pigment 36 and CI yellow pigment 83, and the blue coloring material using a mixture of CI blue pigment 15: 6 and CI violet pigment 23.

Preparation of the composition for color filter formation

As shown in Table 1 below, pentaerythritol triacrylate and propylene glycol (8: 2 weight ratio) were used as an acrylic copolymer resin and a crosslinking agent, and a red pigment and benzoyl peroxide were mixed with propylene monomethyl ether acetate and cyclohexane (85). Dissolved in a mixed solvent of: 15% by weight to prepare a uniform red colored composition having a total solid content of 20-22% by weight of the total composition.

In addition, instead of the red pigment, using a green pigment, a blue pigment, respectively, to prepare a corresponding green and blue pigment.

Red coloring composition Green coloring composition Blue coloring composition Acrylic resin 6% by weight 8% by weight 8% by weight Crosslinking agent 3.3 wt% 4.3 wt% 4.7% by weight Pigment 7 wt% 5.5% by weight 4.8 wt% Initiator 1.5 wt% 2.1 wt% 2.2 wt% Other additives 2.2 wt% 2.1 wt% 2 wt% menstruum 80 wt% 78% by weight 78% by weight

* The weight percentage is based on the total amount of the composition.

Production of donor film

Using a polyethylene terephthalate as a base film, the black layer made of a carbon compound and an intermediate layer for protecting a subsequent color layer were sequentially formed on the base film, and then the red coloring composition was bar-coated to a thickness of 1.2 μm to red A donor film was prepared.

Subsequently, green and blue donor films were produced using green coloring composition and blue coloring composition, respectively.

Manufacture of color filters

First, the red donor film was placed at a position spaced apart from the transparent substrate on which the black matrix was formed, and the laser layer was transferred to transfer the color layer onto the transparent substrate.

Subsequently, laser transfer was also performed on the green and blue donor films to form all of the red, green, and blue patterns on the transparent substrate, and then thermally cured at 230 ° C. under a nitrogen atmosphere to prepare a color filter.

The thermosetting coloring composition for forming a color filter according to the present invention is a composition which can be used when forming a color filter by a laser transfer method which is easier to process and has better yield than a conventional method.

Claims (8)

In the coloring composition for forming a color filter comprising 5-50% by weight solids and the remaining amount of the solvent based on the total amount, the solids are 20-60% by weight of the binding resin represented by the following formula (1), 10 A thermosetting coloring composition for forming a color filter, comprising -40% by weight of a crosslinking agent, 0.1-10% by weight of a polymerization initiator, 30-60% by weight of a coloring material and 0-10% by weight of other additives: Formula 1 Wherein R 1 is hydrogen or a methyl group, R2 is an alkyl group having 1-12 carbon atoms, a hydroxyalkyl group having 2-10 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group having 3-10 carbon atoms, or a benzyl group, R3 is an alkyl group having 1-12 carbon atoms, a substituted or unsubstituted aromatic ring group, a cycloalkyl group having 3-10 carbon atoms, or a benzyl group, X is hydrogen, a vinyl group or an epoxy group, 0.1 ≦ a ≦ 0.65, 0.3 ≦ b ≦ 0.8 and 0 ≦ c ≦ 0.2 (where a, b and c are mole fractions, where a + b + c = 1). The method of claim 1, wherein the bonding resin of Formula 1 is an acrylic resin obtained by polymerizing an unsaturated organic acid, an unsaturated organic acid ester including a hydroxyl group, or an unsaturated organic acid ester including an epoxy or vinyl group. Thermosetting coloring composition. The unsaturated organic acid according to claim 2, wherein the unsaturated organic acid containing a hydroxyl group is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, N-methyl A thermosetting coloring composition for forming a color filter, characterized in that selected from rollacrylamide or allyl alcohol. The thermosetting coloring composition for forming a color filter according to claim 2, wherein the unsaturated organic acid ester is an aliphatic alkyl (meth) acrylate or an aromatic alkyl (meth) acrylate. The method of claim 4, wherein the aromatic alkyl (meth) acrylate is phenyl (meth) acrylate, 2- or 4-chlorophenyl (meth) acrylate, 2- or 4-nitrophenylamino (meth) acrylate, benzyl A thermosetting coloring composition for forming a color filter, characterized in that it is selected from the group consisting of (meth) acrylate, 2- or 4-chlorobenzyl (meth) acrylate and 2- or 4-nitrobenzyl (meth) acrylate. 3. Color filter formation according to claim 2, wherein the unsaturated organic acid ester comprising an epoxy or vinyl group is selected from allyl (meth) acrylate, butylglycidyl (meth) acrylate or glycidyl (meth) acrylate. Thermosetting coloring composition for. The thermosetting coloring composition for forming a color filter according to claim 1, wherein the glass transition temperature of the bonding resin of Chemical Formula 1 is 30 to 120 ° C. The thermosetting coloring composition for forming a color filter according to claim 1, wherein the weight average molecular weight of the bonding resin of Chemical Formula 1 is 1000-100,000.