KR20110097112A - Curable resin composition for ink-jet printing, color filter and liquid crystal display device - Google Patents

Abstract

(상기 화학식 1에서 R₁은 서로 독립적으로 에틸, (이소)프로필, (폴리)테트라에틸렌, (폴리)에틸렌 글리콜 또는 (폴리)프로필렌 글리콜이고, R₂는 수소 또는 메틸이며, Rf는 불소계 폴리올로 하기 화학식 2로 표현된다.)
<화학식 2>

(상기 화학식 2에서 R₃는 메틸 또는 (폴리)에틸렌 글리콜, (폴리)프로필렌 글리콜, (폴리)테트라에틸렌 글리콜 구조로 서로 대칭이며, R4는 탄소 또는 CF₂O-(CF₂CF₂O)_a-(CF2O)_b-OCF₂이고, a과 b는 각각 0 또는 1이상의 정수로서 a+b는 1 내지 20의 정수이며, R₅는 각각 서로 독립적으로 수소, 메틸, 에틸, 프로필, 부틸 또는 CH₂-O-CH₂-C _P F_{2 P +1} 이고, P는 1 내지 10의 정수이며, n은 1 내지 20의 정수이다.)
상기 잉크젯용 착색 경화성 수지 조성물은 적하된 잉크가 격벽내에서 젖음성을 유지하도록 하고, 베이킹 후에도 격벽과 잉크간의 이격발생을 억제시켜 색빠짐 현상이 발생하지 않도록 도와준다. 또한 과량을 투입해도 얼룩이 발생하지 않으며, 경화시에 화합물 내의 아크릴레이트기가 반응함으로써 잉크의 경도, 내열성 등의 물성을 유지 및 향상시켜 주는 역할을 하게 된다. 따라서 상기 잉크젯용 경화성 수지 조성물은 컬러필터와 액정표시장치의 제조에 유용하게 적용될 수 있다. The present invention relates to a curable resin composition for an inkjet, a color filter, and a liquid crystal display device having the same.
Curable resin composition for inkjets which concerns on this invention contains the curable monomer (A) containing a fluorine-type urethane acrylate represented by following formula (1), binder resin (B), a solvent (D), and a polymerization initiator (E).
<Formula 1>

(In Formula 1, R ₁ is independently of each other ethyl, (iso) propyl, (poly) tetraethylene, (poly) ethylene glycol or (poly) propylene glycol, R ₂ is hydrogen or methyl, Rf is a fluorine-based polyol It is represented by the following formula (2).
<Formula 2>

(In Formula 2, R ₃ is symmetric with each other in the structure of methyl or (poly) ethylene glycol, (poly) propylene glycol, (poly) tetraethylene glycol, and R4 is carbon or CF ₂ O- (CF ₂ CF ₂ O) _a — (CF ₂ O) _b —OCF ₂ , a and b are each an integer of 0 or greater than 1, a + b is an integer from 1 to 20, and R ₅ is each independently hydrogen, methyl, ethyl, propyl, butyl or CH ₂ -O-CH ₂ -C _P F _{2 P +1} , P is an integer from 1 to 10, n is an integer from 1 to 20.)
The color-curable resin composition for inkjet helps the dropped ink maintain wettability in the partition wall and suppresses the separation between the partition wall and the ink even after baking, thereby preventing color loss. In addition, staining does not occur even when an excessive amount is added, and an acrylate group in the compound reacts during curing to play a role of maintaining and improving physical properties such as hardness and heat resistance of the ink. Therefore, the curable resin composition for inkjet may be usefully applied to the manufacture of color filters and liquid crystal displays.

Description

Curable resin composition for ink jet, color filter and liquid crystal display device having same {CURABLE RESIN COMPOSITION FOR INK-JET PRINTING, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a curable resin composition for an inkjet, a color filter, and a liquid crystal display device having the same.

The color filter used for a liquid crystal display device is manufactured by the pigment dispersion method mostly. In the pigment dispersion method, a light-shielding material thin film made of chromium is formed into a pattern by photolithography and development, and blue, green, and red photosensitive resins are coated on the partition walls thus formed by spin coating, slit coating, etc. for each color. Patterning is performed by photolithography and development, respectively, and a method of manufacturing by curing.

This method has the advantage that the applied film thickness is uniform, but when the pattern of each color is formed, a loss of about 70% of the applied material is removed, and expensive installation cost of an exposure machine, a developing machine, a curing device, etc. Is required, and also because the process line is long, yield management is difficult. Recently, as the size of the display material substrate increases, the cost of the process and installation equipment is expected to increase.

As an alternative to this, an inkjet method has been proposed. The inkjet method is a technique of spraying the curable resin composition only into the openings of the partition walls formed by using the inkjet head to realize an image in which each ink is colored, and can simultaneously color a plurality of colors including red, green, and blue to produce a manufacturing process, Time and cost can be greatly reduced. In the inkjet method using such a curable resin composition, a specific amount of ink is injected into the pixel openings of the partition walls to satisfy a desired color coordinate or film thickness.

In general, however, the bulkhead used in photolithography has a weak repulsion property with the loaded ink, and thus the amount of ink cannot be filled in the bulkhead or the ink overflows to adjacent pixels, thereby increasing the repulsive force in the partition composition. The method of adding a material to increase the repulsive force, such as by adding a material or after the partition wall fluorine plasma treatment is used.

However, in this method, due to the repulsive force of the partition wall, the dropped ink does not spread properly in the glass in the pixel or is separated from the partition wall after the baking process, and color fading occurs, and this additional process is a manufacturing process and time which is an advantage of the inkjet method. This results in lowering the efficiency of saving money. In addition, in the conventional curable resin composition, a leveling agent may be used as one of the methods for improving the composition to control the shape of the ink in the pixels such as color dropout and separation, but it may be effective only when the amount is added to the total composition content. In addition, problems such as overflow of partition walls, surface abnormalities, and deterioration of intrinsic properties of the curable resin composition occur due to excessive input.

Accordingly, the present invention can increase the leveling property of the curable resin composition for inkjet to suppress the color fading phenomenon caused by the separation caused by the repulsive force with the partition after baking, the ink can be made to have an even thickness overall. It is not an object of the present invention to provide a curable resin composition for inkjet, which can overcome partition overflow and physical property degradation due to excessive input, which is a limitation of the existing leveling agent.

Another object of the present invention is to provide a color filter comprising a black matrix or a color layer formed by applying and curing the curable resin composition for inkjet in a predetermined pattern.

Another object of the present invention is to provide a liquid crystal display device having the color filter.

In order to achieve the above object, the present invention comprises a curable monomer (A), a binder resin (B), a solvent (D) and a polymerization initiator (E) containing a fluorine-based urethane acrylate represented by the following formula (1) The curable resin composition for inkjets provided is provided.

<Formula 1>

(In Formula 1, R ₁ is independently of each other ethyl, (iso) propyl, (poly) tetraethylene, (poly) ethylene glycol or (poly) propylene glycol, R ₂ is hydrogen or methyl, Rf is a fluorine-based polyol It is represented by the following formula (2).

<Formula 2>

(In Formula 2, R ₃ is symmetric with each other in the structure of methyl or (poly) ethylene glycol, (poly) propylene glycol, (poly) tetraethylene glycol, and R4 is carbon or CF ₂ O- (CF ₂ CF ₂ O) _a — (CF ₂ O) _b —OCF ₂ , a and b are each an integer of 0 or greater than 1, a + b is an integer from 1 to 20, and R ₅ is each independently hydrogen, methyl, ethyl, propyl, butyl or CH ₂ -O-CH ₂ -C _P F _{2 P +1} , P is an integer from 1 to 10, n is an integer from 1 to 20.)

The inkjet curable resin composition may further include a colorant (C).

The fluorine-based urethane acrylate may be included 1 to 50 parts by weight based on 100 parts by weight of the total curable resin composition for inkjet.

In order to achieve another object of the present invention, the present invention provides a color filter comprising a black matrix or a color layer formed by applying the curable resin composition for inkjet in a predetermined pattern and then curing.

In order to achieve another object of the present invention, the present invention provides a liquid crystal display device comprising the color filter.

The colored curable resin composition for inkjet according to the present invention contains a fluorine-based urethane acrylate having a predetermined structure so that the dropped ink maintains the wettability in the partition wall and suppresses the separation between the partition wall and the ink even after baking, thereby causing color loss. It helps to avoid the phenomenon. In addition, staining does not occur even when an excessive amount is added, and an acrylate group in the compound reacts during curing to play a role of maintaining and improving physical properties such as hardness and heat resistance of the ink. Therefore, the curable resin composition for inkjet may be usefully applied to the manufacture of color filters and liquid crystal displays.

FIG. 1 is a photograph showing the surface state of the inkjet curable resin composition of Comparative Example 2 after spin coating on glass and cured in a convection oven at 230 ° C. for 30 minutes.
Figure 2 shows the results of photographing the surface photograph between the pixel and the ink after forming a pattern using the curable resin composition for inkjet prepared in Example 2 and Comparative Example 3, Figure 2a is an inkjet prepared in Example 2 11 is a photograph corresponding to dropping 11 drops of curable resin composition, Figure 2b is a photograph corresponding to 15 drops of the curable resin composition for inkjet prepared in Example 2, Figure 2c is prepared in Comparative Example 3 It is a photograph corresponding to 11 drops of one inkjet curable resin composition, and FIG. 2D is a photograph corresponding to 15 drops of the inkjet curable resin composition prepared in Comparative Example 3. FIG.

Hereinafter, the present invention will be described in more detail.

The curable resin composition for inkjet according to the present invention contains a curable monomer (A), a binder resin (B), a solvent (D) and a polymerization initiator (E), and may further include a colorant (C). In addition, the inkjet curable resin composition may further include various additives (F) generally used in the art, if necessary.

Curable Monomer (A)

The curable monomer contains a fluorine-based urethane acrylate represented by the following formula (1).

<Formula 1>

(In Formula 1, R ₁ is independently of each other ethyl, (iso) propyl, (poly) tetraethylene, (poly) ethylene glycol or (poly) propylene glycol, R ₂ is hydrogen or methyl, Rf is a fluorine-based polyol It is represented by the following formula (2).

<Formula 2>

(In Formula 2, R ₃ is symmetric with each other in the structure of methyl or (poly) ethylene glycol, (poly) propylene glycol, (poly) tetraethylene glycol, and R4 is carbon or CF ₂ O- (CF ₂ CF ₂ O) _a — (CF ₂ O) _b —OCF ₂ , a and b are each an integer of 0 or greater than 1, a + b is an integer from 1 to 20, and R ₅ is each independently hydrogen, methyl, ethyl, propyl, butyl or CH ₂ -O-CH ₂ -C _P F _{2 P +1} , P is an integer from 1 to 10, n is an integer from 1 to 20.)

The fluorine-based urethane acrylate represented by the formula (1) can be easily obtained by reacting the fluorine-based polyol and (meth) acrylic isocyanate.

The fluorine-based polyol includes fluorine and at least one ether bond in its molecular structure, and the fluorine may be included in the polyol main chain or in the side chain.

In the fluorine-based urethane acrylate represented by the general formula (1), the main chain of the fluorine-based polyol serves as a leveling agent to maintain the flatness upon dropping the curable resin composition for inkjet according to the present invention by an inkjet method, the curable resin composition for inkjet dropped It helps to maintain the wettability in the bulkhead, and prevents the color separation from occurring by suppressing the separation between the bulkhead after baking. In addition, staining does not occur even when an excessive amount of the fluorine-based urethane acrylate represented by Chemical Formula 1 is added to conventional leveling agents, and acrylate groups react during curing to maintain and improve physical properties such as hardness and heat resistance of the ink.

The fluorine-based urethane acrylate represented by Formula 1 is not limited, but may preferably include at least one selected from compounds represented by Formula 3 or 4.

<Formula 3>

In Formula 3 n is 1 to 20, R ₆ is hydrogen or methyl.

<Formula 4>

In Formula 4, l, m and n are each an integer of 1 or more, and m + n is an integer of 1 to 20.

The curable monomer according to the present invention can be used together with other curable monomers having a bifunctional or higher functional group in addition to the fluorine-based urethane acrylate represented by the formula (1) as necessary.

Specific examples of the curable monomer having a bifunctional or higher functional group are as follows.

As the bifunctional curable monomer, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, nonanediol dimethacrylate 1,4-butanedioldi Acrylate, 1,4-butanediol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene Glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol methacrylate, tetramethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,3-butyl Len glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, tricyclodecane dimethyrol diacrylate, tricycle Rodecane dimethyrol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, bisphenol epoxy diacrylate, dimethol tricyclodecane diacrylate, dimethol dicyclopentanedi Acrylate, 2-n-butyl-2-ethyl-1,3-propanedioldiacrylate, cyclohexanedimethanodiacrylate, cyclohexanedimethanoldimethacrylate, ethoxylated neopentylglycol diacrylate, Ethoxylated neopentyl glycol dimethacrylate, propoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol dimethacrylate, hydroxy pivalate neopentyl glycol diacrylate, ethoxylated bisphenol A diacrylamide Ethoxylated Bisphenol A Dimethacrylate, Propoxylated Bisphenol Aacrylate, Propoxylated Bisphenol A Dimetharate Relate, dipentaerythritol diacrylate, dipentaerythritol dimethacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, hexamethylene glycol diacrylate, bisphenol-A diacrylate, trimetholol Propanediacrylate, trimetholpropanedimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, hexanediacrylate, hexanedimethacrylate, glycerin diacrylate, glycerin dimethacrylate , Propylene glycol diacrylate, dicyclopentanyl diacrylate, triglycerol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, tetrabromobisphenol A dimethacrylate, dicyclopentanyldimetha Acrylate, glycerol dimethacrylate, trigly Roldi may be a methacrylate or the like.

As a trifunctional curable monomer, a trimethol propane triacrylate, a trimethol propane trimethacrylate, a pentaerythritol triacrylate, a pentaerythritol trimethacrylate, a tetramethylol methane triacrylate, tetramethylol Propane triacrylate, tri (2-hydroxyethyl isocyanate) triacrylate, ethoxylated trimetholpropane triacrylate, propoxylated trimetholpropane triacrylate, caprolactone modified trimetholpropane triacrylate, Ethoxy isocyanuric acid triacrylate, propoxylate glycerin triacrylate, sorbitol triacrylate, sorbitol trimethacrylate, trimethyl propane triacrylate, trimethyl propane trimethacrylate, tris (hydroxyethyl) isocyanate tri Acrylate, trimethylol Tantriacrylate, trimethylol ethane trimethacrylate, glycerin triacrylate, glycerin trimethacrylate, tetratrimethylolpropane triacrylate, tetratrimethylolpropane trimethacrylate, ethylene isocyanate oxide modified tree Acrylate, isocyanate ethylene oxide modified trimethacrylate, etc. are mentioned.

4-functional curable monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimetholpropane tetraacrylate, ditrimethyrolpropane tetramethacrylate, dipentaerythritol tetraacrylate, tetra Methylol methane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerine tetraacrylate, glycerine tetramethacrylate, etc. are mentioned.

(5) As a functional type curable monomer, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate, etc. are mentioned. have.

Examples of the 6-functional curable monomer include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

1-50 weight part is preferable with respect to 100 weight part of whole curable resin compositions for inkjets, and, as for content of the said curable monomer, 1-30 weight part is more preferable. If the content is less than 1 part by weight, the degree of curing decreases, making it difficult to form a pattern having a desired thickness. If the content exceeds 50 parts by weight, a problem of increasing the viscosity of the composition may occur.

In addition, the fluorine-based urethane acrylate represented by the formula (1) is preferably included in 50 parts by weight or less based on 100 parts by weight of the total curable monomer. When the content of the fluorine-based urethane acrylate exceeds 50 parts by weight based on the above standard, the effect of flatness may be saturated, and there is a fear that the hardness may be lowered.

Binder Resin (B)

The binder resin can be used without limitation so long as it is generally used in the art. Preferably, an acrylic binder resin can be used.

Specific examples of the acrylic binder resin include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2-acryloxyethyl hydrogen phthalate, 2-acryloxypropyl hydrogen phthalate, and 2-acryloxypropyl hexahydrogen. Phthalate, isobutyl acrylate, t-butyl acrylate, lauryl acrylate, glycidyl acrylate, alkyl acrylate, steacrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2-hydroxy Acrylate, trimethoxybutyl acrylate, ethylcarbitol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl Acrylate, 2-hydroxy-3-phenoxypropylacrylate and methacrylates thereof, 3-ple Acrylate containing halogen compounds, such as oroethyl acrylate and 4-fluoropropyl acrylate, and their methacrylates, The acrylate containing siloxane groups, such as triethylsiloxane ethyl acrylate, and their methacrylates It may be a binder resin formed by polymerizing at least one selected from the group consisting of olefins having an aromatic such as styrene, styrene, and 4-methoxystyrene.

It is preferable that the said binder resin is contained in 5-40 weight part with respect to 100 weight part of whole curable resin compositions for inkjets. If the content is less than 5 parts by weight of adhesion (adhesion) as well as the physical properties such as strength, heat resistance and chemical resistance of the formed pattern may be lowered, if the content exceeds 40 parts by weight there is a problem that the viscosity of the composition is increased .

Colorant (C)

The curable resin composition for inkjet according to the present invention may further include a colorant. The colorant is not limited as long as it is used in the art, and may include an organic pigment or an inorganic pigment.

Examples of the organic pigments and inorganic pigments include compounds classified as pigments in the color index (published by The society of Dyers and Colorists), and more specifically, the organic pigments and inorganic pigments may have the following color indexes. Although pigment of (CI) number is mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 125, C.I. Pigment Yellow 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 173, C.I. Pigment Yellow 194, C.I. Yellow pigments such as pigment yellow 214;

C.I. Pigment Orange 13, C.I. Pigment Orange 31, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 42, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Orange pigments such as pigment orange 73;

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I Pigment Red 254, C.I. Pigment Red 264, C.I. Red pigments such as pigment red 265;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Blue pigments such as pigment blue 60;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Violet color pigments such as pigment violet 38;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as pigment green 58;

C.I. Pigment Brown 23, C.I. Brown pigments such as pigment brown 25;

C.I. Pigment Black 1, C.I. Black pigments such as pigment black 7

Said coloring material can be used individually or in combination of 2 types or more, respectively.

In addition, the inorganic pigment may include titanium oxide, titanium black, carbon black, and the like, and may include one or two or more selected from these.

The organic pigment or inorganic pigment may be subjected to resin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound or the like, or an atomization treatment or impurity by a sulfate atomization method or the like. It is also possible to perform a washing treatment with an organic solvent, water or the like to remove the ionic impurities, and a removal treatment of ionic impurities by an ion exchange method or the like.

It is preferable that the pigment used as the said coloring agent uses the thing of uniform particle diameter, and for this purpose, what disperse | distributed using surfactant as a pigment dispersant can be used.

The colorant may be contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the total ink curable resin composition, and particularly preferably 10 to 30 parts by weight. When the content of the coloring agent is contained in an amount of 1 to 40 parts by weight, the color density of the pixel is sufficient even when a thin film is formed, which is preferable because no residue is generated.

Solvent (D)

The solvent is not limited, and various organic solvents used in the art may be used. Preferably the solvent comprises a boiling point (boiling point) of 170 to 230 ℃. In particular, it is preferable that 70 weight part or more of solvents with the said boiling point of 170-230 degreeC are contained with respect to 100 weight part of total amounts of the whole solvent, and it is more preferable that 80 weight part or more is contained especially. If the composition has a boiling point of less than 70 parts by weight of the solvent in the range of 170 to 230 ℃, the drying speed of the ink is too fast, the ink is dried in the nozzle for ejecting the ink, the nozzle clogging occurs.

Examples of the solvent having a boiling point of 170 to 230 ° C. specifically include ethylene glycol methyl ethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, 1,2-dipropylene glycol diacetate, and diethylene glycol ethyl ether. Acetate and the like.

According to the present invention, a solvent having a boiling point of 170 to 230 ° C. may be used in admixture with other solvents, and may be preferably used in admixture with ether and ester solvents. The ether-based and ester-based solvents that can be used in combination with the solvent having a boiling point of 170 to 230 ° C. may specifically exemplify the following compounds, and these may be used alone or in combination of two or more.

Specific examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxy butyl acetate, methoxypentel Ace Sites, and the like can be 1,3-butylene glycol diacetate, anisole, phenetole, methyl anisole.

Specific examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetate, methoxyacetate butyl, ethoxyacetate, ethyl ethoxyacetate, 3-oxypropionate, 3-oxy Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2 Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl acid, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 3-methyl-3-methoxybutyl acetate, gamma -butylolactone, and the like.

The solvent may be contained in an amount of 40 to 90 parts by weight based on 100 parts by weight of the total ink curable resin composition. When the solvent is contained in the above range, the curable resin composition for ink jet according to the present invention is preferable because it shows good applicability.

Polymerization initiator (E)

The polymerization initiator may be used without limitation in the art, specifically, at least one selected from the group consisting of triazine compounds, acetophenone compounds, xanthone compounds, benzoin compounds and imidazole compounds Can be used.

Specific examples of the polymerization initiator include 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s -Triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2 , 2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,2-bis-2-chloro A phenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole compound etc. are mentioned. The polymerization initiator illustrated above can be used individually or in combination of 2 or more types.

It is preferable that 0.01 to 10 weight part of said polymerization initiators are contained with respect to 100 weight part of curable resin compositions for inkjets, More preferably, it is contained in 0.01 to 0.5 weight part. When the content of the polymerization initiator is included in the above range, the curing time of the curable resin composition for inkjet according to the present invention is shortened, so that productivity is improved, which is preferable.

Additive (F)

Curable resin composition for inkjets of this invention may further contain an additive as needed. The amount of the additive added is not limited but may be contained in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the curable resin composition for inkjet. When the additive is added within the above content range, it is possible to achieve the purpose of the additive without harming the desired physical properties such as flatness of the curable resin composition for inkjet.

As the additive, at least one or more selected from a dispersant, a leveling agent, a wetting agent, a silane coupling agent and an anti-agglomerating agent may be added.

Commercially available surfactants can be used as the dispersant, and the surfactants include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, and mixtures thereof. As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. As a commercial item, toray silicon DC3PA, toray silicon SH7PA, toray silicon DC11PA, toray silicon SH21PA, toray silicon SH28PA, toray silicon 29SHPA, toray silicon SH30PA, polyether modified silicone oil SH8400 (Toray silicon Co., Ltd. product), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.), and the like. have. As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, Prorinate (brand name) FC430, Prorinate FC431 (manufactured by Sumitomo 3M), Megapack (brand name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Mega Pack F183, Mega Pack R30 (manufactured by Dainippon Ink and Chemical Industries, Ltd.), F-top (brand name) EF301, F-top EF303, F-top EF351, f-top EF352 (manufactured by Shin-Aki Takasei Co., Ltd.), suffron (Brand name) S381, Saffron S382, Saffron SC101, Saffron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), BM-1000, BM-1100 (brand name: BMChemie Co., Ltd.) etc. are mentioned. Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Mega Pack (brand name) R08, Mega Pack BL20, Mega Pack F477, Mega Pack F443 (manufactured by Dainippon Ink and Chemical Industries, Ltd.), and the like.

As the leveling agent, those generally used in the art may be used. For example, Megapack F475 (manufactured by Dainippon Ink & Chemical Co., Ltd.) may be used.

Examples of the humectant include glycerin, diethylene glycol, ethylene glycol, and the like, and may include one or more selected from these.

Examples of the silane coupling agent include aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of commercially available products include SH6062 and SZ6030 (Toray-Dow). Corning Silicon co., Ltd.), KBE903, and KBM803 (manufactured by Shin-Etsu silicone co., Ltd.).

Examples of the aggregation inhibitor include sodium polyacrylate.

The above-mentioned curable resin composition for inkjet according to the present invention can be used for formation of spacers, protective films and the like according to known methods. In particular, when the curable resin composition for inkjet according to the present invention further comprises a colorant, it may be used to form a color layer and a black matrix.

Hereinafter, the curable resin composition for inkjet according to the present invention further includes a colorant, and a method of forming a pattern using the same and a color filter including the pattern will be described in more detail.

First, the pattern forming method of the curable resin composition for inkjet according to the present invention comprises applying the above-mentioned curable resin composition for inkjet to a predetermined region in an inkjet method and curing the applied curable resin composition for inkjet. .

First, the curable resin composition for inkjet is injected into an inkjet injector, and it prints in the predetermined area | region of a board | substrate.

The substrate is not limited. For example, a substrate having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, or a GaAs substrate may be used. Can be mentioned. These substrates can be subjected to pretreatment such as chemical treatment with a chemical such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, vapor phase reaction treatment, vacuum deposition treatment, or the like. When a silicon substrate or the like is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT), or the like may be formed on a surface of the silicon substrate or the like. In addition, a partition matrix may be formed.

In order to be ejected from a piezo inkjet head, which is an example of an inkjet ejector, to form an appropriate phase on a substrate, properties such as viscosity, flowability, pigment particles, etc. must be balanced with the inkjet head. The piezo inkjet head used in the present invention is not limited but sprays ink having a droplet size of about 10 pL to 100 pL, preferably about 20 pL to 40 pL.

The viscosity of the curable resin composition for inkjet is suitably about 3 to 30 cP, more preferably in the range of 7 to 20 cP.

The pigment particles used as colorants in the curable resin composition for inkjet preferably have a size of about 50 to 500 nm, more preferably 100 nm or less. When the pigment particle size is 500 nm or more, the fluidity of the pigment particles decreases, so that spraying becomes uneven. When the pigment particle size is 50 nm or less, it is difficult to secure dispersion stability of the pigment.

Next, the color filter according to the present invention includes a color layer formed by the pattern forming method. That is, the color filter comprises a color layer formed by applying and curing the curable resin composition for inkjet according to the present invention described above in a predetermined pattern.

Since the configuration of the color filter is well known in the art, detailed description thereof will be omitted.

According to the present invention, there is provided a liquid crystal display device having the above-described color filter.

The liquid crystal display of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

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 Fluorine-Based Urethane Acrylate Compound of Chemical Formula 3

83.8 parts by mass of fluorinated polyol PolyFox ^TM PF-656 (Omnova Corporation), 15 parts by mass of acryl isocyanate AOI (Showa Denko Corporation), 0.8 parts by mass of dibutyltin lauryl as a catalyst, 0.4 parts by mass of methoxyhydroquinone as a stabilizer, 100 parts by mass of propylene glycol monomethyl ether acetate was added to a three-neck 500 mL reactor as a diluent, and the mixture was stirred in a reactor equipped with a condenser mechanical stirrer thermometer and a heating mantle. When the self-heating proceeded to the initial 60 ℃ and gradually dropped the temperature, the reaction was maintained for 5 hours while maintaining the temperature at 70 ℃ and FT-IR was measured and the reaction was terminated when the characteristic peak of isocyanate 2260cm ^-1 disappeared completely.

The overall scheme is as shown in Scheme 1 below.

Scheme 1

In Scheme 1, n is 1 to 20.

Synthesis Example 2 Synthesis of Fluorine-Based Urethane Acrylate Compound of Formula 4

83.8 parts by mass of fluorine-based polyol Fluorolink E10-H (Solva Co., Ltd.), 15 parts by mass of acryl isocyanate AOI (Showa Denko Co.), 0.8 parts by mass of dibutyltinlauolite as a catalyst, 0.4 parts by mass of methoxyhydroquinone as a stabilizer, and a diluent 100 parts by mass of propylene glycol monomethyl ether acetate was charged into a three-neck 500 mL reactor, and stirred in a reaction apparatus including a condenser mechanical stirrer thermometer and a heating mantle. When the self-heating proceeded to the initial 60 ℃ and gradually dropped the temperature, the reaction was maintained for 5 hours while maintaining the temperature at 70 ℃ and FT-IR was measured and the reaction was terminated when the characteristic peak of isocyanate 2260cm ^-1 disappeared completely.

Overall Scheme As shown in Scheme 2 below.

Scheme 2

In Formula 4, l, m and n are each an integer of 1 or more, and m + n is an integer of 1 to 20.

Pigment Dispersion Preparation

Pigments, dispersants, binder resins and organic solvents were mixed in the compositions shown in the table below to prepare pigment dispersions PB15: 6 (C.I. Pigment Blue 15: 6) and PV23 (C.I. Pigment Violet 23).

Blue / Violet Pigment Dispersion Compounding amount (part by weight) PB15: 6 10.00 PV23 4.00 Dispersant 4.00 Binder resin 2.00 DPMA 80.00

In Table 1, the binder resin is benzyl methacrylate / methacrylic acid (70:30 mol%, styrene equivalent weight average molecular weight 15,000), and DPMA is dipropylene glycol methyl ether acetate as an organic solvent. BYK-2000 (brand name) was used as a dispersing agent.

<Examples 1 to 4 and Comparative Examples 1 to 3> Preparation of curable resin composition for inkjet

The pigment dispersion prepared above was mixed according to the composition shown in Table 2 below to prepare a curable resin composition for inkjet.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pigment Dispersion 28.57 28.57 28.57 28.57 28.57 28.57 28.57 Binder resin 8.48 8.5 8.48 8.50 8.48 8.37 8.57 DPHA 4.24 4.24 4.24 4.24 5.65 5.58 5.58 Fluorine Monomer
<Formula 3> 1.41 1.41 Fluorine Monomer
<Formula 4> 1.41 1.41 AIBN 0.14 0.14 0.14 0.14 0.14 0.14 0.14 F-475 0.02 - 0.02 - 0.02 0.2 - DPMA 57.14 57.14 57.14 57.14 57.14 57.14 57.14

In the above Table 2, the binder resin is benzyl methacrylate / methacrylic acid (70:30 mol%, styrene equivalent weight average molecular weight 15,000), DPHA is a curable monomer, dipentaerythritol hexaacrylate, and AIBN is thermally initiated. It is zero azobisisobutyronitrile, F-475 (made by Dainippon Ink & Chemicals Co., Ltd.) is a leveling agent, and DPMA is dipropylene glycol methyl ether acetate which is an organic solvent.

Experimental Example 1

The curable resin composition for inkjets prepared in the above Examples and Comparative Examples was evaluated for flatness and heat resistance in the following manner and the results are shown in Table 3 below.

(1) flatness

The curable resin composition for inkjet prepared in the above Examples and Comparative Examples was used in an inkjet printing apparatus in a clean room of 23 ° C. and 50% humidity in a volume of 30 pl per ink on a 2.5 m high black matrix (hereinafter referred to as BM). Printed and cured in a convection oven at 230 ° C. for 30 minutes. The level of flatness was evaluated by the difference between the highest part and the lowest part by measuring a step with a stylus profiler of the pixel portion of the cured substrate.

In addition, the curable resin composition for inkjet prepared in Comparative Example 2 was printed in a volume of 30 pl per drop on a black matrix (hereinafter referred to as BM) having a height of 2.5 um using an inkjet printing equipment in a clean room of 23 ° C. and a humidity of 50%, 230 Cured for 30 minutes in a convection oven at ℃. The surface of the cured substrate was photographed and the results are shown in FIG. 1.

In addition, the curable resin compositions for inkjets (hereinafter, also referred to as "inks") prepared in Comparative Example 3 and Example 2 were each prepared by using a black matrix (2.5 m in height) using inkjet printing equipment in a clean room at 23 ° C and 50% humidity. 11 drops and 15 drops were added dropwise to a volume of 30 pl per ink drop in the following BM), and cured in a convection oven at 230 ° C. for 30 minutes. Then, a surface photograph was taken between the pixel and the ink and the results are shown in FIGS. 2A to 2D. Here, FIG. 2A is a photograph corresponding to dropping 11 drops of the curable resin composition for inkjet prepared in Example 2, and FIG. 2B corresponds to dropping 15 drops of the curable resin composition for inkjet prepared in Example 2 2C is a photograph corresponding to 11 drops of the inkjet curable resin composition prepared in Comparative Example 3, and FIG. 2D is a drop of 15 drops of inkjet curable resin composition prepared in Comparative Example 3 This is the picture.

(2) heat resistance

The curable resin composition for inkjet prepared in the above Examples and Comparative Examples was spin-coated on glass, cured in a convection oven at 230 ° C. for 30 minutes, and then resistant to heat for 2 hours in a 230 ° C. convection oven (hereinafter Heat resistance) was evaluated as a color change delta Abi value (ΔEab).

Curable Monomer F-475 content
(Parts by weight) Heat resistance
(△ Eab value) Flatness Surface condition Example 1 Fluorinated monomer (Formula 3)
+ DPHA 0.02 3 or less 0.2um or less - Example 2 Fluorinated monomer (Formula 3)
+ DPHA none 3 or less 0.2um or less Example 3 Fluorinated monomer (Formula 4)
+ DPHA 0.02 3 or less 0.2um or less - Example 4 Fluorinated monomer (Formula 4)
+ DPHA none 3 or less 0.2um or less Comparative Example 1 Introduced only DPHA 0.02 3 or less 0.5um or more - Comparative Example 2 Introduced only DPHA 0.20 3 or less 0.2um or less Spot Comparative Example 3 Introduced only DPHA none 3 or less 0.5um or more Separation from bulkhead after baking

As shown in Table 3, in the case of the embodiment including the fluorine-based urethane acrylate represented by Formula 1 according to the present invention, the flatness of the ink dropped in the BM was increased after the baking, compared to the comparative example without the same. It can be confirmed that the overall height is reduced by reducing the height difference caused by the ink height. In particular, as can be seen in Example 2, it can be seen that the flatness is maintained at a level similar to that of Example 1 without the addition of F-475, a leveling agent added to a conventional curable resin composition. In addition, it can be confirmed that there is no abnormality in heat resistance in the case of using the fluorinated monomers in place of DPHA, which is a commonly used curable monomer.

In addition, Comparative Example 2 corresponds to the case where the leveling agent is used in an excessive amount to improve the flatness of the ink in the pixel, and has a flatness effect similar to that of Example 1. However, when the leveling agent is used in an excessive amount, as shown in the photograph shown in FIG. 1, staining occurs on the surface, resulting in deterioration of product quality.

In addition, as shown in FIG. 2, in the case of Comparative Example 3 in which neither the fluorine monomer nor the leveling agent F-475 was used, separation between the pixels and the ink may be generated, thereby causing color loss.

Claims (5)

Curable resin composition for inkjets containing curable monomer (A) containing a fluorine-type urethane acrylate represented by following formula (1), binder resin (B), a solvent (D), and a polymerization initiator (E).
<Formula 1>

(In Formula 1, R ₁ is independently of each other ethyl, (iso) propyl, (poly) tetraethylene, (poly) ethylene glycol or (poly) propylene glycol, R ₂ is hydrogen or methyl, Rf is a fluorine-based polyol It is represented by the following formula (2).
<Formula 2>

(In Formula 2, R ₃ is symmetric with each other in the structure of methyl or (poly) ethylene glycol, (poly) propylene glycol, (poly) tetraethylene glycol, and R4 is carbon or CF ₂ O- (CF ₂ CF ₂ O) _a — (CF ₂ O) _b —OCF ₂ , a and b are each an integer of 0 or greater than 1, a + b is an integer from 1 to 20, and R ₅ is each independently hydrogen, methyl, ethyl, propyl, butyl or CH ₂ -O-CH ₂ -C _P F _{2 P +1} , P is an integer from 1 to 10, n is an integer from 1 to 20.)
The curable resin composition for inkjet according to claim 1, wherein the silicone urethane acrylate is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total ink curable resin composition.
The curable resin composition for inkjets according to claim 1, wherein the curable resin composition for inkjets further comprises a colorant (C).
A color filter comprising a black matrix or a color layer formed by applying the curable resin composition for inkjet according to any one of claims 1 to 3 in a predetermined pattern and then curing.
A liquid crystal display device comprising the color filter of claim 4.

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