KR100993530B1 - Photosensitive resin composition comprising novel multi-functional monomer - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising a polyfunctional monomer having a plurality of (meth) acrylic groups and polyoxyethylene groups in a molecule. The composition according to the present invention provides excellent sensitivity and fast development speed, excellent surface roughness as well as colorant composition. The effect of increasing dispersion stability can be provided at the same time.

Multifunctional, Acrylic, Polyoxyethylene, Photosensitive, Composition, Development Speed, Surface Roughness

Description

Photosensitive resin composition containing a novel polyfunctional monomer {PHOTOSENSITIVE RESIN COMPOSITION COMPRISING NOVEL MULTI-FUNCTIONAL MONOMER}

The present invention relates to a photosensitive resin composition having improved development speed, surface roughness and dispersion stability.

The color filter manufacturing method includes a dyeing method, a pigment dispersion method, an electrodeposition method and a printing method, and among these, a pigment dispersion method having advantages in productivity, quality and cost is mainly used. In recent years, new technologies such as a film transfer method, an inkjet printing method, and a laser transfer method have been developed in order to improve color characteristics, reduce manufacturing costs, and respond to large area substrates for color purity and transmittance.

Generally, the pigment dispersion photosensitive color composition used in the pigment dispersion method, which is the method most commonly employed, is composed of a solvent, a pigment, a pigment dispersant, a binder polymer, a polyfunctional monomer, a photoinitiator, and an additive. Each component of the composition is specifically a pigment which expresses color when light is transmitted, a dispersant which allows pigments which are fine particles to be stably dispersed without agglomeration in a solvent, and crosslinks with a polyfunctional monomer in an exposed part after application to a substrate. Binder polymers that form a sieve and are easily removed from a developer in a non-exposed part, polyfunctional monomers that form a crosslinked film with a binder polymer in an exposed part, and a photosensitive initiator that generates radicals upon light to initiate a crosslinking reaction.

In general, color filters are manufactured by forming patterns of three primary colors, ie, red, green, and blue, on a glass substrate. Applying a photosensitive color resist containing a pigment corresponding to a color pixel on a substrate, heat-drying the applied composition to form a film, and forming a mask of a desired shape on the formed film ( selective exposure using a mask) and then developing; and heating and curing the developed film.

As the use of liquid crystal displays (LCDs) has recently been expanded from notebook monitors to desktop monitors and LCD TVs, a color filter with excellent color reproducibility and high contrast is required. In order to satisfy this problem, ultrafine particles of pigments and pigments in photosensitive resins are required. Has been developed in the direction of increasing the content of the addition. As the pigment becomes more and more fine particles as described above, the surface area of the pigment is sharply increased, so that the amount of dispersant added to stabilize the pigment is also increased. As such, when the concentration of the pigment contained in the photosensitive resin composition increases, the amount of irradiation energy that can reach the lower portion of the pattern film decreases, and the content of the dispersant that is not easily dissolved in the alkaline developer also increases, thereby lowering the development speed. Therefore, in the production process, there is a problem in that the productivity per unit process decreases because the exposure amount and the development time are inevitably increased.

The most representative method for improving the developability of the photosensitive resin composition is to increase the acid value (AV) or lower the molecular weight (M _W ) of the binder polymer used as the alkali-soluble resin. Increasing the acid value of the binder polymer may impair compatibility with other constituents and storage stability, and thus there is a practical limit to increase. In addition, the method of lowering the molecular weight of the binder polymer improves developability, but since the problem of deteriorating the surface roughness of the pattern occurs after the developing process, it is impossible to improve both developability and surface roughness.

On the other hand, the general method of improving the sensitivity and surface roughness of the photosensitive resin composition is the method of increasing the usage-amount of a polyfunctional monomer. Specific examples of the monomer containing a polyfunctional group include trimethoxysilylpropyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate and the like. Since such general polyfunctional monomers have a problem of lowering alkali developability since they are lipophilic substances, this also cannot improve both developability and surface roughness. Therefore, development of the component of the photosensitive resin composition which satisfy | fills developability, surface roughness, and high sensitivity simultaneously is urgently required.

Conventional techniques for solving the above problems include a method of using a multifunctional monomer having both ethylenically unsaturated bonds and unsaturated carboxylic anhydride bonds in one molecule (Korean Patent Publication No. 10-2007-76083). It is possible to improve the adhesion and surface hardness of, but there is a limit in improving the development speed. In addition, the method of adding a developing residue reducing agent containing a compound containing a polyfunctional acrylic group and two or more carboxyl groups in one molecule (Korean Patent Publication No. 10-2006-7600) has a significant effect on improving the developing speed and surface roughness. However, there is a problem in that the storage stability of the colorant is deteriorated by a high carboxyl group.

Therefore, there is an urgent need for the development of additives that improve the development speed, improve the surface roughness and do not deteriorate the dispersion stability of the colorant composition.

Accordingly, the technical problem to be achieved by the present invention is to speed up the development speed of the photosensitive resin composition including the pigment particles, improve the sensitivity and surface roughness, and increase the storage stability of the colorant.

 This invention provides the photosensitive resin composition characterized by including the polyfunctional monomer which has many (meth) acryl group and polyoxyethylene group in a molecule | numerator.

In the composition of the present invention, the number of moles of repeating units of the polyoxyethylene group is preferably 1 to 30.

In addition, the multifunctional monomer is more preferably a compound represented by any one of the following formulas (4) and (5):

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In Formulas 4 and 5, each R is independently alkylene having 1 to 20 carbon atoms, each X is independently -O-, -NH-, -S- or -COO-, and each R ₁ is independently hydrogen Or alkyl having 1 to 10 carbon atoms, and n is each independently an integer of 1 to 30.

The photosensitive composition according to the present invention is represented by the above formulas (4) and (5) and preferably contains a multifunctional monomer having a plurality of (meth) acryl groups and polyoxyethylene groups, alkali-soluble resin binders, photopolymerization initiators, colorants, and solvents in a molecule thereof. Do.

The components are 0.001 to 10% by weight of the multifunctional monomer of any one of Formulas 4 and 5 based on the total weight of the composition; 1 to 30% by weight of alkali-soluble resin binder; 0.1 to 10% by weight photopolymerization initiator; 0.5 to 40 wt% colorant; It is preferably included in 10 to 95% by weight of the solvent.

In addition, the photosensitive resin composition of the present invention may further include a polymerizable compound having an etellenically unsaturated bond in addition to the above components, the content of which is preferably contained in 0.5 to 10 parts by weight relative to 100 parts by weight of the composition.

Moreover, the photosensitive resin composition of this invention is trimethoxy silyl propyl (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipenta It may further comprise at least one polyfunctional monomer selected from the group consisting of erythritol hexa (meth) acrylate.

In addition, the photosensitive resin composition of the present invention may further include at least one additive selected from the group consisting of a photosensitizer, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, and a surfactant.

The present invention improves the development speed of the pigment dispersion photosensitive resin composition and improves the surface roughness and dispersion stability of the colorant composition.

According to the present invention, the development speed can be greatly improved by adding a monomer having two or more, more preferably two to ten (meth) acryl groups, and a hydrophilic polyoxyethylene group introduced into the photosensitive resin composition to the terminal group. have.

The method for imparting a polyoxyethylene group to a polyfunctional monomer should have a hydroxyl, thiol, primary amino, secondary amino or carboxyl group at the terminal of the polyfunctional monomer precursor and have two or more functional groups. The precursor mentioned above can be introduced with polyoxyethylene group to the activator by injecting ethylene oxide gas with heat of 130 ~ 170 ℃ under the catalyst of KOH or NaOH and under the material synthesized in this way, (meth) acrylic acid, and a small amount of acid catalyst As the esterification proceeds, a compound having a polyfunctional polyoxyethyl group introduced therein can be obtained.

At the time of introduction of polyoxyethylene group excellent in developing speed and storage stability, the suitable mole number of oxyethylene group is about 1 to 30 mole. Too small an oxyethylene group will reduce hydrophilicity, which will not help to improve the development speed. Too much oxyethylene group will cause too long a chain length to reduce the degree of crosslinking. Most preferably, the number-of-moles of an oxyethylene group are 4-15 mol. Specific examples of the compound that can be used as a precursor of the compound into which the polyfunctional polyoxyethylene group is introduced include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, trimethanol, trimethylolpropanol, pentaerythritol, and dipentaerythritol , 3-methoxy-1,2-propanediol, adonitol, L-2-aminoadipic acid, 2-aminobenzenethiol, 4-aminobenzenethiol, DL-2-amino-1-butanol, 4-amino -1-butanol, 2-aminoethanethiol, 2- (2-aminoethylamino) ethanol, 2-amino-1,3-propanediol, N- (3-aminopropyl) diethanolamine, 1,2,3 Butanetriol, 1,3-cyclohexanediamine, 1,4-cyclohexanediol, glycerol may be used at least one selected from the group consisting of, but is not limited to those known in the art Can be used.

The content of the multifunctional monomer is preferably 0.001 to 10% by weight based on the total weight of the composition.

As the alkali-soluble resin binder which may be included in the composition of the present invention, it is preferable to use a binder having an acid value of about 30 to 300 KOHmg / g and a weight average molecular weight of 1,000 to 200,000, and a weight average molecular weight of 5,000 to 100,000 Phosphorus binder is more preferred. As a monomer used for alkali-soluble resin binder manufacture, it is preferable to use 1 or more types of compounds chosen from the group which consists of (meth) acrylic acid, maleic acid, a fumaric acid, etc., but is not limited to these.

Monomers copolymerizable with the monomer containing an acid group include benzyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, styrene, N-vinyl pyrrolidone, 1-adamantane carboxylate-2-vinyloxyethyl ester, 2-methoxybutyl-2-adamantyl methacrylate, 5-methacryloxy-6-hydroxynorbornene Preference is given to using one or more compounds selected from the group consisting of 2-carboxy-6-lactone and 3-hydroxy-1-adamantyl methacrylate, but not limited thereto.

The content of the alkali-soluble resin binder is preferably 1 to 30% by weight based on the total weight of the composition.

In the photosensitive resin composition of this invention, as a photoinitiator, 2, 4- trichloromethyl- (4'-methoxyphenyl) -6-triazine, 4,4'-bis (diethylamino) benzophenone, 2, One or more compounds selected from the group consisting of 4,6-tri methylaminobenzophenone, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, and the like can be used. It is not limited only to. The content of the photopolymerization initiator is preferably 0.1 to 10% by weight based on the total weight of the composition.

In the photosensitive resin composition of this invention, it is preferable to use 1 or more types of pigment, dye, or a mixture thereof as a coloring agent. Preferred colorants include CIPIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 202 , 214, 215, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7,36; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37 and the like. The content of the colorant is preferably 0.5 to 40% by weight based on the total weight of the composition.

In the photosensitive resin composition of this invention, as a solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, cyclohexanone, cyclopentanone, dipropylene It is preferable to use one or more selected from the group consisting of glycol monomethyl ether and the like, but is not limited thereto. The solvent may be included in 10 to 95% by weight based on the total weight of the composition.

The photosensitive resin composition of the present invention may further include a polymerizable compound having an ethylene unsaturated bond in addition to the above components. As a polymeric compound which has an ethylenically unsaturated bond, 1 type chosen from the group which consists of a trimethylol propane di (meth) acrylate, a pentaerythritol tetra (meth) acrylate, and a trimethelol propane triglycidyl ether acrylic acid addition product Although it is preferable to use the above compound, it is not limited only to these. If used, the polymerizable compound having an ethylenically unsaturated bond is preferably included in 0.5 to 10 parts by weight relative to 100 parts by weight of the composition.

In addition, the photosensitive resin composition of the present invention may further include at least one additive selected from the group consisting of photosensitizers, colorants, curing accelerators, thermal polymerization inhibitors, plasticizers, adhesion promoters, fillers, and surfactants. If included, the additive is preferably added at 0.01 to 20 parts by weight based on the total weight of the composition.

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

Synthesis Example 1

100 g of alcohol and 0.2 g of KOH (50% aqueous solution) were injected into the catalytic reactor, and the mixture was heated to 120 to 130 ° C., and then dried under vacuum (water concentration of <200 ppm), and then the mixture was injected into the reactor. At this time, when the reaction temperature rises to 145 ° C, the injection of the external heat exchanger was stopped and the reaction temperature increased to 160-180 ° C while slowly injecting ethylene oxide gas and nitrogen gas. An appropriate amount of ethylene oxide gas was injected to maintain the reaction temperature. After completion of the appropriate amount of ethylene oxide injection, unreacted ethylene oxide was consumed to maintain the reaction temperature until the reaction pressure remained unchanged. After the reaction was completed, the reaction was terminated by neutralizing with HCl. The material thus obtained was filtered to remove salts.

To 100 g of the material thus obtained, 100 g of methacrylic acid, 0.1 g of sulfuric acid, 0.1 g of phenothiazine and 0.1 g of toluene were placed in a reactor equipped with a Dean-stark trap, heated to 80 ° C., and water was removed. The reaction proceeded by heating for 12 hours. After the temperature was lowered, CaCO ₃ was added and the mixture was slightly heated to form calcium sulfate. The sulfuric acid was removed, and then the solvent was removed under vacuum to obtain a compound of Chemical Formula 6 (n = 2, R ₁ = CH ₃ ).

H-NMR (ppm, CDCl ₃ ): 6.13 (s, 1H), 5.58 (s, 1H), 4.30 (t, 2H), 3.65 (t, 2H), 3.57 (d, 2H), 1.95 (s, 3H )

Synthesis Example 2

A compound of Chemical Formula 7 (n = 1, R ₁ = CH ₃ ) was prepared in the same manner as in Synthesis Example 1 except that 100 g of glycerol was used instead of alcohol.

H-NMR (ppm, CDCl ₃ ): 6.13 (s, 1H), 5.58 (s, 1H), 4.30 (t, 2H), 3.75 (t, 2H), 3.65 (b, 8H), 3.57 (b, 1H ), 1.95 (s, 3H)

&Lt; Synthesis Example 3 &

A compound of Chemical Formula 8 was prepared in the same manner as in Synthesis Example 1, except that 100 g of 3,6-bis (hydroxymethyl) morpholine-2,5-diol was used instead of alcohol.

H-NMR (ppm, CDCl ₃ ): 6.13 (s, 4H), 5.58 (s, 4H), 5.34 (d, 1H), 5.01 (d, 1H), 4.54 (d, 1H), 4.30 (t, 8H ), 3.65 (t, 8H), 3.54 (s, 30H), 1.95 (s, 12H)

&Lt; Synthesis Example 4 &

A compound of Chemical Formula 9 was prepared in the same manner as in Synthesis Example 1, except that 100 g of 2-aminobutan-1-ol was used instead of alcohol.

H-NMR (ppm, CDCl ₃ ): 6.13 (s, 3H), 5.58 (s, 3H), 4.32 (m, 6H), 3.65 (m, 8H), 3.54 (s, 16H), 3.47 (t, 4H ), 2.54 (t, 4H), 1.95 (s, 9H), 0.96 (t, 3H)

Comparative Example A

As the organic pigment, 40 g of Pigment Red 254 dispersion liquid was used as the color index name based on the pigment. 25 g of acrylic acid / methacrylic acid / 2-hydroxy ethyl methacrylate / benzyl methacrylate copolymer (copolymerization ratio = 10/10/10/70, number average molecular weight 10,000) as alkali-soluble resin, 2,2 as photoinitiator 5 g of bis (2,4-dichlorophenyl) -4,4,5,5-tetraphenyl-1,2-diimidazole and 5 g of 4,4-bis (diethylamino) benzophenone and 2-benzyl-2 10 g of -dimethylamino-1- (4-morpholinophenyl) butan-1-one, and 10 g of γ-methacryloxypropylmethyldimethoxysilane as a catalyst, and 15 g of the compound of the formula (6) as a polyfunctional monomer 255 g of a photoresist liquid composition was prepared by mixing with 145 g of ethyl ether acetate.

Next, after coating the photoresist liquid composition on a glass substrate, the coated substrate was baked at about 100 ° C. for 2 minutes to obtain a film having a thickness of 2.0 μm. After baking the board | substrate to room temperature, the pattern was formed by exposing the ultraviolet-ray containing each wavelength by the exposure amount of 100mJ / cm <2> using a high pressure mercury lamp, using a photomask between substrates.

<Comparative Example B>

A pattern was formed by exposing a film to the photosensitive resin composition solution in the same manner as in Comparative Example A, except that 15 g of the compound of Formula 7 was used instead of the compound of Formula 6.

&Lt; Example 1 >

A pattern was formed by exposing and then forming a film with the photosensitive resin composition solution in the same manner as in Comparative Example A, except that 15 g of the compound of Formula 8 was used instead of the compound of Formula 6.

<Example 2>

A pattern was formed by exposing and then forming a film with the photosensitive resin composition solution in the same manner as in Comparative Example A, except that 15 g of the compound of Formula 9 was used instead of the compound of Formula 6.

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Comparative Example 1

Except for using 15 g of trimethylolpropane diacrylate instead of the compound of Formula 6 in the same manner as in Comparative Example A to form a film with the photosensitive resin composition solution and then exposed to form a pattern.

Comparative Example 2

Except for using 15 g of pentaerythritol methacrylate instead of the compound of Formula 6 in the same manner as in Comparative Example A to form a film with the photosensitive resin composition solution and then exposed to form a pattern.

Comparative Example 3

The copolymerization ratio of the acrylic acid / methacrylic acid / 2-hydroxy ethyl methacrylate / benzyl methacrylate copolymer, which is an alkali-soluble resin, was set to 10/30/10/50, and as a polyfunctional monomer, Except that 15 g of pentaerythritol hexaacrylate was used, a film was formed using the photosensitive resin composition solution in the same manner as in Comparative Example A and then exposed to form a pattern.

<Comparative Example 4>

Except for using the polyethylene glycol 400 in 1g instead of the compound of formula 6 in the same manner as in Comparative Example A to form a film with the photosensitive resin composition solution and then exposed to form a pattern.

<Evaluation of Examples and Comparative Examples>

Each composition was evaluated using the pattern formed in the Example and the comparative example.

First, the pattern was developed and washed with an aqueous potassium hydroxide solution having a pH of 12.0 and subjected to post-heat treatment at 220 ° C. for about 30 minutes.

Surface roughness:

The state of the glass surface and the pattern was measured by atomic force microscope (AFM).

Developing Speed:

One color filter is displayed as the speed for developing, and the smaller the value, the faster the developing speed.

Minimum exposure:

The minimum exposure dose Eth for forming a pattern for sensitivity evaluation was measured (using a mask having a different transmittance).

Storage stability:

The compositions prepared in Examples 1 and 2 and Comparative Examples A, B and 1 to 4 were measured for initial viscosity at 60 rpm using LDVE II from Brookfield. After 4 weeks in the low temperature incubator maintained at 45 ℃ viscosity was measured to determine the change in viscosity over time. In general, if the viscosity change within 10% for 4 weeks it can be said to have excellent storage stability.

The evaluation results are shown in Table 1 below.

From the results of Table 1, it can be seen that in the case of Examples 1 and 2 to which the compound according to the present invention is added, it is more excellent in development speed, surface roughness and storage stability than Comparative Examples A, B and 1 to 4. have.

Claims (9)

A photosensitive resin composition comprising one or more of the multifunctional monomers represented by the following Chemical Formulas 4 and 5: <Formula 4>

<Formula 5>

In Formulas 4 and 5, each R is independently alkylene having 1 to 20 carbon atoms, each X is independently -O-, -NH-, -S- or -COO-, and each R ₁ is independently hydrogen Or alkyl having 1 to 10 carbon atoms, and n is each independently an integer of 1 to 30. delete delete The photosensitive resin composition of Claim 1 which further contains an alkali-soluble resin binder, a photoinitiator, a coloring agent, and a solvent. The method of claim 4, based on the total weight of the photosensitive resin composition a) 0.001 to 10 wt% of a multifunctional monomer; b) 1 to 30% by weight of alkali-soluble resin binder; c) 0.1 to 10% by weight photoinitiator; d) 0.5 to 40% by weight of a colorant; And e) 10 to 95% by weight solvent Photosensitive resin composition comprising a. The photosensitive resin composition according to claim 5, further comprising a polymerizable compound having an ethylene unsaturated bond. The photosensitive resin composition of claim 6, wherein the polymerizable compound having an ethylenically unsaturated bond is included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the composition. The method of claim 1, wherein the trimethoxysilylpropyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa ( The photosensitive resin composition which further contains 1 or more types of polyfunctional monomers chosen from the group which consists of a meta) acrylate. The photosensitive resin composition according to claim 5, further comprising at least one additive selected from the group consisting of a photosensitizer, a curing accelerator, a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, and a surfactant.