KR102145934B1 - Method of forming photo-curable pattern - Google Patents

Abstract

The present invention relates to a method of forming a photocurable pattern, and more particularly, in a method of forming a photocurable pattern by applying a photosensitive resin composition to at least one surface of a substrate and exposing it with light of a complex wavelength, the exposure is The integral value of the light quantity of the light at the wavelength of the j-line (300 nm or more and 340 nm or less) is 5 to 20% with respect to the integral value of the light quantity of the wavelength of the i-line (more than 340 nm and 380 nm or less), and the photosensitive resin composition has an absorption wavelength By including a photopolymerization initiator of 325 to 340 nm, it is possible to form a fine pattern by improving the adhesion of the pattern, thereby to a method of forming a photocurable pattern capable of realizing high resolution.

Description

Photocuring pattern formation method {METHOD OF FORMING PHOTO-CURABLE PATTERN}

The present invention relates to a method for forming a photocurable pattern capable of remarkably improving the resolution of the pattern by controlling the amount and wavelength of light in the exposure step.

In the display field, the photosensitive resin composition is used to form various photocurable patterns such as photoresist, insulating film, protective film, black matrix, and column spacer. Specifically, a photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photocuring pattern.In this process, a photosensitive resin having high sensitivity to improve the yield of the process and to improve the physical properties of the application object Compositions are in demand.

Meanwhile, in general display devices, silica beads or plastic beads having a certain diameter have been used to maintain a certain distance between upper and lower substrates. However, when such beads are randomly distributed on a substrate and placed inside a pixel, there is a problem that an aperture ratio is lowered and a light leakage phenomenon occurs. In order to solve these problems, a spacer formed by photolithography has been used in a display device, and spacers used in most display devices are currently formed by photolithography.

In a method of forming a spacer by photolithography, a photosensitive resin composition is applied on a substrate, ultraviolet rays are irradiated through a mask, and then spacers are formed at a desired position on the substrate according to a pattern formed on the mask through a development process.

Currently, in forming a photocurable pattern such as a spacer pattern, a complex wavelength mainly including i-line (365 nm) is used during exposure, but the i-line has a very large amount of light, so it is difficult to form a fine pattern, so it is not suitable for realizing high resolution. not. In addition, the absorption wavelength of the photosensitive resin composition for hardening to occur and the amount of light do not coincide with the wavelength range of the i-line, which has the largest amount of light, and thus there is a problem that sensitivity is deteriorated.

An object of the present invention is to provide a method of forming a photocurable pattern capable of forming a fine pattern.

In addition, an object of the present invention is to provide a method of forming a photocurable pattern capable of implementing high resolution.

1. In a method of forming a photocurable pattern by applying a photosensitive resin composition to at least one surface of a substrate and exposing it with light of a complex wavelength,

The exposure is performed so that the integral value of the light quantity of the light of the wavelength of the j-line (300 nm or more and 340 nm or less) of the light is 5 to 20% with respect to the integral value of the light quantity of the wavelength of the i-line (more than 340 nm and 380 nm or less),

The photosensitive resin composition comprises a photopolymerization initiator having an absorption wavelength of 325 to 340 nm, a method of forming a photocuring pattern.

2. The method of 1 above, wherein the exposure is performed using a filter that reduces the integral value of the light quantity of light having a wavelength of the j-line (300 nm or more and 340 nm or less).

3. The method of forming a photocuring pattern according to the above 2, wherein the reduction of the integral value of the light quantity of the light of the wavelength of the j-line (300 nm or more and 340 nm or less) is performed by 20 to 80% compared to the light emitted from the light source.

4. The method of forming a photocuring pattern according to the above 2, wherein the reduction of the integral value of the light quantity of light having a wavelength of 300 nm or more and less than 330 nm among the j-line is performed by 20 to 70% compared to the light emitted from the light source.

5. The method of forming a photocuring pattern according to the above 2, wherein the reduction of the integral value of the light quantity of light having a wavelength of 330 nm or more and 340 nm or less among the j-line is performed by 15 to 90% compared to the light emitted from the light source.

6. The method of 1 above, wherein the photopolymerization initiator is at least one selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, and oxime-based compounds.

7. The method of 1 above, wherein the photopolymerization initiator is contained in an amount of 1 to 30% by weight based on the total solid content of the photosensitive resin composition.

8. The method of 1 above, wherein the photosensitive resin composition further comprises an alkali-soluble resin, a photopolymerizable compound, and a solvent.

9. The method according to 1 above, wherein the photocuring pattern is selected from the group consisting of an array planarization layer pattern, a protective layer pattern, an insulating layer pattern, a photoresist pattern, a black matrix pattern, and a column spacer pattern.

10. A photocurable pattern formed according to any one of 1 to 9 above.

11. An image display device having the photocuring pattern of the above 10.

In the method of forming a photocurable pattern of the present invention, a pattern having excellent adhesion can be formed by controlling the wavelength and amount of light in the exposure step.

In addition, the method of forming a photocurable pattern of the present invention may form a fine pattern capable of implementing high resolution.

1 is a graph showing the integral value of the amount of light according to the absorption wavelength of the photopolymerization initiator used in Preparation Examples 1 to 5 and the wavelength of light used in the exposure step of Examples and Comparative Examples.
2 schematically shows a method for measuring the bottom CD and top CD of the pattern.

The present invention relates to a method of forming a photocurable pattern, and more particularly, in a method of forming a photocurable pattern by applying a photosensitive resin composition to at least one surface of a substrate and exposing it with light of a complex wavelength, the exposure is The integral value of the light quantity of the light at the wavelength of the j-line (300 nm or more and 340 nm or less) is 5 to 20% with respect to the integral value of the light quantity of the wavelength of the i-line (more than 340 nm and 380 nm or less), and the photosensitive resin composition has an absorption wavelength By including a photopolymerization initiator of 325 to 340 nm, it is possible to form a fine pattern by improving the adhesion of the pattern, and thereby, a method of forming a photocurable pattern capable of realizing high resolution, and a photocurable pattern prepared accordingly and an image having the same It relates to a display device.

< Photocuring Pattern formation method>

The method of forming a photocurable pattern according to the present invention enables a fine pattern with excellent adhesion to be formed by controlling the wavelength and amount of light irradiated in the exposure step.

More specifically, the present invention reduces the integral value of the light quantity of light with a wavelength of j-line (300 nm or more and 340 nm or less) in the exposure step to an appropriate range, and at the same time, by using a photopolymerization initiator having an absorption wavelength of 325 to 340 nm, It is determined that a pattern having excellent adhesion can be formed by maintaining an appropriate range of the pattern height while forming the pattern.

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

Film formation step

First, a photosensitive resin composition is applied to at least one surface of a substrate.

The photosensitive resin composition used in the present invention contains a photopolymerization initiator having an absorption wavelength of 325 to 340 nm, so that the generation of radicals that initiate polymerization between unsaturated double bonds is controlled, thereby forming a fine pattern and at the same time, the height of the pattern is appropriate. The range can be maintained, so that a pattern having excellent adhesion can be formed.

First, the photosensitive resin composition is applied and then heated and dried to remove volatile components such as a solvent to obtain a smooth coating film. Examples of coating methods include spin coating, cast coating, roll coating, slit and It can be carried out by spin coating or slit coating.

When a more specific example of the forming step of the coating film is described, it may be performed by heating drying (pre-baking) after application, or by heating after drying under reduced pressure to volatilize volatile components such as a solvent. Here, the heating temperature may be usually 70 to 200°C, preferably 80 to 130°C, and the thickness of the coating film after heating and drying is usually about 1 to 8 μm.

The photosensitive resin composition used in the present invention may contain an alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (D).

Alkali-soluble resin (A)

The alkali-soluble resin (A) usually has reactivity and alkali solubility by the action of light or heat, and acts as a dispersion medium for materials.

The alkali-soluble resin (A) according to the present invention may be a copolymer comprising a structural unit obtained by copolymerization reaction of a compound comprising the following (A1) and (A2).

(A1): a compound having an unsaturated bond and a carboxyl group,

(A2): An aliphatic polycyclic compound having an epoxy group selected from the group consisting of the following formulas 1a and 1b and having an unsaturated bond.

The alkali-soluble resin can be polymerized together by adding other monomers in addition to the above monomers. That is, even when a monomer other than the above-described A1 to A2 is further contained and copolymerized, it is included in the present invention.

<Formula 1a>

<Formula 1b>

In Formulas 1a and 1b, R is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms substituted or unsubstituted with a hydroxyl group, and X is each independently a single bond or a hetero atom containing or not containing 1 to 6 carbon atoms. It is an alkylene group.

As the compound (A1) having an unsaturated bond and a carboxyl group, any carboxylic acid compound having a polymerizable unsaturated double bond may be used without limitation.

The compound (A1) having an unsaturated bond and a carboxyl group includes, for example, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or a polycarboxylic acid having two or more carboxyl groups in the molecule such as unsaturated tricarboxylic acid. have.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

Examples of the unsaturated polyhydric carboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

The polyhydric carboxylic acid may be an acid anhydride, and examples of the unsaturated polyhydric carboxylic anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride.

In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinate mono (2-acryloyloxyethyl), succinate mono (2-methacryloyloxy). Ethyl), monophthalate (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl), and the like.

The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxylic polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. have.

Further, the unsaturated polyhydric carboxylic acid may be an unsaturated acrylate containing a hydroxy group and a carboxyl group in the same molecule, for example, α-(hydroxymethyl)acrylic acid, etc.

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of high copolymerization reactivity.

(A1) exemplified above can be used alone or in combination of two or more.

In Formulas 1a and 1b, R is specifically, a hydrogen atom; Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group; Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy -Isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n -It may be a hydroxyl group-containing alkyl group such as a butyl group. Among them, R is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and particularly preferably a hydrogen atom or a methyl group.

In Formulas 1a and 1b, X is specifically, a single bond; Alkylene groups, such as a methylene group, an ethylene group, and a propylene group; It may be a hetero atom-containing alkylene group such as an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group, and an aminopropylene group. Among them, X is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group, or an oxyethylene group, and particularly preferably a single bond or an oxyethylene group.

The compound represented by Formula 1a may specifically include compounds of Formulas 1a-1 to 1a-15 below.

<Formula 1a-1>

<Formula 1a-2>

<Formula 1a-3>

<Formula 1a-4>

<Formula 1a-5>

<Formula 1a-6>

<Formula 1a-7>

<Formula 1a-8>

<Formula 1a-9>

<Formula 1a-10>

<Formula 1a-11>

<Formula 1a-12>

<Formula 1a-13>

<Formula 1a-14>

<Formula 1a-15>

The compound represented by Formula 1b may specifically include compounds represented by the following Formulas 1b-1 to 1b-15.

<Formula 1b-1>

<Formula 1b-2>

<Formula 1b-3>

<Formula 1b-4>

<Formula 1b-5>

<Formula 1b-6>

<Formula 1b-7>

<Formula 1b-8>

<Formula 1b-9>

<Formula 1b-10>

<Formula 1b-11>

<Formula 1b-12>

<Formula 1b-13>

<Formula 1b-14>

<Formula 1b-15>

The compounds represented by the compound represented by Formula 10a and the compound represented by Formula 10b may be used alone or in combination of two or more.

In the alkali-soluble resin (A), in the copolymer of (A1) and (A2), a compound having a polymerizable unsaturated bond with (A1) and (A2) in addition to the above (A1) and (A2) may be copolymerized together. have.

Compounds having an unsaturated bond polymerizable with (A1) and (A2) are specific examples, such as 2-aminoethylacrylate, 2-aminoethylmethacrylate, 2-dimethylaminoethylacrylate, and 2-dimethylaminoethylmethacryl. Rate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3 -Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; Vinyl carboxylic acid esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; And a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. And macromonomers to have.

When the alkali-soluble resin (A) is a copolymer obtained by copolymerizing (A1) and (A2) as described above (also included in the present invention when a monomer other than A1 and A2 is further included and copolymerized), the copolymer In the coalescence, the proportion of the constituent units derived from each of (A1) and (A2) is preferably in the following range in terms of a molar fraction with respect to the total number of moles of the constituent units constituting the copolymer.

A structural unit derived from (A1); 5 to 75 mol%,

A structural unit derived from (A2); 25-95 mol%.

In particular, it is more preferable if the ratio of the structural unit is in the following range.

A structural unit derived from (A1); 10 to 70 mol%

A structural unit derived from (A2); 30-90 mol%

When the ratio of the structural units is in the above range, it becomes possible to manufacture a photosensitive resin composition having good developability, solvent resistance, heat resistance, and mechanical strength.

The alkali-soluble resin (A) is, for example, a method described in the document ``Experimental method for polymer synthesis'' (Otsu Takayuki, Ltd., Chemical Co., Ltd., first edition, first edition, issued on March 1, 1972) and the document It can be prepared by referring to the cited documents described in.

Specifically, by placing predetermined amounts of the units (A1) and (A2) constituting the copolymer, a polymerization initiator and a solvent into a reaction vessel, and replacing oxygen with nitrogen, in the absence of oxygen, the polymer is stirred, heated, and kept warm. Is obtained. In addition, the obtained copolymer may be used as it is the solution after the reaction, may be a concentrated or diluted solution, may be used as a solid (powder) extracted by a method such as reprecipitation.

The alkali-soluble resin (A) preferably has an acid value in the range of 20 to 200 (KOHmg/g). When the acid value is in the above range, it is possible to manufacture a pattern having an excellent elastic recovery rate.

The alkali-soluble resin (A) has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, preferably 5,000 to 50,000. When the weight average molecular weight of the unsaturated group-containing resin is in the above range, film reduction during development is prevented, and the omission of the pattern portion is improved, and thus it is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin (A) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. If the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is within the above range, developability becomes excellent, which is preferable.

The content of the alkali-soluble resin (A) is in the range of usually 5 to 90% by mass, preferably 10 to 70% by mass, based on the total solid content in the photosensitive resin composition. If the content of the alkali-soluble resin (A) is 5 to 90% by mass based on the above criteria, it has sufficient solubility in a developer to improve developability, has excellent elastic recovery rate, and has a hard characteristic with little deformation due to external pressure. It becomes possible to manufacture.

Photopolymerization Compound (B)

The photopolymerizable compound (B) contained in the photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator (C) described later, and includes monofunctional monomers, bifunctional monomers, and other polyfunctional monomers. Can be lifted.

The photopolymerizable compound (B) used in the present invention can be used by mixing two or more photopolymerizable compounds having different structures or number of functional groups in order to improve the developability, sensitivity, adhesion, and surface problems of the composition, There is no limit to its scope. Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroly. Such as money. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri (Meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol Hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned. Among these, a bifunctional or higher polyfunctional monomer is preferably used.

The photopolymerizable compound (B) is in the range of 1 to 90 parts by mass, preferably 10 to 80 parts by mass, based on the total amount of the alkali-soluble resin (A) and the photopolymerizable compound (B) based on the solid content of the composition. Used in If the photopolymerizable compound (B) is within the range of the above criteria, the strength and smoothness of the pattern become good, so it is preferable.

Light polymerization Initiator (C)

As long as the photopolymerization initiator (C) used in the present invention satisfies the above-described absorption wavelength range (325 to 340 nm), its kind and content are not particularly limited. For example, one or more known photopolymerization initiators may be combined and the component ratio thereof may be adjusted to satisfy the desired absorption wavelength range of the present invention.

For a more specific example, the photopolymerization initiator (C) may be one or more compounds selected from the group consisting of triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds, and oxime-based compounds.

The photosensitive resin composition containing the photopolymerization initiator (C) is highly sensitive and can implement a fine pattern upon exposure, and when using it, strength and surface smoothness become good when a pattern is formed.

Examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2) -Yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro Methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2). -Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane And 1-one oligomers.

Further, examples of the acetophenone-based compound include a compound represented by the following formula (41).

<Formula 41>

In Formula 41, R1 to R4 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or a carbon number. It represents a naphthyl group which may be substituted by an alkyl group of 1 to 12.

Specific examples of the compound represented by Formula 41 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-butyl-2-amino(4-morpholinophenyl)ethan-1-one, 2-methyl-2 -Amino(4-morpholinophenyl)propan-1-one,2-methyl-2-amino(4-morpholinophenyl)butan-1-one, 2-ethyl-2-amino(4-morpholino Phenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, and the like. .

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) ratio Imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, the phenyl group at 4,4',5,5' And imidazole compounds substituted with a boalkoxy group. Among these, 2,2'bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole is preferably used.

As the oxime compound, 0-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-ㅐ- Benzoyloxime, the following Chemical Formulas 42, 43, 44, etc. are mentioned.

<Formula 42>

<Formula 43>

<Formula 44>

In addition, other photopolymerization initiators commonly used in this field can also be used in combination as long as the effect of the present invention is not impaired. Examples of other photoinitiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. These may be used alone or in combination of two or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As the thioxanthone compound, for example, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, etc. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be lifted.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, campoquinone, phenylclioxylic acid Methyl, titanocene compounds, etc. are mentioned as other photoinitiators.

Further, a photopolymerization initiator having a group capable of causing chain transfer as the photopolymerization initiator (C) may be used. As such a photoinitiator, what is described in Japanese Patent Publication No. 2002-544205 is mentioned, for example.

Examples of the photopolymerization initiator having a group capable of causing the chain transfer include compounds represented by the following formulas 45 to 50.

<Formula 45>

<Formula 46>

<Formula 47>

<Formula 48>

<Formula 49>

<Formula 50>

The photopolymerization initiator (C) may be used in combination with a photopolymerization initiator (C-1). When the photopolymerization initiator (C) is used in combination with the photopolymerization initiator (C-1), the photosensitive resin composition containing them becomes more sensitive, and thus productivity can be improved when the spacer is formed.

As the photopolymerization initiation aid (C-1), an amine compound and a carboxylic acid compound are preferably used.

Specific examples of the amine compound in the photopolymerization initiation aid (C-1) include aliphatic amine compounds such as triethanolamine, methyl diethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Isoamyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N,N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone) And aromatic amine compounds such as 4,4'-bis(diethylamino)benzophenone. Among them, an aromatic amine compound is preferably used as the amine compound.

Specific examples of the carboxylic acid compound in the photopolymerization initiation aid (C-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenyl And aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiator (C) may be 1 to 30 parts by weight, and preferably 1 to 10 parts by weight, based on the total solid content of the photosensitive resin composition. If the amount of the photopolymerization initiator (C) is within the above range, a fine pattern and an appropriate pattern height can be realized when a pattern is formed using a photosensitive resin composition, and it is highly sensitive, so that the strength or smoothness of the pattern formed using this composition is improved. It is preferable because it becomes good.

Solvent (D)

The solvent (D) may be used without limitation, as long as it is commonly used in the art.

Specific examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether, and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, and butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, and butoxybutyl acetate; Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, and butoxybutyl propionate; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl ethylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , Hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxybutylacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl, 2-methoxypropionate propyl, 2-methoxypropionate butyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl, 2-ethoxypropionate propyl, 2-ethoxypropionate butyl, 2-butoxypropionate methyl , Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 3-ethoxy propyl propionate, 3-ethoxy butyl propionate, 3-propoxy methyl propionate, 3-propoxy propionate ethyl, 3-propoxy propionate propyl, 3 -Esters such as butyl propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate; Cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as γ-butyrolactone. The solvents (D) exemplified herein can be used alone or in combination of two or more.

When considering coating properties and drying properties, the solvent (D) is alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, 3-ethoxy ethyl propionate, 3-ethoxyethyl propio Esters such as nate and methyl 3-methoxypropionate can be preferably used, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, 3-methoxy 1-butanol, 3-ethoxyethylpropionate and the like can be used.

The content of the solvent (D) may be included in a mass fraction of 30 to 90% by weight, preferably 40 to 85% by weight, based on the photosensitive resin composition containing the same. If the content of the solvent (D) is within the above range, coating properties are good when applied with a coating device such as a spin coater, a slit & spin coater, a slit coater (also called a die coater or curtain flow coater), or inkjet. It is preferable because it loses.

The photosensitive resin composition according to the present invention may further include additives (E) such as fillers, other polymer compounds, curing agents, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, chain transfer agents, and the like, if necessary. .

Specific examples of the filler may include glass, silica, and alumina.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used to increase deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxidation, isoprene (co ) Polymer epoxidation, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used in combination with a curing agent and a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators.

The carboxylic anhydrides may be commercially available as an epoxy resin curing agent. As the epoxy resin curing agent, for example, a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries Co., Ltd.), a brand name (Rikashido HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) ( Shin Nippon Ewha Co., Ltd.) and the like. The curing agent exemplified above may be used alone or in combination of two or more.

As the leveling agent, commercially available surfactants can be used, and for example, surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, etc. can be used. You may use it in combination of 2 or more types.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, In addition to polyethyleneimines, under brand names, KP (manufactured by Shin-Etsu Chemical Industries, Ltd.), Polyflow (manufactured by Kyei Chemical Corporation), Ftop (manufactured by Tochem Products), Megapak (manufactured by Tochem Products), Megapak (manufactured by Dai Nippon Ink Chemical Industries, Ltd.) Co., Ltd.), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Saffron (above, manufactured by Asahi Glass Co., Ltd.), Sor Spas (manufactured by Geneca Co., Ltd.), EFKA (EFKA Chemicals Co. Manufacturing), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As the adhesion promoter, a silane-based compound is preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

Specifically, the antioxidant is 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)prop Foxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine, 3,9-bis[2-{3-(3-tert) -Butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis( 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5- Methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''- Hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert) -Butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol, etc. are mentioned.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate.

Specific examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

Exposure stage

A step of exposing light through a mask to form a desired pattern on the coating film formed by applying the photosensitive resin composition is performed.

The exposure according to the present invention uses light of a complex wavelength, and the integral value of the amount of light of the wavelength of the j-line (300 nm or more and 340 nm or less) of the light is compared to the integral value of the light amount of the wavelength of the i-line (more than 340 nm and 380 nm or less). It is carried out to be 5 to 20%, preferably it can be carried out by adjusting to be 10 to 19%. In addition, it may be performed by reducing it to 20% to 80% compared to 100% of light of the j-line (300 nm or more and 340 nm or less) emitted from the light source.

When the light quantity value is adjusted within the above range, light reaching the deep portion of the coating film is reduced to maintain the activity of the photopolymerization initiator in an appropriate range, thereby forming a fine pattern. In addition, the height of the pattern is maintained in an appropriate range, so that a pattern having excellent adhesion can be realized. On the other hand, when the light quantity value is reduced to less than 5% with respect to the light quantity integral value of the wavelength of the i-line (more than 340 nm and not more than 380 nm), it is difficult to accelerate the decomposition of the photopolymerization initiator, making it difficult to form a pattern, and if it exceeds 20%, on the contrary, It may be difficult to implement a fine pattern due to a problem of increasing decomposition of the photopolymerization initiator.

The exposure may be performed by reducing an integral value of the amount of light of light having a wavelength of 300 nm or more and less than 330 nm among light having a complex wavelength to 20 to 70% compared to light emitted from the light source. By adjusting the light intensity integral value of light having a wavelength of 300 nm or more and less than 330 nm among the j-line to the above range, the light reaching the core of the coating film is reduced to adjust the activity of the photopolymerization initiator to an appropriate range, thereby forming a fine pattern. To be.

The exposure may be performed by reducing an integral value of the amount of light of light having a wavelength of 330 nm or more and 340 nm or less among the light having a complex wavelength to 15 to 90% compared to light emitted from the light source. By adjusting the integral value of the amount of light of light having a wavelength of 330 nm or more and 340 nm or less among the j-line to the above range, the light reaching the core of the coating film is reduced to adjust the activity of the photopolymerization initiator to an appropriate range, so that a fine pattern can be formed. do.

In the exposure, the integral value of the light quantity of light of the wavelength of the j-line (300 nm or more and 340 nm or less) can be reduced to the above-described range by using a filter, and the filter is disposed between the light source and the coating film, and the light emitted from the light source is The amount of light can be reduced.

The exposure step may be performed by uniformly irradiating a light beam whose intensity range of light of the above-described wavelength is adjusted to the entire exposure portion, and also use a device such as a mask aligner or a stepper so that the exact position of the mask and the substrate is performed. It is desirable to do. When light is irradiated, the light-irradiated portion is cured.

Development stage

The method of forming a photocurable pattern of the present invention may further include developing a cured coating film through exposure.

The developing step is performed by contacting the cured coating film with a developer, and dissolving the non-exposed portion to form a target pattern.

The developing method may be any of a liquid addition method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development.

The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The said alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, and the like. In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, or Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride or lauryltrimethylammonium chloride, or quaternary ammonium salts.

These surfactants can be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10 mass%, preferably 0.05 to 8 mass%, and more preferably 0.1 to 5 mass%.

After image development, it can wash with water, and post-baking for 10 to 60 minutes at 150-230 degreeC as needed can be performed.

< Photocuring Pattern and image display device>

The present invention relates to a photocurable pattern manufactured by the method of forming a photocurable pattern according to the present invention and an image display device including the photocurable pattern.

The photocurable pattern manufactured according to the pattern formation method of the present invention has excellent adhesion and can be implemented in high resolution. Accordingly, in an image display device, it can be used as various patterns, for example, an adhesive layer, an array planarization film, a protective film, an insulating film pattern, etc., and may be used as a photoresist, a black matrix, a column spacer pattern, etc., but is limited thereto. In particular, excellent developability and mechanical properties are excellent, which is very suitable as a spacer pattern.

As an image display device having such a photocurable pattern, there may be a liquid crystal display device, an OLED, a flexible display, and the like, but the present invention is not limited thereto, and all image display devices known in the art may be applied.

Hereinafter, examples will be described in detail to illustrate the present invention in detail.

Synthesis example 1: Synthesis of alkali-soluble resin (A-1)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared, and as a monomer dropping lot, 3,4-epoxytricyclodecane-8-yl (meth)acrylate (chemical formula 1) and A mixture of 3,4-epoxytricyclodecane-9-yl (meth)acrylate (chemical formula 2) (50:50 molar ratio) 40 parts by weight, methyl methacrylate 50 parts by weight, acrylic acid 40 parts by weight, vinyl toluene 70 parts by weight Parts, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added and prepared by stirring and mixing, and as a dropping tank for a chain transfer agent, n-dodecanethiol 6 A mixture by stirring and mixing was prepared in parts by weight and 24 parts by weight of PGMEA. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. Next, dropping of the monomer and chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90°C, and after 1 hour, the temperature was raised to 110°C and maintained for 5 hours to obtain a resin (A-1) having a solid acid value of 75 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthesis example 2: Synthesis of alkali-soluble resin (A-2)

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, the atmosphere in the flask was changed from air to nitrogen, and then heated to 100°C (A-2- 1) Monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 66.0 g (0.3 mol), (A-2-2) alpha-methylstyrene 35.0 g (0.30 mol), (A-2 -3) A solution in which 3.6 g of azobisisobutyronitrile was added to a mixture containing 28.8 g (0.40 mol) of acrylic acid and 136 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping lot to the flask over 2 hours at 100°C. Stirring was continued for 5 more hours. Then, the atmosphere in the flask was made from nitrogen to air, and (A-2-4) 42.0 g (0.28 mol) of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were added into the flask, The reaction was continued at for 6 hours to obtain a resin (A-2) having a solid acid value of 170.7 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 22.180, and the molecular weight distribution (Mw/Mn) was 2.3.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the binder polymer was performed under the following conditions using the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40°C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 µl

Detector: RI

Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and the number average molecular weight obtained above was taken as the molecular weight distribution (Mw/Mn).

Manufacturing example : Preparation of photosensitive resin composition

A photosensitive resin composition was prepared with the components and contents shown in the following table, and a solution diluted in PGMEA at a concentration of 1 mg/mL was used with a UV-Vis Spectrometer (Shimadzu, UV-2100), and the absorption wavelength of the photopolymerization initiator of each preparation example It was measured, and it is shown in FIG. 1.

division
(Parts by mass) Manufacturing example One 2 3 4 5 (A) Alkali-soluble resin A-1 25 25 25 25 25 A-2 25 25 25 25 25 (B) photopolymerizable compound 50 50 50 50 50 (C) photopolymerization initiator C-1 2.8 2.8 2.8 4.3 2.8 C-2 8.4 8.4 5.6 12.9 5.6 C-3 1.4 1.4 1.4 6.5 - (c-1) photopolymerization
Initiation aid c-1 4.2 7 8.4 2.6 2.8 Photopolymerization initiator
Absorption wavelength (nm) 325 330 335 318 351 (D) solvent D-1 37.1 37.1 37.1 37.1 37.1 D-2 29.4 29.4 29.4 29.4 29.4 D-3 3.5 3.5 3.5 3.5 3.5 (E-1) additive E-1 0.7 0.7 0.7 0.7 0.7 A-1: Alkali-soluble resin prepared in Synthesis Example 1
A-2: Alkali-soluble resin prepared in Synthesis Example 1
B-1: Dipentaerythritol hexaacrylate (KAYAKUD DPHA, Nippon Chemical Co., Ltd.)
C-1: 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (Hodogaya Chemical Co., Ltd.)
C-2: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-ㅐ-benzoyloxime (Shiba Corporation)
C-3: 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure-907, Shiva Corporation)
c-1: 4,4'-bis(diethylamino)benzophenone (EAB-F, Hodogaya Chemical Co., Ltd.)
D-1: Propylene glycol monomethyl ether acetate
D-2: 3-ethoxyethylpropionate
D-3: 3-methoxy-1-butanol
E-1 (antioxidant): 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)-1.3.5-triazine-2,4,6 (1H,3H, 5H)-trion (Itganox3114, Ciba Specialty Chemicals)

Example And Comparative example

(One) Example

Example 1 to 3

A 2 inch wide glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol, and then dried. On this glass substrate, the photosensitive resin composition prepared in Table 1 (Preparation Example 1 (Example 1), Production Example 2 (Example 2), and Production Example 3 (Example 3)) was spin-coated, respectively, and then a clean oven It was prebaked in 90 degreeC for 3 minutes. After cooling the prebaked substrate to room temperature, light was irradiated with the distance between the quartz glass photomask being 150 μm. The light emitted from the exposure machine was irradiated onto the substrate using a filter so that the integral value of the light intensity of light with a wavelength of 300 to 340 nm was 16% compared to the integral value of the light intensity of the i-line and 72% compared to the emitted light (5.0 mW). At this time, a photomask with the following pattern formed on the same plane was used as the photomask. It has a square-shaped light-transmitting portion (pattern) having a side of 10 µm, and the spacing of the squares is 100 µm. After light irradiation, the coating was developed by immersing the coating film in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 100 seconds, followed by washing in an oven at 220°C for 20 minutes post-baking. The obtained film thickness was 3 µm. The film thickness was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). The obtained pattern was evaluated for physical properties as follows, and the results are shown in Table 2 below.

Example 4

The light emitted from the exposure machine was irradiated to the substrate so that the integral value of the light intensity of light of 300 to 340 nm wavelength was 17% compared to the integral value of the light intensity of i-line and 76% compared to the emitted light using a filter (5.2mW, UV- A pattern was formed in the same manner as in Example 1 except for 31).

Example 5

The light emitted from the exposure machine was irradiated to the substrate using a filter so that the integral value of the light intensity of light with a wavelength of 330 to 340 nm became 12% compared to the integrated value of the light intensity of the i-line and 46% compared to the emitted light (3.5mW, UV-33 Except for ), a pattern was formed in the same manner as in Example 1.

(2) Comparative example

Comparative example 1 to 3

Photosensitive resin compositions (Production Example 1 (Comparative Example 1), Production Example 2 (Comparative Example 2), Production Example 3 (Comparative Example 3)) prepared according to the components and contents of Preparation Examples 1 to 3 described in Table 1, respectively And irradiated to the substrate (6.2mW, Not-Use) with the light emitted from the exposure machine without using a separate filter (the integral value of the intensity of light of the wavelength of 300 to 340 nm is 21% of the integral value of the amount of light of the i-line) Except for, a pattern was formed in the same manner as in Example 1.

Comparative example 4 to 6

The photosensitive resin composition (Production Example 1 (Comparative Example 4), Production Example 2 (Comparative Example 5), Production Example 3 (Comparative Example 6)) prepared according to the components and contents of Preparation Examples 1 to 3 described in Table 1 was used. And, the light emitted from the exposure machine was irradiated to the substrate using a filter so that the integral value of the light intensity of light with a wavelength of 300 to 340 nm is 3% compared to the integral value of the light intensity of the i-line and 14% compared to the emitted light (1.0mW, UV Except for -35), a pattern was formed in the same manner as in Example 1.

Comparative example 7 and 8

The photosensitive resin composition (Production Example 4 (Comparative Example 7), Production Example 5 (Comparative Example 8)) prepared according to the components and contents of Preparation Examples 4 and 5 described in Table 1 was used, respectively, and the light emitted from the exposure machine was Except for irradiation to the substrate (5.2mW, UV-31) using a filter so that the integrated light intensity of light with a wavelength of 300 to 340 nm is 17% compared to the integrated light intensity value of i-line and 76% compared to the emitted light A pattern was formed in the same manner as in Example 1.

Comparative example 9 and 10

Photosensitive resin compositions (Preparation Example 4 (Comparative Example 9), Preparation Example 5 (Comparative Example 10)) prepared according to the components and contents of Preparation Examples 4 and 5 described in Table 1 were used, respectively, and light emitted from the exposure machine was Except for irradiation to the substrate (3.5mW, UV-33) using a filter so that the integrated light intensity of light with a wavelength of 300 to 340 nm is 12% compared to the integrated light intensity value of i-line and 46% compared to the emitted light A pattern was formed in the same manner as in Example 1.

Comparative example 11 and 12

Photosensitive resin compositions (Preparation Example 4 (Comparative Example 11), Preparation Example 5 (Comparative Example 12)) prepared according to the components and contents of Preparation Examples 4 and 5 described in Table 1 were used, respectively, and light emitted from the exposure machine was In the same manner as in Example 1 except for irradiation (6.2mW, Not-Use) without using a separate filter (integral value of the intensity of light of light with a wavelength of 300 to 340 nm is 21% of the integral value of light of i-line) A pattern was formed.

Comparative example 13 and 14

Photosensitive resin compositions (Production Example 4 (Comparative Example 13), Production Example 5 (Comparative Example 14)) prepared according to the components and contents of Preparation Examples 4 and 5 shown in Table 1 were used, respectively, and light emitted from the exposure machine was Except for irradiation to the substrate (1.0mW, UV-35) using a filter so that the integrated light intensity of light with a wavelength of 300 to 340 nm is 3% compared to the integrated light intensity of i-line and 14% compared to the emitted light A pattern was formed in the same manner as in Example 1.

Test Methods

(1) the height of the pattern and Bottom CD

Using a three-dimensional shape measuring device (SIS-2000 Systems; manufactured by SNU Precision Co., Ltd.), the cured film obtained above was subjected to the height of the pattern and the line width of 10% of the height as shown in FIG. The line width of Top CD was measured, and the results are shown in Table 2 below.

The smaller the bottom CD(㎛), the better, and the higher the height than the target 3.0㎛, the better the sensitivity, so the better.

(2) pattern shape

The Bottom CD and Top CD measured in Test Method (1) were calculated by the following equation (1), and the results are shown in Table 2 below.

The closer to 100%, the closer it is to a cylindrical shape, which is better.

[Equation 1]

(Type of pattern)%=(Top CD)/(Bottom CD)*100

(3) cross-sectional shape

The cured film obtained above was evaluated for its cross-sectional shape as follows using a scanning electron microscope (S-4600; manufactured by Hitachi Corporation). The cross-sectional shape was determined as a pure taper when the angle of the pattern with respect to the substrate was less than 90 degrees, and an inverse taper when it was 90 degrees or more.

The pure taper is preferable because disconnection of the ITO wiring hardly occurs during formation of the display device.

(4) sensitivity

The development adhesion is evaluated by a microscope to evaluate the actual size of 100% of the pattern formed with a film thickness of 3㎛ by a photomask with 1000 circular patterns each of 1㎛ intervals from 5㎛ to 20㎛ diameter (size) without missing And the results are shown in Table 2 below.

The smaller the size, the better the sensitivity.

division pattern Cross-sectional shape Sensitivity
(Mask Size) Height
(㎛) Bottom CD
(㎛) shape
(%) Example 1 3.1 8 68 Pure taper 5 Example 2 3.2 8 66 Pure taper 5 Example 3 3.2 9 65 Pure taper 5 Example 4 3.2 9 60 Pure taper 6 Example 5 3.2 7 66 Pure taper 5 Comparative Example 1 3.2 12 57 Pure taper 6 Comparative Example 2 3.2 13 57 Pure taper 9 Comparative Example 3 3.2 13 54 Pure taper 9 Comparative Example 4 2.6 6 70 Pure taper 10 Comparative Example 5 2.7 7 67 Reverse taper 13 Comparative Example 6 2.7 8 66 Reverse taper 11 Comparative Example 7 2.5 8 61 Pure taper 11 Comparative Example 8 3.2 15 51 Pure taper 9 Comparative Example 9 2.6 7 61 Pure taper 10 Comparative Example 10 3.2 15 52 Reverse taper 10 Comparative Example 11 3.0 12 57 Pure taper 9 Comparative Example 12 3.2 16 50 Pure taper 9 Comparative Example 13 2.4 6 69 Pure taper 10 Comparative Example 14 3.2 14 65 Reverse taper 14

Referring to Table 2, it was confirmed that the patterns (Examples 1 to 5) prepared according to the present invention were small in size and exhibited an appropriate height (3.0 μm), so that they were suitable for realizing high resolution.

On the other hand, in the case of Comparative Examples 1 to 3, in which a photopolymerization initiator having an absorption wavelength within the range of the present invention was used, but the amount of light of the absorption wavelength in the 330 to 340 nm region was not adjusted during exposure, the height of the pattern was at the same level as the Example. However, it was confirmed that the bottom CD value of the pattern was very high, and the sensitivity was significantly lowered compared to the example.

In addition, in Comparative Examples 4 to 6, in which a photopolymerization initiator having an absorption wavelength within the range of the present invention was used, but the integral value of the amount of light of the absorption wavelength in the 330 to 340 nm region was significantly reduced during exposure, the height of the pattern was very small, and the sensitivity It was also confirmed that it was significantly lowered compared to the Example.

Claims (11)

In a method of forming a photocurable pattern by applying a photosensitive resin composition to at least one surface of a substrate and exposing it with light of a complex wavelength,
The exposure is performed so that the integral value of the light quantity of the light of the wavelength of the j-line (300 nm or more and 340 nm or less) of the light is 5 to 20% with respect to the integral value of the light quantity of the wavelength of the i-line (more than 340 nm and 380 nm or less),
The photosensitive resin composition comprises a photopolymerization initiator having a maximum absorption wavelength of 325 to 340 nm, a method of forming a photocurable pattern.
The method of claim 1, wherein the exposure is performed using a filter that reduces the integral value of the light quantity of light having a wavelength of a j-line (300 nm or more and 340 nm or less).
The method of claim 2, wherein the reduction of the integral value of the light quantity of light having a wavelength of the j-line (300 nm or more and 340 nm or less) is performed by 20 to 80% compared to the light emitted from the light source.
The method of claim 2, wherein the reduction in the integral value of the light quantity of light having a wavelength of 300 nm or more and less than 330 nm among the j-line is performed by 20 to 70% compared to light emitted from the light source.
The method of claim 2, wherein the integrated value of light having a wavelength of 330 nm or more and 340 nm or less among the j-line is reduced by 15 to 90% compared to the light emitted from the light source.
The method of claim 1, wherein the photopolymerization initiator is at least one selected from the group consisting of an acetophenone compound, a biimidazole compound, and an oxime compound.
The method of claim 1, wherein the photopolymerization initiator is contained in an amount of 1 to 30% by weight based on a total solid content of the photosensitive resin composition.
The method of claim 1, wherein the photosensitive resin composition further comprises an alkali-soluble resin, a photopolymerizable compound, and a solvent.
The method of claim 1, wherein the photocuring pattern is selected from the group consisting of an array planarization layer pattern, a protective layer pattern, an insulating layer pattern, a photoresist pattern, a black matrix pattern, and a column spacer pattern.
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