KR101359470B1 - Photosensitive resin composition and spacer preprared from the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, and more specifically, to a photosensitive resin composition which includes an alkali-soluble resin, a photocurable monomer, a photopolymerization initiator, an amino acetophenone-based or amino benzaldehyde acetophenone-based hydrogen donor, and a solvent, thereby improve photoreactivity by activating alkyl radicals generated from the photopolymerization initiator and providing improved sensitivity by maximizing light efficiency.

Description

Photosensitive resin composition and spacer manufactured therefrom {PHOTOSENSITIVE RESIN COMPOSITION AND SPACER PREPRARED FROM THE SAME}

The present invention relates to a photosensitive resin composition and a spacer prepared therefrom, and more particularly, to a photosensitive resin composition having a high sensitivity and high crosslinking density and a spacer prepared therefrom.

In general display devices, silica beads or plastic beads having a certain diameter have been used to maintain constant spacing of the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and located inside the pixel, there is a problem that the aperture ratio is lowered and light leakage phenomenon occurs. In order to solve these problems, it has begun to use spacers formed by photolithography inside the display device, and photolithography has become a common technique for manufacturing spacers used in image display devices.

A method of forming a spacer by photolithography is a method in which a photosensitive resin composition is coated on a substrate, ultraviolet rays are irradiated through the mask, and a spacer is formed at a desired position on the substrate in accordance with a pattern formed on the mask.

By the way, in order to prevent the contamination of the applied photosensitive resin composition and a mask, the board | substrate with which the mask and the photosensitive resin composition was applied needs to maintain constant space | interval. However, there is a problem that the light passing through the mask diffuses in the gap, so that the exposure is wider than the design size of the mask pattern.

In order to improve image quality, the pixel size is getting smaller, and since the spacer is also required to have a fine pattern having a smaller size according to the smaller pixel size, it is urgent to solve the above problem.

In order to solve this problem, Korean Patent Laid-Open Nos. 2001-0100808 and 2002-0053757 use a binder polymer as an acrylic copolymer and apply a photosensitive resin composition composed of a polyvalent acrylate crosslinking agent and a photopolymerization initiator onto a substrate. Although a technique is disclosed in which a spacer having a dot shape or a stripe shape is formed by interposing a predetermined mask, irradiating ultraviolet rays, curing a desired portion, and washing and removing the uncured portion with a basic aqueous solution. I can't let you.

Korean Laid-Open Patent No. 2001-0100808 Korean Laid-Open Patent No. 2002-0053757

An object of the present invention is to provide a photosensitive resin composition having high sensitivity and high crosslinking density even at a low exposure amount.

In addition, the present invention is excellent in adhesion to the substrate does not cause the loss of the pattern in the development process, it is possible to form a spacer having an excellent elastic recovery rate and T / B ratio, but a hard characteristic with little deformation in the external pressure It is an object to provide a photosensitive resin composition.

Another object of the present invention is to provide a spacer formed by applying and curing the photosensitive resin composition in a predetermined pattern.

Another object of the present invention is to provide an image display device having the spacer.

1. A photosensitive resin composition comprising an alkali-soluble resin, a photocurable monomer, a photopolymerization initiator, an aminoacetophenone-based or amino benzaldehyde-based hydrogen donor, and a solvent.

2. according to the above 1, wherein the aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor is a photosensitive resin composition represented by the following formula (1):

[Formula 1]

Wherein R ₁ and R ₂ are each independently a linear or branched alkyl having 1 to 6 carbon atoms; R ₃ is hydrogen, a hydroxy group or a straight or branched alkyl having 1 to 10 carbon atoms.

3. The photosensitive resin composition of 1 above, wherein the aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the composition.

4. The photosensitive resin composition according to the above 1, wherein the photopolymerization initiator comprises at least one photopolymerization initiator selected from the group consisting of acetophenone series, biimidazole series, and oxime series.

5. In the above 4, wherein the acetophenone-based photopolymerization initiator is diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldi methyl ketal, 2-hydroxy-1- [ 4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino Propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) -butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino -1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl ) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2, 4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2 -Methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -Butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1- Methylvinyl) phenyl] propan-1-one oligomer, 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) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-mor Polynophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1 Group consisting of -one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, and 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one Photosensitive resin composition which is at least 1 sort (s) chosen from.

6. In the above 4, wherein the biimidazole-based photopolymerization initiator 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) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole and an imidazole compound in which a phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group Photosensitive resin composition which is at least 1 sort (s) chosen from.

7. In the above 4, wherein the oxime-based photopolymerization initiator is O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, a compound represented by the following formula (5) and a compound represented by the following formula (6) At least one photosensitive resin composition selected from the group consisting of:

[Chemical Formula 5]

[Chemical Formula 6]

8. Spacer formed of the photosensitive resin composition of any one of the above 1 to 7.

9. The image display device having the spacer of the above eight.

The photosensitive resin composition of the present invention includes an aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor, thereby activating alkyl radicals generated in the photopolymerization initiator to further improve photoreactivity and maximize light efficiency to have significantly improved sensitivity. Due to such an improvement in sensitivity, it is possible to have a sufficient crosslinking density even for a small exposure amount during curing, and to shorten the exposure time.

In addition, after the photosensitive resin composition of the present invention is cured, the adhesion to the substrate is excellent, so that no loss of the pattern occurs in the developing step, and the shape retention performance of the pattern is excellent.

In addition, the spacer made of the photosensitive resin composition of the present invention has excellent elastic recovery rate and T / B ratio, and has hard properties with little deformation in external pressure.

In addition, when the photosensitive resin composition of the present invention is used in combination with an oxime ester-based photopolymerization initiator, the sensitivity is further improved, and the adhesion and pattern formation characteristics during curing are further improved to improve solvent resistance, heat resistance, and transparency.

1 is a view schematically showing the definition of the T / B ratio.

The present invention includes an alkali-soluble resin, a photocurable monomer, a photopolymerization initiator, an aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor and a solvent, thereby activating alkyl radicals generated in the photopolymerization initiator to further improve photoreactivity and maximize light efficiency. It relates to a photosensitive resin composition having a greatly improved sensitivity.

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

< Aminoacetophenones  or Aminobenzaldehyde  Hydrogen Donor>

The photosensitive resin composition of this invention contains an aminoacetophenone type or an aminobenzaldehyde type hydrogen donor.

The aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor activates an alkyl radical generated from a photopolymerization initiator upon light irradiation to further improve photoreactivity and maximize light efficiency, thereby improving sensitivity of the photosensitive resin composition. In this aspect, since hydrogen is donated at the alpha position of the nitrogen element in the aminoacetophenone-based or aminobenzaldehyde-based hydrogen donor, it is preferable that the nitrogen element is substituted with an alkyl group for more hydrogen donation.

More specific examples of the aminoacetophenone-based or aminobenzaldehyde-based hydrogen donors according to the present invention may be represented by the following Chemical Formula 1:

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a linear or branched alkyl having 1 to 6 carbon atoms; R ₃ is hydrogen, a hydroxy group, linear or branched alkyl of 1 to 10 carbon atoms; Preferably R ₃ is hydrogen or alkyl having 1 to 10 carbon atoms, straight or branched chain, more preferably R ₃ is hydrogen.

The content of the aminoacetophenone-based and aminobenzaldehyde-based hydrogen donors according to the present invention may be appropriately adjusted as necessary. For example, 0.1 to 20 parts by weight relative to 100 parts by weight of the photosensitive resin composition may be included in the photosensitive resin composition. It may be desirable to improve the sensitivity without reducing other physical properties, but is not limited thereto.

The photosensitive resin composition of the present invention includes, without particular limitation, components used in the photosensitive resin composition in the art in addition to the aminoacetophenone-based and aminobenzaldehyde-based hydrogen donors. For example, alkali-soluble resin, a photocurable monomer, a photoinitiator, a solvent, etc. can further be included.

<Alkali-soluble resin>

Alkali-soluble resins usually have reactivity and alkali solubility by the action of light or heat and act as a dispersion medium of other components. The alkali-soluble resin contained in the photosensitive resin composition of the present invention is preferably prepared by including a monomer having an epoxytricyclodecane ring structure and an unsaturated bond, and such a monomer is at least one of monomers represented by the following formulas (2) and (3). It is more preferable to include the above:

(2)

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is a single bond or an alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms; R ₁ and R ₂ may be independently substituted with a hydroxyl group,

(3)

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is a single bond or an alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms; R ₁ and R ₂ may be independently substituted with a hydroxyl group.

In Formula 2 and Formula 3, more specific examples of R ₁ , independently from each other, hydrogen; An alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group; Hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-1-hydroxypropyl group, N-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2-hydroxy- -Butyl group and the like. Among them, R ₁ is preferably independently of each other hydrogen, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

In Formula 2 and Formula 3, more specific examples of R ₂ , a single bond independently of each other; Alkylene groups such as a methylene group, an ethylene group and a propylene group; Containing alkylene groups such as a methylene group, an oxyethylene group, an oxyethylene 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, R ₂ is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group. In the present invention, when R ₂ is a single bond, it means that the carbon at the 8- or 9-position of the tricyclodecanyl group and the oxygen of the acrylate group are directly connected.

More specific examples of such a monomer having an epoxy tricyclodecane ring structure and an unsaturated bond include epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-9-yl (meth) acrylate; 3,4-epoxytricyclodecane-9-yl (meth) acrylate; Epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-8-yl (meth) acrylate; 3,4-epoxytricyclodecane-8-yl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-9-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-8-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyhexyl (meth) acrylate; Epoxidized dicyclodecaneyl (meth) acrylate etc. are mentioned, Preferably, epoxidized dicyclodecaneyl (meth) acrylate, epoxidized dicyclopentanyloxyethyl (meth) acrylate, etc. are mentioned. These may be used alone or in combination of two or more.

In the present invention, (meth) acrylate means acrylate and / or methacrylate.

Alkali-soluble resins according to the present invention can be prepared by copolymerizing monomers including the monomer having the epoxytricyclodecane ring structure and an unsaturated bond. More specifically, (a) a monomer having an epoxytricyclodecane ring structure and an unsaturated bond, (b) a monomer copolymerizable with the monomer having the epoxytricyclodecane ring structure and an unsaturated bond, and (c) a carboxyl group and an unsaturated bond. It can be prepared by copolymerizing a monomer having.

Specific examples of the (b) monomer are as follows.

First, styrene, chlorostyrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether and aromatic vinyl monomers such as p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene. Toluene is preferable because it is excellent in developability and processability. Further, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, N-phenyl maleimide, No-hydroxyphenyl maleimide, Nm-hydroxyphenyl maleimide, Np-hydroxyphenyl maleimide N-substituted maleimide systems such as No, methylphenyl maleimide, Nm-methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide Monomers; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylic Ethylene, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, Methoxytripropylene Glycol (Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonyl phenoxy polyethylene glycol (meth) acrylate, p-nonyl phenoxy polypropylene glycol (meth) Acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluoro Decyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acyloloxyethylhydrogensuccinate, methylα-hydroxymethylacrylate, ethylα-hydroxymethylacrylate, propyl (meth) acrylate-based monomers such as α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxylic acids such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Alkyl ester monomers; Carboxylic acid vinyl ester monomers, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Aliphatic conjugated diene monomers such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. The macromonomer which has, etc. are mentioned. These may be used alone or in combination of two or more.

The monomer having an unsaturated bond with the (c) carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and specific examples thereof include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, at least one other acid may be used. As other acid, unsaturated monocarboxylic acid or unsaturated polyhydric carboxylic acid can be used, and specifically, it uses together the carboxylic acid selected from 1 or more types of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, mesaconic acid, citraconic acid, maleic acid, and fumaric acid together. It is also possible. The monomer having an unsaturated bond with the carboxyl group may be in the form of an acid anhydride, and the unsaturated polyhydric carboxylic anhydride may be, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, or the like.

In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate mono (2-acryloyloxyethyl), monosuccinate mono (2-methacryloyloxyethyl ), Mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), etc. are mentioned.

The unsaturated polyhydric carboxylic acid may be a mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. .

Moreover, the said unsaturated polyhydric carboxylic acid may be unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, For example, (alpha)-(hydroxymethyl) acrylic acid etc. are mentioned.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of high copolymerization reactivity.

According to the present invention, in the copolymers obtained by copolymerizing the above-mentioned (a) to (c) (which is included in the present invention even when a monomer other than a to c is further included and copolymerized), each of (a) to (c) The proportion of the constituents derived from is preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

structural units derived from (a): 2-50 mol%,

structural units derived from (b): 2-50 mol%,

structural units derived from (c): 2 to 70 mole%

As described above, when the ratio of the constituents derived from each of (a) to (c) is within the above range, a good balance of developability, solubility and heat resistance can be obtained, so that a preferable copolymer can be obtained.

According to an embodiment of the present invention, the alkali-soluble resin is added to the copolymer obtained by the copolymerization reaction of the monomers (a) to (c) to add a compound having an unsaturated bond and an epoxy group in (d) 1 molecule to the alkali-soluble resin. Thermosetting property can be given.

Specific examples of the compound having an unsaturated bond and an epoxy group in the above (d) molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth). ) Acrylate, methylglycidyl (meth) acrylate, and the like. Of these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more. In the present invention, (meth) acrylate means acrylate and / or (meth) acrylate.

The compound having an unsaturated bond and an epoxy group in the (d) 1 molecule is preferably reacted at a molar fraction of 5 to 80 mol% with respect to the number of moles of the component derived from the compound having an unsaturated bond (c) in the copolymer. , And 10 to 70 mol% is more preferable. (d) When the compound which has an unsaturated bond and an epoxy group exists in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and it is excellent in reliability, and it is preferable.

Alkali-soluble resins according to the present invention can be prepared by adopting a known method known in the art, a solution polymerization method is more preferable among known polymerization methods. The polymerization temperature and polymerization time vary depending on the type and ratio of the monomers to be introduced, the molecular weight of the target binder resin and the acid value, but preferably polymerization is carried out at 60 to 130 ° C for 1 to 10 hours.

As the solvent used in the above process, a solvent used in a normal radical polymerization reaction may be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether , Toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

As the polymerization initiator to be used in the above step, a commonly used polymerization initiator may be added and is not particularly limited. Specifically, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexyl carbonate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl 2,2'-azobis (2-methylpropionate), etc. And nitrogen compounds. These can be used individually or in combination of 2 or more types.

In addition, the copolymer may use a mercapto-based chain transfer agent such as n-dodecyl mercapto, mercaptoacetic acid, methyl mercaptoacetate, α-methylstyrene dimer, or the like as a chain transfer agent in order to control the molecular weight or molecular weight distribution during the polymerization process. have. The amount of the α-methylstyrene dimer or mercapto compound is 0.005 to 5% by mass based on the total amount of monomers. In addition, the above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

In the present invention, the acid value of the alkali-soluble resin is preferably in the range of 20 to 200 mgKOH / g based on solid content. If the acid value is in the above range, it may have excellent elastic recovery after curing.

The alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of alkali-soluble resin exists in the range of 3,000-100,000, film | membrane decrease does not occur at the time of image development, and since the missing property of a non-pixel part at the time of image development is preferable, it is preferable.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of alkali-soluble resin, it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because it is excellent in developability.

The content of the alkali-soluble resin is preferably contained in a mass fraction of 5 to 90% by mass, more preferably 20 to 70% by mass, based on the total solids of the composition. If it is the said range, since the residue can remain at the time of image development, and a desired coating film can be formed, it is preferable.

< Photocurable  Monomer>

A photocurable monomer is a compound which can superpose | polymerize by the action | action of light and the said photoinitiator, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

The photocurable monomer used in the present invention may be used by mixing two or more photocurable monomers having different functional groups or functional groups in order to improve the developability, sensitivity, adhesion, and surface problems of the photosensitive resin composition. Do not limit range

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.

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) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (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.

Of these, multifunctional monomers having two or more functional groups are preferably used.

The photocurable monomer is normally used in 1 to 60 mass%, preferably 5 to 50 mass% in mass fraction with respect to solid content in the photosensitive resin composition. Since the intensity | strength and smoothness of a pixel part become it favorable that a photocurable monomer is the range of 1-60 mass% on the said reference | standard, it is preferable.

< Light curing Initiator >

In the photosensitive resin composition of the present invention, a photopolymerization initiator used in the art may be used without particular limitation.

For example, acetophenone compounds, biimidazole compounds, oxime compounds, triazine compounds, acylphosphine oxide compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, etc. Each can be used individually or in mixture of 2 or more types.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2- methyl-1- phenyl propane- 1-one, benzyl di methyl ketal, 2-hydroxy-1- [4- ( 2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholino Phenyl) -butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2 , 3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethyl Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholi Nophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino- 1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxy Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone , 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2 -Bro -4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones.

Moreover, as an acetophenone type compound which can be used other than the acetophenone type compound enumerated above, the compound represented by following formula (4) is mentioned, for example.

[Chemical Formula 4]

In the formula, each of R ₁ to R ₄ is 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 or carbon number which may be substituted by an alkyl group having 1 to 12 carbon atoms. The naphthyl group which may be substituted by the alkyl group of 1-12 is shown.

Specific examples of the compound represented by Formula 4 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 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) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4, The imidazole compound etc. which the phenyl group of a 4 ', 5,5'- tetra (trialkoxy phenyl) biimidazole or the 4,4', 5,5 'position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole are preferably used.

As said oxime type compound, O-ethoxycarbonyl- (alpha)-oxyimino- 1-phenyl propane- 1-one, the compound represented by following formula (5), the compound represented by following formula (6), etc. are respectively independently or 2 types It can mix and use the above.

[Chemical Formula 5]

[Chemical Formula 6]

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

As said acylphosphine oxide type compound, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned, for example.

Examples of the benzoin 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'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

In addition, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. are illustrated as a photoinitiator.

Moreover, as a photoinitiator which has group which can cause chain transfer, the photoinitiator described in Unexamined-Japanese-Patent No. 2002-544205 can be used.

As a photoinitiator which has the group which can generate the said chain transfer, the photoinitiator of following formula (7)-(12) is mentioned, for example.

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

Further, a light and / or thermal cationic polymerization initiator may be used.

The light and / or thermal cationic polymerization initiator may be composed of an onium cation and an anion derived from a Lewis acid.

As a specific example of the said onium cation, diphenyl iodonium, bis (p-tolyl) iodonium, bis (p-tert- butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octa) Decylphenyl) iodium, bis (p-octyloxyphenyl) iodium, bis (p-octadecyloxyphenyl) iodium, phenyl (p-octadecyloxyphenyl) iodium, (p-tolyl) (p-iso Propylphenyl) iodium, triphenylsulfonium, tris (p-tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butyl Phenyl) sulfonium, tris (p-cyanophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, Dimethyl (butoxy) sulfonium, Dimethyl (octyloxy) sulfonium, Dimethyl (octadecanoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, Dimethyl (tert-butoxy) sulfonium, Dimethyl (cyclopentyloxy) Sulfonium, Dimethyl (Cicle Hexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, Dimethyl (8-nitrooctyloxy) sulfonium, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, or dimethyl (tris (trichloromethyl) methyl) Sulfonium etc. are mentioned.

Preferable examples of the onium cation include bis (p-tolyl) iodonium, p-tolyl (p-isopropylphenyl) iodonium, bis (p-tert- butylphenyl) iodonium, triphenylsulfonium or tris -tert-butylphenyl) sulfonium, and the like. Specific examples of the anion derived from the Lewis acid include hexafluorophosphate, hexafluoroarsenate, hexafluoro antimonate, tetrakis (pentafluorophenyl) borate, and the like. Preferred examples of the anion derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.

The onium cation and the anion derived from the Lewis acid may be arbitrarily combined.

As a specific example of a cationic polymerization initiator, diphenyl iodonium hexafluoro phosphate, bis (p-tolyl) iodonium hexafluoro phosphate, bis (p-tert- butylphenyl) iodonium hexafluoro phosphate, bis (p -Octylphenyl) iodonium hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) Iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluoro Phosphate, ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexaple Orophosphate, tris (2,6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, Tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) Sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecaneoxy) sulphate Phosphorous hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclo Pentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluoro Phosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl ( 18-trifluoromethyloctadecaneoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluorophosphate ;

Diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis ), Iodonium hexafluoroarsenate, bis (p-octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (P-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate (p-phenylphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, , Methyl naphthyl iodonium hexafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate , Tris (p-isopropylphenyl) sulfonium hexafluoro Recetate, tris (2,6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexa Fluoroarsenate, tris (p-chlorophenyl) sulfoniumhexafluoroarsenate, dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate, dimethyl (methoxy) Sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate , Dimethyl (octyloxy) sulfonium hexafluoroarsenate, dimethyl (octadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-part Methoxy) sulfonium hexafluoro Recetate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoroarsenate, dimethyl (fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulphate Phonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarsenate;

Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis ), Iodonium hexafluoroantimonate, bis (p-octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis Iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate , Methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate , Tris (p-isopropylphenyl) sulfonium hexafluoro Timonate, tris (2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexa Fluoroantimonate, tris (p-chlorophenyl) sulfoniumhexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate, diethylnaphthylsulfonium hexafluoroantimonate, dimethyl (methoxy) Sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate , Dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-part Methoxy) sulfonium hexafluoro Timonate, dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-Chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulphate Phonium hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate;

Diphenyl iodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) ) Borate, bis (p-octylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluoro Phenyl) borate, (p-tolyl) (p-isopropylphenyl) iodium tetrakis (pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyl iodonium tetrakis (Pentafluorophenyl) borate, Triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) Borate, tris (2,6-dimethylphenyl) sulfoniumtetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfoniumtetrakis (pentafluorophenyl) borate, tris (p-cyano Phenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaph Tyl sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy Sulfonium Tet Kis (pentafluorophenyl) borate, dimethyl (butoxy) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (octyloxy) sulfoniumtetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulphate Phosphorium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl ( Cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl ) Borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobu Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) Borate, etc., Preferably, bis (p-tolyl) iodonium hexafluoro phosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoro phosphate, bis (p-tert- butylphenyl) is mentioned. Iodide hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (ptert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl ) (p-isopropylphenyl) Odenium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium hexafluoro Arsenate, Bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, Bis (p-tert-butylphenyl) iodine Hexafluoro antimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluoro Lophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodium, triphenylsulfonium tetrakis (pentafluoro Lophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorofe Ni)) borate and the like, and more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p- Tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetra Kiss (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, etc. are mentioned.

In addition, in this invention, a photoinitiator can also be used combining the photoinitiation adjuvant. When a photoinitiation adjuvant is used together with a photoinitiator, since the photosensitive resin composition containing these is more sensitive, productivity at the time of forming a spacer using this composition is preferable.

As a photoinitiation adjuvant, an amine compound, a carboxylic acid compound, a polyfunctional thiol compound, and the compound represented by following formula (13) are used preferably.

Specific examples of the amine compound in the photoinitiation aid include aliphatic amine compounds such as triethanolamine, methyl diethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4 -Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis Aromatic amine compounds, such as (diethylamino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichlorophenylthioacetic acid. And aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the polyfunctional thiol compound include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane trithiothioglycol Butanediol bisthio propionate, trimethylol propane tristyroopionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakistielopionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tris Thiopropionate, pentaerythritol tetrakis (3-mercaptobutylate), 1,4-bis (3-mercaptobutyryloxy) butane and the like.

The compound of formula 13 is

[Chemical Formula 13]

In Formula 13, the dotted line represented by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom,

Y represents an oxygen atom, a sulfur atom,

R ¹ represents an alkyl group having 1 to 6 carbon atoms,

R <^2> represents the C1-C12 alkyl group which may be substituted by the halogen atom, or the aryl group which may be substituted by the halogen atom.

Specific examples of the compound represented by the general formula (13) and the compound represented by the general formula (13) in the formula (13) is incorporated in the present invention as a whole matters described in Korean Patent Publication No. 10-2008-0059048.

The content of the photopolymerization initiator according to the present invention is usually 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin and the photocurable monomer, based on the solid content. On the basis of the above, it is usually 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight. When the usage-amount of a photoinitiator exists in the said range, since the photosensitive resin composition becomes high sensitivity, since the intensity | strength of the spacer formed using this composition and the smoothness of a spacer surface become favorable, it is preferable. Moreover, when the usage-amount of a photoinitiation adjuvant exists in said range, since the sensitivity of the photosensitive resin composition becomes high and the productivity of the spacer formed using this composition improves, it is preferable.

<Solvent>

In the photosensitive resin composition of the present invention, a solvent used in the art may be used without particular limitation.

Specific examples 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 methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl 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, 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate butyl, 2-hydroxy 3-Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, propoxy Methyl acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; Cyclic esters, such as (gamma) -butyrolactone, etc. can be used individually or in mixture of 2 or more types, respectively.

Among the above solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferably used in the above solvents in terms of applicability and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and butanediol alkyl ether acetates. Esters such as butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate may be preferably used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like may be used alone or in combination of two or more thereof.

The content of the solvent in the photosensitive resin composition of the present invention is 60 to 90 parts by weight, preferably 70 to 85 parts by weight, relative to 100 parts by weight of the photosensitive resin composition. When the content of the solvent is in the range of 60 to 90 parts by weight, the applicability is improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. desirable.

<Additives>

Optionally, the photosensitive resin composition of the present invention may further include additives such as fillers, other polymer compounds, curing agents, leveling agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, chain transfer agents, and the like.

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

Specific examples of the other high molecular 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 the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

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 type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ) Polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane.

The curing agent may be used together with a curing agent in combination with 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. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The hardeners illustrated above can be used individually or in mixture of 2 or more types.

As said leveling agent, commercially available surfactants can be used, For example, surfactants, such as a silicone type, a fluorine type, ester type, a cation type, an anion type, a nonionic type, an amphoteric, etc., are mentioned, These are each independently, either You may use in combination of 2 or more type.

As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoi Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), MegaPac (Dainippon Ink Chemical Co., Ltd.) Co., Ltd., Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahigard, Saffron (above, Asahigarasu Co., Ltd.), Soapaspa (Geneka Co., Ltd.), EFKA (EFKA CHEMICALS Co., Ltd.) Manufacture), PB821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As said adhesion promoter, a silane type compound is preferable, Specifically, a vinyl trimethoxysilane, a vinyl triethoxysilane, a vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 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] dioxaphosphine, 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, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-te (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

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

As said aggregation inhibitor, sodium polyacrylate etc. are mentioned specifically ,.

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

< Spacer  And image display device>

The present invention provides a spacer formed by forming a photosensitive resin composition in a predetermined pattern and then exposing and developing the same, and an image display display device having the same. The said image display apparatus spacer can be manufactured by apply | coating the photosensitive resin composition on a base material as follows, photocuring and developing, and forming a pattern, for example.

First, a photosensitive resin composition is coated on a substrate (usually glass) or a layer composed of a solid content of a previously formed photosensitive resin composition, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coat method or a slit coat method. It heats after application | coating and heat-drying (prebaking) or drying under reduced pressure, and volatilizes volatile components, such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline 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 nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually from 0.01 to 10% by mass, preferably from 0.05 to 8% by mass, more preferably from 0.1 to 5% by mass. After development, it is washed with water and optionally 150 to 230 ° C. Post-baking of 10 to 60 minutes can also be performed.

Using the photosensitive resin composition of this invention, a pattern can be formed on a board | substrate or a color filter substrate through each process as mentioned above. This pattern is useful as a photo spacer used in an image display device.

The spacer formed from the photosensitive resin composition of this invention is excellent in T / B ratio. The T / B ratio means a value obtained by dividing the upper diameter by the lower diameter in the spacer pattern. In the present invention, the top of the pattern is defined as the horizontal plane of the point that is 95% of the overall height from the bottom surface relative to the overall height of the pattern, and the bottom of the pattern is 5% of the total height from the bottom surface relative to the overall height of the pattern. It is defined as the horizontal plane of the point.

The larger the T / B ratio is, the more preferable it is. The spacer of the present invention may have a T / B ratio of 40 to 100%, preferably 50 to 90%.

As described above, the spacer of the present invention can be usefully used for an image display device such as a liquid crystal display device, and has excellent sensitivity, high crosslinking density even at low exposure amount, excellent adhesion to a substrate, high elastic recovery rate, and external It has mechanical strength with little deformation even under pressure.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Synthetic example : Alkali  Soluble Resin (A-1)

In a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto. It heated to 70 degreeC, stirring. Subsequently, 240 mass parts of mixtures of the following formula (28) and formula (29:50:50), 60 mass parts of methacrylic acid, and 140 mass parts of 3-methoxybutyl acetate were dissolved to prepare a solution.

(28)

[Chemical Formula 29]

The prepared solution was dripped in the flask kept warm at 70 degreeC over 4 hours using the dropping funnel. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetate, the flask over 4 hours using the other dropping funnel. It dripped in the inside. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, followed by copolymerization of a solid content of 32.6 mass% and an acid value of 110 mg-KOH / g (in terms of solid content). The solution of 1) was obtained.

The weight average molecular weight Mw of obtained resin A-1 was 13,400, and molecular weight distribution was 2.50.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer was carried out under the following conditions using the GPC method.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

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

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

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

Standard materials 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 number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

Example  1-5 and Comparative Example  1-3

To the photosensitive resin composition was prepared using the components and compositions shown in Table 1 below (units by weight).

Example Comparative Example One 2 3 4 5 6 One 2 3 Alkali-soluble resin (A) A-1 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 55.0 Photocurable Monomer (B) 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 Photopolymerization
Initiator
(C) C-1 1.5 1.5 1.5 - - - 1.5 1.5 1.5 C-2 1.5 1.5 1.5 - - - 1.5 1.5 1.5 C-3 - - 3.0 - 1.5 - - - C-4 - - - - 3.0 1.5 - - - Solvent (D) D-1 53.0 53.0 53.0 53.0 53.0 53.0 53.0 53.0 53.0 D-2 42.0 42.0 42.0 42.0 42.0 42.0 42.0 42.0 42.0 D-3 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Hydrogen donor (E) E-1 3.0 - - 3.0 3.0 3.0 - - - E-2 - 3.0 - - - - - - E-3 - - 3.0 - - - - - E-4 - - - - - - 3.0 - E-5 - - - - - - - 3.0 Additive (F) 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 B: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.)

C-1: 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM: Hodogaya Chemical Co., Ltd.) Produce)
C-2: 2-methyl2-morpholino (4-thiomethylphenyl) propan-1-one (Irgacure-907: manufactured by Ciba Specialty Chemicals)
C-3: OXE-1 (manufactured by Ciba Specialty Chemicals)
C-4: OXE-2 (manufactured by Ciba Specialty Chemicals)

D-1: Propylene Glycol Monomethyl Ether Acetate
D-2: diethylene glycol methylethyl ether
D-3: 3-methoxy-1-butanol

E-1: PAA (p-dimethylaminoacetophenone)
E-2: 4-dimethylaminobenzaldehyde
E-3: 4-dimethylaminobenzoic acid
E-4: acetophenone
E-5: 4,4'-bis (dimethylamino) benzophenone

F (antioxidant): 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Irganox3114; manufactured by Ciba Specialty Chemicals)

Test Example

&Lt; Pattern formation >

A glass substrate (Eagle 2000; manufactured by Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. On this glass substrate, the photosensitive resin composition was exposed at an exposure dose (405 nm) of 100 mJ / cm 2, and spin-coated so that the film thickness when developing, washing with water and postbaking was 3.0 μm, and then in a clean oven at 90 ° C. Prebaked for 3 minutes at. After cooling, the interval between the substrate coated with the photosensitive resin composition and the quartz glass photomask was 10 µm, and 100 mJ / exposure amount (405 nm standard) was used under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Light irradiation). Moreover, the light irradiation to the photosensitive resin composition at this time passed the light emitted from an ultrahigh pressure mercury lamp through the optical filter (LU0400; Asahi spectrometer), and cut and used the light of 400 nm or less.

A photomask in which the following pattern is formed on the same plane was used as the photomask.

(1) One side had a square light-transmitting part (pattern) of 10 micrometers, and the said space | interval was 100 micrometers.

(2) One side has a square light-transmitting part (pattern) of 15 micrometers, and the said space | interval is 100 micrometers.

After light irradiation, the substrate was developed by immersing the coating film at 25 ° C. for 100 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, and after washing with water, the post was washed for 20 minutes at 220 ° C. in an oven. Bake was performed. After cooling, the film thickness of the obtained cured film was 3.0 micrometers as a result of using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

<Transmittance>

The transmittance | permeability (%) in 400 nm of the cured film obtained above was measured using the microscope spectrophotometer (OSP-SP200; the product made by OLYMPUS). The transmittance is shown in Table 2 below in terms of transmittance at a film thickness of 3.0 μm. The transmittance is better near 100%.

< Line width , Cross-sectional shape>

The line width was measured for the cured film obtained above using the scanning electron microscope (S-4200; the Hitachi Corporation make), and the cross-sectional shape was evaluated as follows. The cross sectional shape was determined as a reverse taper when the angle of the pattern with respect to the substrate was less than 90 degrees and as a reverse taper when the angle was greater than 90 degrees.

A forward taper is preferable because disconnection of the ITO wiring hardly occurs at the time of forming the display device.

Mechanical Characteristics (Total Displacement and Recovery Rate)

The cured film obtained above was measured using a dynamic ultra-micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) and its total displacement amount (µm) and elastic displacement amount (µm) were measured according to the following measurement conditions. The recovery rate (%) was calculated as follows. It was judged that the total recovery was hard and the recovery rate was large.

Recovery rate (%) = [elastic displacement amount (占 퐉)] / [total displacement amount (占 퐉)] 占 100

Measuring conditions:

(a) Test mode: load-unload test

(b) Test force: 5gf [SI unit conversion value; 49.0mN]

(c) Load speed: 0.45 gf / sec [SI unit conversion value; 4.41 mN / sec]

(d) holding time: 5sec

(e) Indenter: truncated indenter (diameter 50㎛)

<Sensitivity>

Sensitivity is evaluated by a microscope for the size of a mask in which 100% of patterns having a film thickness of 3 μm remain without a dropout by a photomask having 1000 circular patterns each having a diameter ranging from 5 μm to 20 μm in 1 μm intervals. It was.

The smaller the size of the mask, the better the sensitivity.

<T / B ratio measurement>

After the pattern was formed on the glass substrate on which the ITO was spattered, the pattern was formed and observed with SNU Precision's 3D shape measuring instrument SIS-2000, and the bottom CD (a) was positioned at 5% of the total height from the bottom surface of the pattern. Define the top CD (b) where 95% of the total height is from the bottom surface, divide the length of (b) by the length of (a), and multiply by 100 (= b / a × 100). Defined by B ratio.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Transmittance (%) 99 98 99 99 99 99 98 99 99 pattern Line width (μm) 14.7 14.3 14.5 14.3 14.4 14.6 13.0 13.2 12.8 shape Sun Taper Sun Taper Sun Taper Sun Taper Sun Taper Sun Taper Reverse taper Reverse taper Sun Taper Mechanical characteristics Total displacement (㎛) 0.72 0.72 0.75 0.82 0.79 0.77 1.03 1.20 1.12 % Recovery 63.7 67.8 64.4 65.2 65.3 65.0 57.7 55.7 58.2 Mask Size 6 μm 5㎛ 7 탆 7 탆 7 탆 7 탆 10 탆 11㎛ 9㎛ T / B ratio (%) 60 65 53 62 61 61 31 25 35

Referring to Table 2, in Examples 1 to 6 according to the present invention, the adhesion and the pattern shape to the substrate is good at a low exposure amount, compared to Comparative Examples 1 to 3 which do not use it, the elastic recovery rate is excellent and the total displacement amount This has not only low mechanical properties but also excellent sensitivity, and in particular, it can be seen that the T / B ratio is improved.

In addition, Comparative Example 3 using a bisphenone-based hydrogen donor can be seen that the T / B ratio is particularly reduced compared to the embodiment of the present invention.

Claims (9)

Alkali soluble resins;
Photocurable monomers;
A photopolymerization initiator;
hydrogen donors which are p-dimethylaminoacetophenone compounds or aminobenzaldehyde compounds; And
A photosensitive resin composition comprising a solvent.
The photosensitive resin composition of claim 1, wherein the aminobenzaldehyde-based compound hydrogen donor is represented by Formula 1 below:
[Chemical Formula 1]

(Wherein R ₁ and R ₂ are each independently straight or branched alkyl having 1 to 6 carbon atoms; R ₃ is hydrogen).
The photosensitive resin composition of claim 1, wherein the hydrogen donor is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the composition.
The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator comprises at least one photopolymerization initiator selected from the group consisting of acetophenone series, biimidazole series, and oxime series.
The method of claim 4, wherein the acetophenone-based photopolymerization initiator is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldi methyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholi Nophenyl) -butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl)- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- ( 2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholino Phenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholi Nophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl)- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butane On , 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- ( Oligomer of 1-methylvinyl) phenyl] propan-1-one, 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 -Morpholinophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane -1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one At least one photosensitive resin composition selected from the group consisting of.
The method of claim 4, wherein the biimidazole-based photopolymerization initiator is 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 ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) Selected from the group consisting of -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole and an imidazole compound in which a phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group Photosensitive resin composition which is at least 1 sort (s).
The method of claim 4, wherein the oxime-based photopolymerization initiator is O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, a compound represented by the following formula (5) and a compound represented by the following formula (6) At least one photosensitive resin composition selected from:
[Chemical Formula 5]

[Chemical Formula 6]

The spacer formed from the photosensitive resin composition of any one of Claims 1-7.
An image display device comprising the spacer of claim 8.

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