WO2014193165A1 - Photosensitive resin composition for forming spacer, and spacer prepared therefrom - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a spacer, and more specifically, to a photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin comprises an alicyclic epoxy group and an aliphatic epoxy group, thereby allowing a spacer to be prepared having an excellent elastic recovery rate and having a hardness enabling little deformation from external pressure.

Description

Photosensitive resin composition for forming spacer and spacer prepared therefrom

The present invention relates to a photosensitive resin composition for forming a spacer and a spacer manufactured therefrom, and more particularly, to a photosensitive resin composition for forming a spacer which can be applied to an image display device because of excellent elastic restoring force and less deformation in external pressure. It relates to a spacer produced from.

In general, display devices have used silica beads or plastic beads having a constant diameter in order to maintain a constant distance between upper and lower substrates. However, when such beads are randomly dispersed on the substrate and positioned inside the pixel, the aperture ratio is lowered and light leakage occurs. In order to solve these problems, a spacer formed by photolithography is started to be used inside a display device. Currently, spacers used in most display devices are formed by photolithography.

The method of forming a spacer by photolithography is to apply a photosensitive resin composition on a substrate, irradiate ultraviolet rays through a mask, and then form the spacer at a desired position on the substrate according to a pattern formed on the mask through a developing process.

Recently, as the demand for touch panels increases due to the popularization of smartphones and tablet PCs, external pressure is applied as well as elastic recovery rate, which is a basic characteristic of spacers to maintain a gap between the color filter substrate and the array substrate constituting the display device. In the case of losing, a hard characteristic is demanded so that there is no pixel deformation. However, in the case of the conventional photosensitive resin composition for forming a spacer, the elastic recovery rate is sufficiently realized, but the rigid characteristics without pixel deformation due to external pressure are not realized to a satisfactory level.

In this regard, Japanese Patent Laid-Open No. 1999-133600 discloses a photosensitive resin composition for forming a spacer comprising a copolymer resin having a carboxyl group and a glycidyl ether group as a binder resin. Although the composition of JP-A-1999-133600 secured some degree of heat-resistant dimensional stability and strength, it still did not satisfy satisfactory elastic recovery rate and strength.

[Preceding technical literature]

[Patent Documents]

Patent Document 1: Japanese Patent Application Laid-Open No. 1999-133600

An object of the present invention is to provide a photosensitive resin composition for forming a spacer, the crosslinking density of which is dramatically increased when subjected to a heating step.

Moreover, an object of this invention is to provide the photosensitive resin composition for spacer formation which has the rigid characteristic which has the outstanding elastic recovery rate and little deformation in external pressure.

Moreover, an object of this invention is to provide the spacer formed by apply | coating and hardening the said photosensitive resin composition for spacer formation in a predetermined pattern.

Moreover, an object of this invention is to provide the image display apparatus provided with the said spacer.

1. A photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin is a compound having an (A-1) unsaturated bond and a carboxyl group, (A-2) A photosensitive resin composition for forming a spacer, which is a copolymer comprising a compound which is at least one of 2 and a compound of formula (A-3)

[Formula 1]

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 alkylene having 1 to 20 carbon atoms, with or without heteroatoms or Cycloalkylene; wherein R ₁ and R ₂ may be independently substituted with a hydroxy group)

[Formula 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 alkylene having 1 to 20 carbon atoms, with or without heteroatoms or Cycloalkylene; wherein R ₁ and R ₂ may be independently substituted with a hydroxy group)

[Formula 3]

(Wherein R ₁ is hydrogen, alkyl having 1 to 10 carbon atoms or cycloalkyl having 3 to 10 carbon atoms, the alkyl and cycloalkyl may be independently of each other a hetero atom, R _2, and R ₃ are independently of each other) Linear or branched alkylene having 1 to 20 carbon atoms, wherein R ₁ , R _2, and R ₃ may be independently substituted with a hydroxy group)

2. In the above 1, wherein in Formula 3 R ₁ is hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, 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 In the group consisting of -hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group and 4-hydroxy-n-butyl group The photosensitive resin composition for spacer formation which is any one selected.

3. In the above 1, wherein R ₂ and R ₃ of the formula 3 independently of each other selected from the group consisting of methylene group, ethylene group, propylene group, butylene group, tetramethylene group, ethylethylene group and pentamethylene group Photosensitive resin composition for spacer formation which is one.

4. according to the above 1, wherein the (A-3) compound is 2-hydroxyethyl acrylate glycidyl ether; 2-hydroxyethyl methacrylate glycidyl ether; 4-hydroxybutyl acrylate glycidyl ether; 4-hydroxybutyl methacrylate glycidyl ether; 6-hydroxyhexyl acrylate glycidyl ether; 6-hydroxyhexyl methacrylate glycidyl ether; A spacer that is at least one selected from the group consisting of 2-propenoic acid, 2- (2-oxyranylethoxy) ethyl ether and 2-propenoic acid, 4- (4-oxyranylbutoxy) butyl ether Photosensitive resin composition for formation.

5. In the above 1, wherein the alkali-soluble resin is 5 to 80 mol% of the structural unit derived from the compound (A-1), 10 to 85 mol% of the structural unit derived from the compound (A-2) and (A-3 The photosensitive resin composition for spacer formation containing 10-85 mol% of structural units derived from the compound.

6. Spacer made of a photosensitive resin composition for spacer formation of any one of the above 1 to 5.

7. Image display device having a spacer of the above six.

Since the photosensitive resin composition for forming a spacer of the present invention includes at least two epoxy substituents having different reactivity, the alkali-soluble resin includes a highly reactive epoxy substituent, particularly an aliphatic epoxy group, under heating conditions during the spacer manufacturing process. As the ring-opening reaction proceeds, the spacer to be produced may have a significantly high crosslinking density and thus excellent mechanical properties.

In addition, the spacer made of the photosensitive resin composition for forming a spacer of the present invention has excellent elastic recovery rate, and has a hard property with little deformation in external pressure.

The present invention relates to a photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin is a compound having a (A-1) unsaturated bond and a carboxyl group, (A-2) By including a compound having at least one compound of Formulas 1 to 2 and a copolymerized resin including the compound of formula (A-3) below, a spacer having excellent elastic recovery and having hard deformation with little deformation at external pressure can be prepared. The present invention relates to a photosensitive resin composition.

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

<Alkali-soluble resin (A)>

Alkali-soluble resins have reactivity to light or heat and alkali solubility, and serve as dispersion mediums for the respective components in the composition of the present invention.

Alkali-soluble resin of this invention contains an alicyclic epoxy group and an aliphatic epoxy group. Alicyclic means a hydrocarbon having a ring other than an aromatic ring, and aliphatic refers to a hydrocarbon having a linear structure including a straight or branched chain. Therefore, an alicyclic epoxy group means the structure which the epoxy group connected to the ring, and an aliphatic epoxy group means the structure which the epoxy group connected to the linear carbon chain.

Since the aliphatic epoxy group has high reactivity, the ring-opening reaction proceeds under heating conditions during the spacer manufacturing process, thereby remarkably improving the crosslinking density of the photosensitive resin composition.

In one embodiment of the alkali-soluble resin according to the present invention, a compound having a (A-1) unsaturated bond and a carboxyl group, (A-2) a compound of at least one of the formulas (1) to (2) and (A-3) It may be a copolymer copolymerized with the compound of formula (3).

[Formula 1]

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 alkylene having 1 to 20 carbon atoms, with or without heteroatoms or Cycloalkylene; wherein R ₁ and R ₂ may be independently substituted with a hydroxy group)

[Formula 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 alkylene having 1 to 20 carbon atoms, with or without heteroatoms or Cycloalkylene; wherein R ₁ and R ₂ may be independently substituted with a hydroxy group)

[Formula 3]

(Wherein R ₁ is hydrogen, alkyl of 1 to 10 carbon atoms or cycloalkyl of 3 to 10 carbon atoms, and the alkyl and cycloalkyl may independently include a hetero atom,

R _2, and R ₃ are each independently a linear or branched alkylene having 1 to 20 carbon atoms,

R ₁ , R ₂ and R ₃ may be further substituted with a hydroxyl group independently of each other)

The hetero atom in Chemical Formula 3 is not particularly limited, and for example, at least one of nitrogen, oxygen, and sulfur may be exemplified.

 (A-1) Compound having an unsaturated bond and a carboxyl group

The compound having an unsaturated bond and a carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond which can be polymerized. Specific examples thereof include two compounds in a molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or unsaturated tricarboxylic acid. The polyhydric carboxylic acid etc. which have the above carboxy group are mentioned.

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

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

The polyhydric carboxylic acid may be an acid anhydride, and the unsaturated polycarboxylic dianhydride 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-methacryloyloxy Ethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), and the like.

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

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.

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

The compounds having an unsaturated bond and a carboxyl group according to the present invention can be used alone or in combination of two or more.

(A-2) A compound which is at least one of Formulas 1 to 2

The compound of at least one of the formulas (1) to (2) according to the present invention is a compound containing an epoxy group which increases the polymerizable unsaturated bond and the crosslinking density.

In Formula 1 and Formula 2, more specific examples of R ₁ , independently from each other, hydrogen; 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 Or a hydroxy group-containing alkyl group such as -butyl group. Especially, it is preferable that R <_1> is hydrogen, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or 2-hydroxyethyl group independently from each other, and it is more preferable that it is especially a hydrogen or a methyl group.

In Formula 1 and Formula 2, more specific examples of R ₂ , a single bond independently of each other; Alkylene groups such as methylene group, ethylene group and propylene group; Hetero atom-containing alkylene groups such as oxymethylene group, oxyethylene group, oxypropylene group, thiomethylene group, thioethylene group, thiopropylene group, aminomethylene group, aminoethylene group and aminopropylene group. Among them, R ₂ is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, and more preferably a single bond or an oxyethylene group. In the present invention, the case where R ₂ is a single bond means a case where carbon at the 8 or 9 position of the tricyclodecaneyl group and oxygen of the acrylate group are directly connected.

More specific examples of the compound represented by formula (1) include the following formulas (1-1) to (1-15).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

More specific examples of the compound represented by Formula 2 include the following Formulas 2-1 to 2-15.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

[Formula 2-14]

[Formula 2-15]

Compounds exemplified as the compounds represented by Formula 1 and Formula 2 may be used alone or in combination of two or more.

(A-3) Compound of Formula 3

The compound of formula 3 is a compound containing an aliphatic epoxy group. The aliphatic epoxy group has high reactivity, and thus the ring-opening reaction proceeds during the manufacturing process of the spacer using the photosensitive resin composition of the present invention to increase the crosslinking density, thereby enhancing mechanical properties such as strength of the spacer.

In addition, the compound of formula 3 includes an ether bond in the linking structure between the acrylate group and the epoxy group. By including such ether linkages, spacers made from the compositions of the present invention can have excellent cumulative mechanical properties (cumulative recovery) among the mechanical properties. Cumulative recovery rate refers to the ability to return to the original state even after repeated deformations. In the present invention, but was carried out by taking the repetition number of times as an example, but is not limited thereto.

In Formula 3, more specific examples of R ₁ , independently from each other, hydrogen; 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 Or a hydroxy group-containing alkyl group such as -butyl group. Especially, it is preferable that R <_1> is hydrogen, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or 2-hydroxyethyl group.

In the above formula (3) straight or branched one such specific example, the group of methylene, independently of each other, an ethylene group, a propylene group, a butylene group, a tetramethylene group, ethyl ethylene, pentamethylene group than R ₂ and R ₃ It may be an alkylene group. Especially, it is preferable that R <_2> and R <_3> is a methylene group, ethylene group, or butylene group.

Specific examples of the compound of Formula 3 include 2-hydroxyethyl acrylate glycidyl ether, 2-hydroxyethyl methacrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, 4 Unsaturated carboxylic ester compounds containing glycidyl groups such as -hydroxybutyl methacrylate glycidyl ether, 6-hydroxyhexyl acrylate glycidyl ether, 6-hydroxyhexyl methacrylate glycidyl ether; Unsaturated carboxylic acid esters containing oxiranyl groups, such as 2-propenoic acid, 2- (2-oxyranylethoxy) ethyl ether, 2-propenoic acid, 4- (4-oxyranylbutoxy) butyl ether A compound etc. can be mentioned, They can be used individually or in combination of 2 types or more, respectively.

Further, in the alkali-soluble resin (A) according to the present invention, the copolymers of (A-1), (A-2) and (A-3) include (A-1), (A-2) and (A). In addition to -3), a compound having an unsaturated bond polymerizable with (A-1), (A-2) and (A-3) can be copolymerized together.

Specific examples of the compound having an unsaturated bond polymerizable with the above (A-1), (A-2) and (A-3) include 2-aminoethyl acrylate, 2-aminoethyl methacrylate and 2-dimethylaminoethyl Acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate Unsaturated carboxylic acid aminoalkyl esters such as 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; Carboxylic acid vinyl 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 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.

Copolymer ((A-1), (A-2) and (A) obtained by alkali-soluble resin (A) according to the present invention copolymerizing the above (A-1), (A-2) and (A-3) -3) is included in the present invention even when a monomer other than -3) is included in the copolymer), and in the copolymer, a component derived from each of (A-1), (A-2) and (A-3) It is preferable that a ratio exists in the following ranges by a mole fraction with respect to the total number of moles of the structural unit which comprises said copolymer.

Structural unit derived from (A-1): 5 to 80 mol%,

Structural unit derived from (A-2): 10-85 mol%,

Structural unit derived from (A-3): 10-85 mol%.

In particular, it is more preferable if the ratio of the said structural unit is the following ranges.

Structural unit derived from (A-1): 10 to 70 mol%

Structural unit derived from (A-2): 15 to 75 mol%

Structural unit derived from (A-3): 15-75 mol%.

If the ratio of the said structural unit exists in the said range, manufacture of the photosensitive resin composition with favorable developable solvent resistance, heat resistance, and mechanical strength will be attained.

For the alkali-soluble resin (A), for example, with reference to the method described in the document "Experimental method of polymer synthesis" (first edition March 1, 1972, first edition of Otsu Takayuki Kogyo Co., Ltd.) It can manufacture.

Specifically, oxygen is absent by placing a predetermined amount, a polymerization initiator and a solvent of units (A-1), (A-2) and (A-3) constituting the copolymer in a reaction vessel and replacing oxygen with nitrogen. The polymer is obtained by stirring, heating, and keeping warm under the following. Moreover, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and the thing extracted as solid (powder) by methods, such as reprecipitation, may be used.

It is preferable that alkali-soluble resin has an acid value of 20-200 (KOHmg / g). When the acid value is in the above range, the spacer having excellent aging stability and elastic recovery rate can be produced.

The weight average molecular weight of polystyrene conversion of alkali-soluble resin is 3,000-100,000, Preferably it is 5,000-50,000. When the weight average molecular weight of alkali-soluble resin exists in the said range, since film reduction is prevented at the time of image development, the omission property of a pattern part becomes favorable, and 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. When the said molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is contained in the said range, since developability becomes excellent, it is preferable.

The content of the alkali-soluble resin is in the range of 5 to 90% by weight, preferably 10 to 70% by weight based on the total solids in the photosensitive resin composition for spacer formation. When the content of the alkali-soluble resin is 5 to 90% by weight based on the above standards, the solubility in the developing solution is sufficient, so that the developability is excellent, and the preparation of the spacer having a hard property having excellent elastic recovery rate and low deformation at external pressure It becomes possible.

<Photopolymerizable compound (B)>

The photopolymerizable compound contained in the photosensitive resin composition for spacer formation of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. .

The photopolymerizable compound used in the present invention may be used by mixing two or more photopolymerizable compounds having different structure or number of functional groups in order to improve the developability, sensitivity, adhesion, surface problem, etc. of the resin composition for spacer formation. It does not limit its scope. Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc. 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, 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, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound is used in the range of 1 to 90 parts by weight, preferably 10 to 80 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin and the photopolymerizable compound based on the solids in the photosensitive for spacer formation. The photopolymerizable compound is preferable because the strength and smoothness of the spacer pattern become good in the above content range.

<Photoinitiator (C)>

The photopolymerization initiator may be applied without limitation to those generally used in the art.

For example, one or more compounds selected from the group consisting of triazine compounds, acetophenone compounds, biimidazole compounds, and oxime compounds can be used. The photosensitive resin composition containing the said photoinitiator is high sensitivity, and the intensity | strength and surface smoothness of the spacer pattern formed using this composition become favorable.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 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.

As said acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones.

Moreover, as said acetophenone type compound, the compound represented by following formula (4) is mentioned, for example.

[Formula 4]

In formula (4), R ₁ to R ₄ are independently of each other 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 naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 4 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) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-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, etc. may be mentioned. .

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 (trialkoxyphenyl) biimidazole, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among these, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetra phenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include 0-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the following formulas (5), (6) and (7).

[Formula 5]

[Formula 6]

[Formula 7]

Moreover, as long as it does not impair the effect of this invention, the other photoinitiator etc. which are normally used in this field can also be used together. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound etc. are mentioned, for example. These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. 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 mentioned.

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenyloxyoxylate, A titanocene compound etc. are mentioned as another photoinitiator.

Moreover, you may use the photoinitiator which has group which can cause chain transfer as a photoinitiator. As such a photoinitiator, what was described in Unexamined-Japanese-Patent No. 2002-544205 is mentioned, for example.

As a photoinitiator which has group which can cause said chain transfer, the compound represented by following formula (8) -13 is mentioned, for example.

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

In addition, in this invention, you may use combining a photoinitiator as a photoinitiator. When a photoinitiation adjuvant is used together with the said photoinitiator, since the photosensitive resin composition containing these becomes more sensitive and can improve productivity at the time of spacer formation, it is preferable.

As the photopolymerization start adjuvant, an amine compound and a carboxylic acid compound are preferably used.

Specific examples of the amine compound in the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid isoamyl. , 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4 ' Aromatic amine compounds, such as -bis (diethylamino) benzophenone, are mentioned. Among them, an aromatic amine compound is preferably used as the amine compound.

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

The content of the photopolymerization initiator is 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 photopolymerizable compound, and the content of the photopolymerization initiator is 0.1 to 50 parts by weight based on the above criteria. Parts, preferably 1 to 40 parts by weight.

When the content of the photopolymerization initiator is in the above range, the photosensitive resin composition is highly sensitive, and thus the strength and smoothness of the spacer formed by using the composition are good, which is preferable. In addition, when the content of the photopolymerization initiation aid is in the above range, the sensitivity of the photosensitive resin composition is higher and the productivity of the spacer pattern formed by using the composition is preferable.

<Solvent (D)>

The solvent can be used without any limitation as long as it is conventionally used in the art.

Specific examples of the solvent 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, methoxy butyl acetate, and methoxy pentyl 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; Butyl diol monoalkyl ethers such as methoxy butyl alcohol, ethoxy butyl alcohol, propoxy butyl alcohol and butoxy butyl alcohol; Butanediol monoalkyl ether acetates such as methoxy butyl acetate, ethoxy butyl acetate, propoxy butyl acetate and butoxy butyl 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, 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 ester, such as (gamma) -butyrolactone, etc. are mentioned. The solvent illustrated here can be used individually or in mixture of 2 or more types, respectively.

The solvents include esters such as alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate in consideration of coating properties and drying properties. May be preferably used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Methyl and the like can be used.

The content of the solvent is 60 to 90% by weight, preferably 70 to 85% by weight relative to the total weight with respect to the photosensitive resin composition including the same. When the content of the solvent is in the above range, it is preferable because the applicability becomes good when applied with a coating device such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater), or an inkjet. Do.

<Additive (E)>

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

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, cyclohexane dicarboxylic acid bis oxetane and the like.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.) etc. are mentioned. 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. 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 rt-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, 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 the above-described photosensitive resin composition in a predetermined pattern and then exposing and developing the same, and an image display device having the same.

The spacer for an image display apparatus can be manufactured by apply | coating a photosensitive resin composition on a base material as follows, photocuring and developing, and forming a pattern, for example.

First, a photosensitive resin composition is apply | coated on a board | substrate (usually glass) or the layer which consists of solid content of the photosensitive resin composition formed previously, and heat-drying removes volatile components, such as a solvent, and obtains a smooth coating film.

As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example.

Heating after drying (pre-baking) or drying under reduced pressure to volatilize 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.

The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, the site to which ultraviolet light is irradiated is hardened.

G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation dose of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto.

When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the spacer which has a target 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. In addition, during development, the substrate may be tilted at an arbitrary angle.

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

The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium 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 can be used individually or in combination of 2 or more types, respectively. 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 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 surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, 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 and lauryl trimethylammonium chloride, or quaternary ammonium salts.

These surfactant can be used individually or in combination of 2 or more types, respectively.

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

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

In the photosensitive resin composition of the present invention, the epoxide ring-opening reaction of the resin (A-1) may be performed in a heating environment during the spacer forming process, for example, may be performed in a postbaking process.

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 photospacer used for a display device.

Therefore, the spacer having the pattern thus obtained may be usefully used for an image display device such as a liquid crystal display device. In particular, when applied to a touch panel, the spacer having an elastic recovery rate similar to that of a conventional spacer, but having a high crosslinking density, has excellent mechanical properties. Hardness with little deformation in pressure.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Synthesis Example 1 Synthesis of Alkali-Soluble Resin (A-a)

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 (Formula 1) and 20 parts by weight of a mixture of 3,4-epoxytricyclodecane-9-yl (meth) acrylate (Formula 2) (50:50 molar ratio), 20 parts by weight of 4-hydroxybutyl acrylate glycidyl ether, methylmetha 50 parts by weight of acrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), and then stirred and mixed Prepared and prepared by stirring and mixing 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA as a chain transfer agent dropping tank. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the 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-a) having a solid acid value of 75 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 17,000, and molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 2: Synthesis of Alkali-Soluble Resin (A-b)

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-epoxycyclodecane-8-yl (meth) acrylate and 3,4- 30 parts by weight of a mixture of epoxytricyclodecane-9-yl (meth) acrylate (50:50 molar ratio), 30 parts by weight of 4-hydroxybutyl acrylate glycidyl ether, 50 parts by weight of methyl methacrylate, acrylic acid 40 Part by weight, 50 parts by weight of benzyl maleimide, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate, and prepared by stirring and mixing, n as a chain transfer agent dropping tank, -6 parts by weight of dodecanethiol and 24 parts by weight of PGMEA were added to prepare a mixture of stirring. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed 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-b) having a solid acid value of 73 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 18,000, and molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 3: Synthesis of Alkali-Soluble Resin (A-c)

The solid acid value was the same as in Synthesis Example 1, except that 2-propenoic acid, 4- (4-oxyranylbutoxy) butyl ether was added instead of 4-hydroxybutyl acrylate glycidyl ether. Resin (Ac) which was 72 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 16,700, and molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 4: Synthesis of Alkali-Soluble Resin (A-d)

A resin having a solid acid value of 73 mgKOH / g was prepared in the same manner as in Synthesis Example 1 except that 6-hydroxyhexyl acrylate glycidyl ether was added instead of 4-hydroxybutyl acrylate glycidyl ether. Ad) was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 16,500, and molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 5 Synthesis of Alkali-Soluble Resin (A-e)

The same procedure as in Synthesis Example 1 was conducted except that 2-ethyl-3-oxetanyl methyl methacrylate was added instead of 4-hydroxybutyl acrylate glycidyl ether to have a solid acid value of 73 mgKOH / g. Resin (Ae) was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 16,500, and molecular weight distribution (Mw / Mn) was 2.1.

Synthesis Example 6 Synthesis of Alkali-Soluble Resin (A-f)

The same procedure as in Synthesis Example 1 was conducted except that glycidyl methacrylate was added instead of 4-hydroxybutyl acrylate glycidyl ether to obtain a resin (A-f) having a solid acid value of 74 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 17,300, and molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 7: Synthesis of Alkali-Soluble Resin (A-g)

3,4-Epoxytricyclodecane-8-yl (meth) acrylate (Formula 1) and 3,4-epoxytricyclodecane-9-yl without adding 4-hydroxybutyl acrylate glycidyl ether A mixture of (meth) acrylate (Formula 2) (50:50 molar ratio) was carried out in the same manner as in Synthesis Example 1 except that 40 parts by weight of a solid (acid) had a solid acid value of 73 mgKOH / g (Ag). . The weight average molecular weight of polystyrene conversion measured by GPC was 18,200, and molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 8: Synthesis of Alkali-Soluble Resin (A-h)

3,4-Epoxytricyclodecane-8-yl (meth) acrylate (Formula 1) and 3,4-epoxytricyclodecane-9-yl without adding 4-hydroxybutyl acrylate glycidyl ether A mixture of (meth) acrylate (Formula 2) (50:50 molar ratio) was carried out in the same manner as in Synthesis Example 2 except for using 60 parts by weight, to obtain a resin (Ah) having a solid acid value of 73 mgKOH / g. . The weight average molecular weight of polystyrene conversion measured by GPC was 18,000, and molecular weight distribution (Mw / Mn) was 2.4.

Synthesis Example 9: Synthesis of Alkali-Soluble Resin (A-i)

The solid acid value was 74 mgKOH / in the same manner as in Synthesis Example 1, except that 3,4-epoxycyclohexyl (meth) acrylate was added instead of 4-hydroxybutyl acrylate glycidyl ether. Resin (Ai) which is g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 17,800, and molecular weight distribution (Mw / Mn) was 2.3.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said alkali-soluble resin, it carried out on condition of the following using GPC method.

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

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

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

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

Calibration standard: 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).

<Production of Photosensitive Resin Composition for Spacer Formation>

The photosensitive resin composition for spacer formation was produced with the component and composition of following Table 1 (unit is a weight part).

Table 1

<Test Example>

A glass substrate (Eagle 2000; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and dried. The photosensitive resin compositions prepared in Examples and Comparative Examples were spin coated on the glass substrate, respectively, and then prebaked at 90 ° C. for 3 minutes in a clean oven. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was 150 μm, and light was emitted at an exposure amount (405 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Investigate. The irradiation to the polymerizable resin composition at this time passed the light emitted from the ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectro Co., Ltd.), and cut and used light of 400 nm or less. In this case, a photomask in which the next pattern was formed on the same plane was used.

One side has a square light-transmitting part (pattern) which is 10 micrometers, and the said space | interval is 100 micrometers. After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 100 seconds at 25 ° C for development. After washing with water, postbaking was carried out at 220 ° C for 20 minutes in an oven. The obtained film thickness was 3 micrometers. The film thickness was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). The physical properties were evaluated for the pattern thus obtained as follows, and the results are shown in Table 2 below.

1. CD-bias of Pattern

The pattern size at the film thickness of 3.0 mu m obtained above was measured using a three-dimensional shape measuring apparatus (SIS-2000 system; manufactured by SNU Precision), and the difference from the Mask Size was calculated as CD-bias as follows. CD-bias is better as it is closer to 0, and (+) means that the pattern is larger in size than the mask and (-) is smaller in size than the mask.

CD-bias = (Formed Pattern Size)-(Mask Size used during formation)

2. Line width, cross-sectional shape

The line width of the pattern formed by Mask 14 micrometers was measured for the cured film obtained above using the scanning electron microscope (S-4600; the Hitachi company make), and the cross-sectional shape was evaluated as follows. The cross-sectional shape was judged as a forward taper when the angle of the pattern with respect to the board | substrate was less than 90 degree, and when it was 90 degree or more as a reverse taper.

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

3. Mechanical characteristics (total displacement and recovery rate)

The cured film obtained above was measured using a dynamic ultra-fine hardness tester (HM-2000; Helmut Fischer GmbH + Co.KG) to measure the total amount of displacement (μm) and the amount of elastic displacement (μm) 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 (μm)] / [total displacement (μm)] × 100

Measurement conditions are as follows.

Test mode; Load-Unload Test

Test force; 50.0mN

Load speed; 4.41mN / sec

Holding time; 5sec

Indenter; Square pyramid indenter (50㎛ diameter)

4. Cumulative mechanical characteristics (cumulative recovery rate)

Using the cured film obtained above, a dynamic ultra-micro hardness tester (HM-2000; Helmut Fischer GmbH + Co.KG) was applied to the same pattern 10 times under the following conditions, and the load was applied. Measurement is performed using a three-dimensional shape measuring device (SIS-2000 system; manufactured by SNU Precision).

The smaller the change in height before and after the load, the better the cumulative recovery rate.

Measurement conditions are as follows.

Test mode; Load-Unload Test

Test force; 50.0mN

Load speed; 4.41mN / sec

Holding time; 5sec

Indenter; Square pyramid indenter (50㎛ diameter)

Count: 10

5. Sensitivity

Development adhesiveness is the size of the mask with 100% of the pattern formed with the thickness of 3㎛ by the photomask with 1000 circular patterns with the diameter of 1㎛ interval from 5㎛ to 20㎛. Evaluated. The smaller the size of the mask, the better the sensitivity.

TABLE 2

Referring to Table 2, in the case of the embodiment including the second resin according to the present invention, it can be confirmed that the mechanical properties are superior to the comparative examples that do not include it. In addition, it can be confirmed that the adhesion and the pattern shape to the substrate is good at a low exposure amount, the elastic recovery rate is excellent, the mechanical displacement is small, and the sensitivity is good.

In particular, in the case of the present invention using the compound (A-3) having an ether bond, it can be seen that the cumulative mechanical properties are significantly superior to the comparative examples without an ether bond.

Claims (7)

1. As a photosensitive resin composition containing alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,

   The alkali-soluble resin is copolymerized to include a compound having a (A-1) unsaturated bond and a carboxyl group, (A-2) at least one of the following formulas (1) to (2) and (A-3) a compound of the formula (3) Photosensitive resin composition for spacer formation which is resin:

   [Formula 1]

   

   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 alkylene having 1 to 20 carbon atoms, with or without heteroatoms or Cycloalkylene; wherein R ₁ and R ₂ may be independently substituted with a hydroxy group)

   [Formula 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 alkylene having 1 to 20 carbon atoms, with or without heteroatoms or Cycloalkylene; wherein R ₁ and R ₂ may be independently substituted with a hydroxy group)

   [Formula 3]

   

   (Wherein R ₁ is hydrogen, alkyl of 1 to 10 carbon atoms or cycloalkyl of 3 to 10 carbon atoms, and the alkyl and cycloalkyl may independently include a hetero atom,

   R _2, and R ₃ are each independently a linear or branched alkylene having 1 to 20 carbon atoms,

   R ₁ , R ₂ and R ₃ may be further substituted with a hydroxyl group independently of each other)
2. The method according to claim 1, R ₁ of the formula (3) is hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, 1-hydroxy Ethyl 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 Hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group and 4-hydroxy-n-butyl group The photosensitive resin composition for spacer formation which is either.
3. The method according to claim 1, R ₂ and R ₃ of the formula 3 is independently of each other any one selected from the group consisting of methylene group, ethylene group, propylene group, butylene group, tetramethylene group, ethylethylene group and pentamethylene group , Photosensitive resin composition for spacer formation.
4. The method of claim 1, wherein the compound (A-3) is 2-hydroxyethyl acrylate glycidyl ether; 2-hydroxyethyl methacrylate glycidyl ether; 4-hydroxybutyl acrylate glycidyl ether; 4-hydroxybutyl methacrylate glycidyl ether; 6-hydroxyhexyl acrylate glycidyl ether; 6-hydroxyhexyl methacrylate glycidyl ether; A spacer that is at least one selected from the group consisting of 2-propenoic acid, 2- (2-oxyranylethoxy) ethyl ether and 2-propenoic acid, 4- (4-oxyranylbutoxy) butyl ether Photosensitive resin composition for formation.
5. The method of claim 1, wherein the alkali-soluble resin is 5 to 80 mol% of the structural units derived from the compound (A-1), 10 to 85 mol% of the structural units derived from the compound (A-2) and the compound (A-3). The photosensitive resin composition for spacer formation containing 10-85 mol% of structural units derived from.
6. The spacer made from the photosensitive resin composition for spacer formation of any one of Claims 1-5.
7. An image display device provided with the spacer of claim 6.