JP2013041153A - Photosensitive resin composition for photospacer and photospacer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in a profile of a halftone pattern, dynamic characteristics and a post-bake margin.SOLUTION: The photosensitive resin composition comprises (A) a photopolymerization initiator, (B) a solvent, (C) a polymerizable monomer, and (D) an alkali-soluble resin. At least kind of (D) alkali-soluble resins has an acid value of 150 to 400 mgKOH/g, and a glass transition temperature (Tg) of 50 to 120°C. With the photosensitive resin composition, two or more independent patterns can be simultaneously formed.

Description

  The present invention relates to a photosensitive resin composition for a photospacer capable of simultaneously forming two independent patterns. The present invention also relates to a pattern formation method using such a photosensitive resin composition for photospacers and a photospacer manufacturing method including the pattern formation method. Furthermore, the present invention relates to a photospacer using a photosensitive resin composition for photospacer and a display device using the photospacer.

  Conventionally, photospacer materials used in liquid crystal display devices and the like have been studied (Patent Documents 1 and 2). In recent years, as one of the cost reduction measures for photo spacers (hereinafter sometimes referred to as “PS”), there is a movement to reduce the manufacturing cost (equipment cost) by using a combination of existing facilities with advanced depreciation. . In recent years, higher definition has been advanced. Conventionally, the photo-spacer has been mainly produced by proxy exposure ghi-line exposure, but when a new production line is set up, a high-definition stepper or scanner (gh-line exposure machine) is suspended. If you can use this, you can reduce capital investment and increase production efficiency. Therefore, a photo spacer material having particularly excellent exposure suitability for the gh line has been desired. However, the above Patent Document 1 is for ghi line, and there is almost no photospacer material having particularly excellent sensitivity for gh line exposure.

  In addition, in the case of a PS in which a main photo spacer (main PS) and a sub photo spacer (sub PS) are formed at the same time, there is a problem that the shape of the sub PS is particularly deviated.

JP 2010-96846 A

  The present invention aims to solve the above-mentioned problems, and in particular, to provide a photosensitive resin composition that can be exposed with g-line and h-line and has excellent halftone properties. And An object of the present invention is to provide a photosensitive resin composition having excellent PS shape, mechanical properties and post-bake margin.

  Under such circumstances, the inventors of the present application have conducted intensive studies, and as an alkali-soluble resin, an acid value of 150 to 400 mgKOH / g and a glass transition point (Tg) of 50 to 120 ° C. are adopted. As a result, it was found that a photo-spacer that can be exposed with g-line and h-line and that is excellent in both main PS and sub-PS shapes was obtained, and the present invention was completed. Specifically, it was achieved by the following means <1>, preferably by the following <2> to <15>.

<1> (A) a photopolymerization initiator, (B) a solvent, (C) a polymerizable monomer, and (D) an alkali-soluble resin, and (D) at least one of the alkali-soluble resins has an acid value of 150 to 400 mgKOH / G and a glass transition point (Tg) of 50 to 120 ° C., and two or more independent patterns can be simultaneously formed.
<2> The (D) alkali-soluble resin contains a crosslinkable group, or separately from the (D) alkali-soluble resin, further contains an alkali-soluble resin (D2) having a crosslinkable group in the side chain, <1 > Photosensitive resin composition.
<3> The photosensitive resin composition according to <2>, wherein a weight ratio of the alkali-soluble resin (D1) and the alkali-soluble resin (D2) is in the range of 5:95 to 70:30.
<4> (A) The photosensitive resin composition according to any one of <1> to <3>, wherein at least two or more kinds are used in combination as a photopolymerization initiator.
<5> (A) Any one of <1> to <3>, including one or more oxime ester compounds and a photopolymerization initiator other than the one or more oxime ester compounds as a photopolymerization initiator. The photosensitive resin composition as described.
<6> The photosensitive resin composition according to any one of <1> to <5>, further comprising (E) a photosensitizer or a co-initiator.
<7> The total addition amount of (A) the photopolymerization initiator and (E) the photosensitizer or the co-initiator is 0.1 to 15.0% by weight in the total solid content. The photosensitive resin composition according to any one of <1> to <6>.
<8> (C) The photosensitive resin composition according to any one of <1> to <7>, wherein the polymerizable monomer has an acid group and has an acid value of 20 to 150 mgKOH / g.
<9> (D) The photosensitive resin composition according to any one of <1> to <8>, wherein the alkali-soluble resin is an acrylic resin.
<1> to <9>, wherein the <10> alkali-soluble resin (D2) is an acrylic resin having an acid value of 150 to 400 mgKOH / g and a glass transition point (Tg) of 50 to 120 ° C. The photosensitive resin composition of any one.
<11> The photosensitive resin composition according to any one of <1> to <10>, which is for gh-line exposure.
<12> A step of applying the photosensitive resin composition according to any one of <1> to <11> onto a substrate to form a photosensitive resin composition layer, and the photosensitive resin composition layer On the other hand, the exposure is performed by changing the exposure amount in a pattern-like manner, and an exposure step for curing the exposed portion, and development for removing the uncured portion of the photosensitive resin composition layer by development to form two or more independent patterns. And a pattern forming method.
<13> A method for producing a photospacer, comprising a step of forming two or more kinds of independent photospacer patterns on a substrate using the photosensitive resin composition according to any one of <1> to <11>.
<14> A photospacer having two or more independent patterns manufactured by the manufacturing method according to <12>.
<15> A display device having a photospacer having two or more types of independent patterns according to <14>.

  According to the present invention, it is possible to provide a photosensitive resin composition that can be exposed with at least g-line and h-line and has excellent halftone properties. Furthermore, it has become possible to provide a photosensitive resin composition excellent in PS shape, mechanical properties and post-bake margin.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The photosensitive resin composition of the present invention includes (A) a photopolymerization initiator, (B) a solvent, (C) a polymerizable monomer, and (D) an alkali-soluble resin, and (D) at least one of the alkali-soluble resins. However, it has an acid value of 150 to 400 mgKOH / g and a glass transition point (Tg) of 50 to 120 ° C., and two or more independent patterns can be simultaneously formed. By using such (D) alkali-possible resin, it is possible to provide a photosensitive resin composition excellent in halftone suitability, PS shape, mechanical properties and post-bake margin.
Here, “two or more types of independent patterns can be formed simultaneously” means that two or more types of patterns having different heights are formed by one exposure. One exposure means exposure performed at the same time. As the exposure performed at the same time, the exposure method is not limited, and examples thereof include a method using halftone masks having different transmittances, and a method in which exposure is performed by simultaneously irradiating two or more exposure amounts.
For example, when there are two types of patterns, the pattern group (1) composed of a plurality of patterns with a high height and the pattern group (2 composed of a plurality of patterns with a low height) ) Exists. The height difference between the pattern group (1) and the pattern group (2) is preferably 0.4 to 1.1 μm. The height of the pattern group can be determined as an average value of each. In addition, the height of each independent pattern group is preferably constant, and for example, it is preferable that the standard deviation 3σ is ± 0.1 μm.
On the other hand, there are also known methods of forming protrusions as rib members and rib members at the same time as photo spacers. However, rib members basically control liquid crystal alignment, and are therefore more suitable for angle control than height control. There is. The photospacer is required to have a high elastic recovery rate (for example, an elastic recovery rate of 60% or more).
Usually, using the photosensitive resin composition for a photospacer of the present invention, two types of main PS and sub-PS are formed, but it goes without saying that forming three or more types of PS is not excluded. .
Hereinafter, each component of the present invention will be described in detail.

<(A) Photopolymerization initiator>
The photosensitive resin composition of the present invention contains a photopolymerization initiator. As the photopolymerization initiator, known compounds capable of initiating polymerization by light irradiation can be used in a wide range without limitation.

  Known photopolymerization initiators generally used include, for example, camphorquinone, benzophenone, benzophenone derivatives, O-oxime ester compounds, acylphosphine, acylphosphine derivatives, acetophenone, acetophenone derivatives, such as α-hydroxycycloalkyl phenyl ketones Or 2-hydroxy-2-methyl-1-phenyl-propanone, dialkoxyacetophenones, α-hydroxy- or 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzyl ketals, such as benzyl dimethyl ketal , Phenyl glyoxalate and derivatives thereof, dimer phenyl glyoxalate, peresters such as benzophenone tetracarboxylic acid peresters (eg European Patent No. 11 No. 26,541), halomethyltriazines such as 2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl [1,3,5 ] Triazine, 2- (4-methoxy-phenyl) -4,6-bis-trichloromethyl [1, 3, 5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl Combined with [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl [1,3,5] triazine, hexaarylbisimidazole / co-initiator system, eg 2-mercaptobenzothiazole Ortho-chlorohexaphenyl-bisimidazole; ferrocenium compounds or titanocenes, for example dicyclopentadiene Le - bis (2,6-difluoro-3-pyrrolo-phenyl) - titanium; for example, it is also possible to use mixtures of O- oxime ester compounds as described in EP GB2,339,571. A boric acid compound can also be used as a co-initiator.

  Among these, as the photopolymerization initiator, an O-oxime ester compound is preferable from the viewpoint of exposure sensitivity.

O-oxime ester compound The O-oxime ester compound used in the present invention is not particularly defined, but preferably has an aromatic ring, more preferably has a condensed ring containing an aromatic ring, and has a benzene ring and a heterocyclic ring. It is more preferable to have a condensed ring containing. The O-oxime ester compound used in the present invention preferably has a structure in which an oxime ester group is directly bonded to the condensed ring. Here, the condensed ring containing an aromatic ring should just be an aromatic ring at least 1 ring.
The O-oxime ester compound can be appropriately selected from known photopolymerization initiators such as the O-oxime ester compounds described in JP-A Nos. 2000-80068 and 2001-233842. Specifically, 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate Etc. One type of O-oxime ester compound may be used, or two or more types of compounds may be used in combination.

上記一般式（１）中、Ｒ¹は、水素原子、置換基を有してもよいアシル基、置換基を有してもよいアルコキシカルボニル基、及び置換基を有してもよいアリールオキシカルボニル基のいずれかを表し、Ｒ²は、それぞれ独立に、ハロゲン原子、アルキル基、アリール基、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、及びアミノ基のいずれかを表し、ｍは、０〜４の整数を表す。ｍが２以上のとき、Ｒ²は互いに結合して環を形成していてもよい。Ｘは、ＣＨ₂、Ｏ、及びＳのいずれかを表す。ｌは、１〜３の整数を表す。 In addition to the above, a compound represented by the following general formula (1) can also be mentioned as a suitable photopolymerization initiator from the viewpoint that a pattern with a good rectangular profile can be obtained with a smaller exposure amount.

In the general formula (1), R ¹ is a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and an aryloxycarbonyl which may have a substituent. Any one of the groups, each R ² independently represents any of a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, and an amino group; Represents an integer of 0 to 4; When m is 2 or more, R ² may be bonded to each other to form a ring. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3.

一般式（３）

上記一般式（２）及び（３）中、Ｒ¹は、水素原子、置換基を有してもよいアシル基、置換基を有してもよいアルコキシカルボニル基、及び置換基を有してもよいアリールオキシカルボニル基のいずれかを表し、Ｒ²は、それぞれ独立に、ハロゲン原子、アルキル基、アリール基、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、及びアミノ基のいずれかを表し、ｍは、０〜４の整数を表す。ｍが２以上のとき、Ｒ²は互いに結合して環を形成していてもよい。Ｘは、ＣＨ₂、Ｏ、及びＳのいずれかを表す。ｌは、１〜３の整数を表す。 The O-oxime ester compound is more preferably an O-oxime ester compound represented by any one of the following general formulas (2) and (3).
General formula (2)

General formula (3)

In the general formulas (2) and (3), R ¹ may have a hydrogen atom, an acyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, and a substituent. Each of R ² represents each independently a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or an amino group. , M represents an integer of 0-4. When m is 2 or more, R ² may be bonded to each other to form a ring. X represents any of CH ₂ , O, and S. l represents an integer of 1 to 3.

The O-oxime ester compound according to any one of the general formulas (1) to (3) is, in the general formulas (1), (2), and (3), X is any one of O and S, It is preferable that l is any one of 1 and 2, and R ¹ is any one of an acyl group which may have a substituent and an alkoxycarbonyl group.

In the general formulas (1), (2) and (3), R ¹ represents a hydrogen atom, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a substituent. Any of the aryloxycarbonyl groups that may be present.
The acyl group may be any of aliphatic, aromatic and heterocyclic rings. Those having 2 to 30 carbon atoms are preferred, those having 2 to 20 carbon atoms are more preferred, and those having 2 to 16 carbon atoms are particularly preferred. The acyl group may further have a substituent. As the substituent, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable.
The acyl group may have a substituent, for example, acetyl group, n-propanoyl group, i-propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group. , Decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, toluenecarbonyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl Group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, methacryloyl group, acryloyl group and the like.

  The alkyloxycarbonyl group may have a substituent, preferably has 2 to 30 carbon atoms, more preferably has 2 to 20 carbon atoms, and more preferably has 2 to 16 carbon atoms. Particularly preferred. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, allyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. Is mentioned.

  The aryloxycarbonyl group may have a substituent and is preferably an alkoxycarbonyl group having a total carbon number of 7 to 30, more preferably a total carbon number of 7 to 20, and a total carbon number of 7 to 16. Is particularly preferred. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.

In the general formulas (1), (2) and (3), each R ² is independently a halogen atom, alkyl group, aryl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, or amino group. Any of the groups may be mentioned, and in particular, aliphatic, aromatic, heteroaromatic, halogen atom, —OR ³ , —SR ³ , —NR ³ R ⁴ may be mentioned. R ³ and R ⁴ may be connected to each other to form a ring. R ³ and R ⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heteroaromatic group. When m is 2 or more and are connected to each other to form a ring, each R ² may be independently formed to form a ring, and a ring may be formed via at least one of R ³ and R ^4. Also good.

前記構造式中、Ｙ及びＺは、それぞれ、ＣＨ₂、−Ｏ−、−Ｓ−、及び−ＮＲ−のいずれかを表す。 In the case where a ring is formed through the substituent R ² , the following structures are exemplified.

In the structural formulas, Y and Z each represent CH ₂ , —O—, —S—, or —NR—.

  As an alkyl group, you may have a substituent and a C1-C18 thing is preferable, and a C1-C10 thing is especially preferable. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-hexyl group, n -An octyl group, t-octyl group, and n-decyl group are mentioned.

  The aryl group may have a substituent and preferably has a total carbon number of 6 to 20, particularly preferably a total carbon number of 6 to 12. Examples of such an alkyl group include a phenyl group, a biphenyl group, a naphthyl group, a chlorophenyl group, and a methoxyphenyl group.

  As an alkyloxy group, you may have a substituent and a C1-C18 thing is preferable, and a C1-C12 thing is especially preferable. Such alkyloxy groups include methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy, t-butyloxy, 2-ethylhexyloxy, n-decyloxy, phenethyloxy Group and phenoxyethoxy group.

  The aryloxy group may have a substituent and preferably has 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples of such an aryloxy group include a phenoxy group, a naphthyloxy group, a chlorophenyloxy group, and a methoxyphenyloxy group.

  As an alkylthio group, you may have a substituent and a C1-C18 thing is preferable, and a C1-C12 thing is especially preferable. Examples of such an alkylthio group include a methylthio group, an ethylthio group, an i-propylthio group, an n-butylthio group, an n-octylthio group, an n-dodecylthio group, and a 2-ethylhexylthio group.

  As the arylthio group, those having 6 to 20 carbon atoms are preferable, and those having 6 to 12 carbon atoms are particularly preferable. Examples of such an arylthio group include a phenylthio group, a tolylthio group, a chlorophenylthio group, and an ethoxycarbonylphenylthio group.

As the amino group, at least one of an alkyl group and an aryl group may be substituted, and those having 1 to 20 carbon atoms are preferable, and those having 1 to 12 carbon atoms are particularly preferable. Examples of such an amino group include —NH ₂ group, diethylamino group, diphenylamino group, and methylphenylamino group.

Specific examples of the aliphatic group, aromatic group, and heteroaromatic group represented by R ² , R ³ , and R ⁴ include the same groups as those described above for R ¹ .

Specific examples of the O-oxime ester compounds represented by the general formulas (1) to (3) include the following compounds, but the present invention is not limited thereto.

  The oxime ester group may exist in two types of configuration (Z) or (E). The isomers may be separated by conventional methods, or the isomer mixture may be used as it is as a photoinitiating seed. Therefore, the O-oxime ester compound in the present invention may be a mixture of isomers on the configuration of the above-mentioned compound.

The above compounds can be identified by measuring ¹ H-NMR spectrum and UV-is absorption spectrum.

(Method for producing the above compound)
As a manufacturing method of the said compound, description of Unexamined-Japanese-Patent No. 2007-231000, especially description of paragraph number 0033-0036 can be referred.

The photosensitive resin composition of the present invention may contain two or more kinds of polymerization initiators, and preferably contains two or more kinds of polymerization initiators. By blending two or more kinds of polymerization initiators, the shape, mechanical properties, and post-bake margin of the resulting PS tend to be more excellent.
When the photosensitive composition of the present invention contains two or more polymerization initiators, one of them is preferably an O-oxime ester compound, which is a combination of an O-oxime ester compound and an α-aminoacetophenone compound. It is more preferable.

  Specific examples of the α-aminoacetophenone compound include 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, and 2-methyl. 2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- (4-ethylphenyl) 2-methylpropan-1-one, 2-dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methyl Propan-1-one, 2-dimethylamino-1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl 1- (4-methylthiophenyl) propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE 907), 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one (IRGACURE 369), 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, 2-dimethylamino- And 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRGACURE 379).

  (A) It is preferable that a polymerization initiator is contained in the ratio of 0.1-10 mass% with respect to the total solid content except the solvent contained in the photosensitive resin composition of this invention, 0.3- More preferably, it is contained at a rate of 8% by mass, and more preferably at a rate of 0.5-5% by mass. In particular, when two or more kinds of polymerization initiators are included, it is preferable that 10 to 80% by mass of the polymerization initiator is an O-oxime ester compound.

(B) Solvent The (B) solvent that can be used in the present invention is not particularly defined unless departing from the gist of the present invention, but is classified into esters, ethers, ketones, aromatic hydrocarbons, and the like. A solvent is mentioned.
Examples of esters used as (B) solvents include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, In addition to alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc., 3-oxypropion 3-oxypropionic acid alkyl esters such as methyl acid and ethyl 3-oxypropionate; methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-oxy-2-methylpropionic acid Methyl, 2- 2-oxypropionic acid alkyl esters such as ethyl x-2-methylpropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Alkoxypropionic acid alkyl esters such as ethyl propionate; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.

Examples of ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether Examples include acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Examples of aromatic hydrocarbons include toluene, xylene, and the like.

Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
A solvent may be used independently and may be used in combination of 2 or more type.
The content of the solvent (B) in the photosensitive resin composition of the present invention is appropriately determined in consideration of the applicability of the photosensitive resin composition, but in general, ( B) The content of the solvent is 45 to 85% by mass.

(C) Polymerizable monomer (polymerizable monomer)
In the photosensitive resin composition of this invention, (C) 1 or more types of polymerizable monomers are contained as a sclerosing | hardenable component. As the polymerizable monomer, a plurality of polymerizable monomers may be used in combination, or one or more of a polymerizable monomer containing an acid group and a polymerizable monomer having no acid group may be used in combination. In order to improve the halftone suitability and development latitude, it is preferable to use a polymerizable monomer having an acid group. In this case, the acid value is preferably 5 to 200 mgKOH / g, more preferably 10 to 180 mgKOH / g, and still more preferably 20 to 150 mgKOH / g. By setting the acid value to 5 mgKOH / g or more, the developer permeability tends to be high, and the halftone suitability and development latitude tend to improve. By setting the acid value to 200 mgKOH / g or less, a more appropriate pattern can be obtained. It becomes possible to obtain.

  By using a polymerizable monomer having an acid group in the structure, surface dissolution and film reduction in a low exposure amount region are promoted, so that halftone suitability is greatly improved. Further, development latitude is improved because development of unexposed portions is promoted. Among them, a polymerizable monomer having an acid group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a phosphoric acid group is preferable because it contributes greatly to improving developability and suppressing residues because alkali solubility increases. More preferably, it is a carboxyl group. In addition to the effect of imparting alkali solubility of the alkali-soluble resin described later (C), the effect of using a polymerizable monomer having an acid group also causes a development latitude even in a resin composition in which the photoinitiator concentration is increased to improve sensitivity. A wide and stable production of a photo spacer is possible.

  Examples of polymerizable monomers containing carboxyl groups include polyfunctional acrylates modified with carboxyl groups in addition to unsaturated fatty acids such as acrylic acid, methacrylic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and cinnamonic acid. Compounds. Examples of carboxyl group-modified polyfunctional acrylate compounds include succinic acid-modified pentaerythritol triacrylate, succinic acid-modified trimethylolpropane triacrylate, succinic acid-modified pentaerythritol tetraacrylate, succinic acid-modified dipentaerythritol pentaacrylate, and succinic acid-modified dipenta. Erythritol hexaacrylate, adipic acid modified pentaerythritol triacrylate, adipic acid modified trimethylolpropane triacrylate, adipic acid modified pentaerythritol tetraacrylate, adipic acid modified dipentaerythritol pentaacrylate, adipic acid modified dipentaerythritol tetraacrylate, etc. Aronix M-510, Aronix M-520, Aronix T -2349, Aronix TO-2359 (manufactured by Toagosei Co., Ltd.) can be preferably used commercially available compounds such as.

  Examples of the polymerizable monomer containing a phenolic hydroxyl group include p-hydroxystyrene, 3,4-dihydroxystyrene, 3,5-dihydroxystyrene, 2,4,6-trihydroxystyrene, (p-hydroxy) benzyl acrylate, and salicylic acid. Modified pentaerythritol triacrylate, salicylic acid-modified trimethylolpropane triacrylate, salicylic acid-modified pentaerythritol tetraacrylate, salicylic acid-modified dipentaerythritol pentaacrylate, salicylic acid-modified dipentaerythritol hexaacrylate, and the like, salicylic acid-modified dipentaerythritol is preferred Hexaacrylate, salicylic acid-modified dipentaerythritol pentaacrylate.

  Examples of the polymerizable monomer containing a sulfonic acid group include vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and butyl sulfonic acid-modified acrylamide. Examples of the polymerizable monomer containing a phosphoric acid group include vinyl phosphoric acid, styrene phosphoric acid, and butyl phosphoric acid-modified acrylamide. Of these, butylsulfonic acid-modified acrylamide is preferable, and a commercially available compound is ATBS (manufactured by Toagosei Co., Ltd.).

  Among these polymerizable monomers having an acid group, a polymerizable monomer having a carboxyl group and a polymerizable monomer having a phenolic hydroxyl group are preferable, and a polymerizable monomer having a carboxyl group is more preferable, from the viewpoint of production suitability and cost. .

(Polymerizable monomer having no acid group)
In the present invention, the polymerizable monomer having no acid group that can be used in combination with the polymerizable monomer having an acid group is not particularly limited as long as it is polymerizable, and is a low molecular compound having at least one ethylenic double bond, dimer Compounds capable of addition polymerization such as isomers, trimers, and oligomers can be suitably used.
Examples of the ethylenic compound include an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and an unsaturated carboxylic acid. Reaction of ester, polyisocyanate compound and (meth) acryloyl-containing hydroxy compound obtained by esterification reaction of acid with polyhydric carboxylic acid and polyhydric hydroxy compound such as fatty acid polyhydroxy compound and aromatic polyhydroxy compound described above And an ethylenic compound having a urethane skeleton.

  Specific polymerizable monomers can be classified according to the number of polymerizable groups in one molecule as shown below, but are not limited thereto.

(1) Compound having one polymerizable group in one molecule Examples of the compound having one polymerizable group in one molecule include, for example, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl glycol (meth) Acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, cyanoethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2,2, 2-tetrafluoro Ethyl (meth) acrylate, 1H, 1H, 2H, 2H perfluorodecyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxy Methyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene oxide monomethyl ether ( ) Acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified Examples include cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, PO-modified nonylphenol (meth) acrylate, and EO-modified-2-ethylhexyl (meth) acrylate.

(2) Compound having two polymerizable groups in one molecule Examples of a compound having two polymerizable groups in one molecule include two (meth) acryloyl groups in the same molecule as the polymerizable group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, tripropylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [ 4- (acryloxydiethoxy) phenyl] propane, bis (acryloyloxyethyl) ether of bisphenol A, (meth) acrylic acid modified product of bisphenol A type epoxy resin, 3-methylpentanediol di (meth) acrylate, 2 -Hydroxy-3-acryloyloxypropyl methacrylate, dimethylol-tricyclodecane di (meth) acrylate and the like, preferably dimethylol-tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylation Bisf Nord A di (meth) acrylate, and bisphenol A type epoxy resin (meth) acrylic acid modified product.

(3) Compound having three polymerizable groups in one molecule Examples of the compound having three polymerizable groups in one molecule include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid Alkylene oxide modified tri (meth) acrylate, dipentaerythritol propionate tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylol group Examples include lopantri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

(4) Compound having four or more polymerizable groups in one molecule Examples of the compound having four or more polymerizable groups in one molecule include pentaerythritol tetra (meth) acrylate and sorbitol tetra (meth) acrylate. , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol propionate tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol Penta (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, captolactone modified dipentaerythritol hexa (me And urethane acrylates such as UA-306H, UA-306T, and UA-306I manufactured by Kyoeisha Chemical Co., Ltd.

Among these, from the viewpoint of suitably maintaining solvent resistance and ITO sputtering suitability, (meth) acrylate monomers having two or more (meth) acryloyl groups in the same molecule are preferred, and three or more (meth) acryloyl are preferred. A (meth) acrylate monomer having a group is more preferable.
In particular, a (meth) acrylate monomer having 4 or more (meth) acryloyl groups is advantageous. For example, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable in terms of solvent resistance and suitability for ITO sputtering. A mixture of (a mixing ratio in terms of mass is dipentaerythritol pentaacrylate: dipentaerythritol hexaacrylate = 2-4: 8-6) is preferably used.

  When a polymerizable monomer having an acid group and a polymerizable monomer having no acid group are used in combination, the total of the polymerizable monomer having an acid group and the polymerizable monomer having no acid group is preferably 100 parts by mass. The addition ratio is not particularly limited as long as it is within the preferable acid value range shown above.

  In the photosensitive resin composition of the present invention, the content of the polymerizable monomer is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total solid content excluding the solvent of the photosensitive resin composition. %, More preferably in the range of 20 to 60% by mass.

<(D) Alkali-soluble resin>
The photosensitive resin composition of the present invention includes (D) an alkali-soluble resin having an acid value of 150 to 400 mgKOH / g and a glass transition point (Tg) of 50 to 120 ° C. as an alkali-soluble resin. .
The acid value is preferably from 180 to 380 mgKOH / g, more preferably from 200 to 350 mgKOH / g. When the acid value is less than 150 mgKOH / g, the developer permeability is low, so halftone suitability and development latitude cannot be obtained. When the acid value is greater than 400 mgKOH / g, the developer solubility is too high to obtain an appropriate pattern. I can't.
The glass transition point (Tg) is preferably 55 to 110 ° C, more preferably 60 to 100 ° C. When Tg is lower than 50 ° C., desired mechanical properties cannot be obtained when used at room temperature, and film thickness reduction (thermal sag) during post-baking is significant, making pattern design difficult. On the other hand, when Tg exceeds 120 ° C., the halftone suitability cannot be obtained because there is little decrease in the film thickness of the low exposure portion due to thermal sagging during post-baking.
1000-100000 are preferable and, as for the weight average molecular weight (Mw) of alkali-soluble resin (D1) used by this invention, 5000-50000 are more preferable.

  The acid value and Tg of the alkali-soluble resin are intended to improve the halftone suitability so that the film thickness difference between the main exposure pattern and the sub-exposure pattern is within a certain range. In the case where both of these are within an appropriate range, a desired halftone property is realized, and compatibility with resist performance such as mechanical characteristics can be achieved.

  The alkali-soluble resin is preferably a linear organic polymer having an alkali-soluble polymer having at least one alkali-soluble group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) More preferably, it is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin.
Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxyl group in the side chain is preferable.
For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.
The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.

  Examples of other alkali-soluble resins include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-11-174224, and JP-A-11-174224. Known polymer compounds described in JP 2000-56118 A, JP 2003-233179 A, JP 2009-52020 A, and the like can be used.

  Regarding the specific structural unit of the alkali-soluble resin, in particular, the acrylic resin (polymer of (meth) acrylic acid or (meth) acrylic acid and the co-polymerization of other monomers copolymerizable therewith) Are preferably used because they can be easily obtained and adjustment of alkali solubility is easy.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

  Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, polystyrene macromonomer, and polymethyl methacrylate macro. Monomer, CH ₂ = CR ³¹ R ³² [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. CH ₂ ═C (R ³¹ ) (COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or 6 carbon atoms. Represents -12 aralkyl groups. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more.
Preferred other copolymerizable monomers are selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. At least one, and particularly preferably CH ₂ ═CR ³¹ R ³² and / or CH ₂ ═C (R ³¹ ) (COOR ³³ ). These R ³¹ , R ³² and R ³³ are as defined above.

(Alkali-soluble resin D2)
In this invention, it is preferable that (D) alkali-soluble resin contains alkali-soluble resin (D2) which has a crosslinkable group in a side chain. The alkali-soluble resin (D2) has an acid value of 150 to 400 mgKOH / g, and the glass transition point (Tg) is 50 to 120 ° C. The alkali-soluble resin (D1) has a crosslinkable group in the side chain. In addition to the alkali-soluble resin (D1) having an acid value of 150 to 400 mgKOH / g and a glass transition point (Tg) of 50 to 120 ° C., an alkali having a crosslinkable group in the side chain A soluble resin (D2) may be used. By using together an alkali-soluble resin having a crosslinkable group in the side chain, the mechanical properties are improved by the effect of cross-linking during post-baking, and the post-bake margin is expanded. This greatly improves process stability when used as a resist such as a photospacer.

The type of the alkali-soluble resin (D2) is not particularly limited except that it has a crosslinkable group in the side chain, but the same as the above (D1) is preferable except that it has a crosslinkable group. For example, as for the specific structural unit of the alkali-soluble resin, in particular, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith can be easily obtained, and adjustment of alkali solubility, etc. Since it is easy, it is used suitably.
The kind of the crosslinkable group of the side chain is preferably an allyl group, an acrylic group, or a glycidyl group from the viewpoint of ease of synthesis.

The acid value of the alkali-soluble resin (D2) is preferably 150 to 400 mgKOH / g, more preferably 180 to 380 mgKOH / g, and further preferably 200 to 350 mgKOH / g. The glass transition point (Tg) of the alkali-soluble resin (D2) is preferably 50 to 120 ° C, more preferably 55 to 110 ° C, and further preferably 60 to 100 ° C.
1000-100000 are preferable and, as for the weight average molecular weight (Mw) of alkali-soluble resin (D2) used by this invention, 5000-50000 are more preferable.

  Moreover, as content of alkali-soluble resin in the photosensitive resin composition, with respect to the total solid content excluding the solvent contained in the photosensitive resin composition, the total amount of (D1) and (D2), 5-60 mass% is preferable, More preferably, it is 10-55 mass%, Most preferably, it is 15-50 mass%. The blending ratio of (D1) and (D2) is preferably 5:95 to 70:30, and more preferably 20:80 to 60:40.

  The ratio of the content of (C) the polymerizable monomer and (D) the alkali-soluble resin is 0.1 to 10 in terms of mass ratio (total mass of polymerizable monomer / mass of alkali-soluble resin). Preferably, the range of 0.4-8 is more preferable, and the range of 0.5-5 is more preferable.

(E) Photosensitizer or co-initiator (E) A photosensitizer or co-initiator may be further added to the photosensitive resin composition of the present invention. By adding these, spectral sensitivity can be moved or expanded, and photopolymerization of the photosensitive resin composition of the present invention can be promoted.
As the photosensitizer or co-initiator, an aromatic compound is particularly preferably used. For example, benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, coumarin and phenothiazine and derivatives thereof, 3- (alloy Lumethylene) thiazoline, rhodanine, camphorquinone, eosin, rhodamine, erythrosine, xanthene, thioxanthene, acridine (eg 9-phenylacridine), 1,7-bis (9-acridinyl) heptane, 1,5-bis (9 -Acridinyl) pentane, cyanine, merocyanine dyes.

Examples of the thioxanthone include thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxy. Carbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3- (2-methoxyethoxycarbonyl) thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl- 3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl Bonyl-3-phenylsulfylthioxanthone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonyl] thioxanthone, 1,3-dimethyl-2-hydroxy-9H-thioxanthen-9-one 2-ethylhexyl ether 1-ethoxycarbonyl-3- (1-methyl-1-morpholinoethyl) thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6- (1,1-dimethoxybenzyl) thioxanthone, 2-morpholinomethyl Thioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N- (1,1,3,3-tetra Methylbutyl) thioxanthone-3,4 Dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylic acid polyethylene glycol ester, 2-hydroxy-3- (3,4 Dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of the benzophenone include benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bis ( Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (methylethylamino) benzophenone, 4,4′-bis (p-isopropylphenoxy) benzophenone, 4-methylbenzophenone, 2, 4,6-trimethylbenzophenone, 4- (4-methylthiophenyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate, 4- (2-hydroxyethylthio) benzophenone, 4- (4-tri Thio) benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (toluene-4-sulfonyl) propan-1-one, 4-benzoyl-N, N, N-trimethylbenzene Methanaminium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanaminium chloride monohydrate, 4- (13-acryloyl-1,4,7, 10,13-pentaoxatridecyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethylbenzenemethananium chloride.

  Examples of the coumarin include coumarin 1, coumarin 2, coumarin 6, coumarin 7, coumarin 30, coumarin 102, coumarin 106, coumarin 138, coumarin 152, coumarin 153, coumarin 307, coumarin 314, coumarin 314T, coumarin 334, coumarin. 337, coumarin 500, 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-dipropoxycoumarin, 3-benzoyl-6,8- Dichlorocoumarin, 3-benzoyl-6-chlorocoumarin, 3,3′-carbonyl-bis [5,7-di (propoxy) coumarin], 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-iso Butyroylcoumarin, 3-benzoyl-5 7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di (methoxyethoxy) coumarin, 3-benzoyl-5 7-di (allyloxy) coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3- (1-naphthoyl) Coumarin, 5,7-diethoxy-3- (1-naphthoyl) coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3- (4-cyanobenzoyl) -5,7-dimethoxy Coumarin, 3- (4-cyanobenzoyl) -5,7-dipropoxycoumarin, 7-dimethyl Tilamino-3-phenylcoumarin, 7-diethylamino-3-phenylcoumarin, coumarin derivatives disclosed in JP-A-9-179,299 and 9-325,209, such as 7-[{4-chloro- 6- (Diethylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin.

  Examples of the 3- (aroylmethylene) thiazoline include 3-methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-naphtho. Thiazoline.

  Examples of the rhodanine include 4-dimethylaminobenzalrhodanine, 4-diethylaminobenzalrhodanine, 3-ethyl-5- (3-octyl-2-benzothiazolinylidene) rhodanine, and JP-A-8-305,019. And rhodanine derivatives represented by the formulas [1], [2] and [7] disclosed in Japanese Patent Publication No.

  In addition to the above compounds, acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 4,4′-bis (dimethylamino) benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, dansylic acid derivatives, 9,10 -Anthraquinone, anthracene, pyrene, aminopyrene, perylene, phenatrene, phentolenquinone, 9-fluorenone, dibenzosuberone, curcumin, xanthone, thiomiherketone, α- (4-dimethylaminobenzylidene) ketone, 2,5-bis (4-diethylaminobenzylidenecyclopentanone, 2- (4-dimethylaminobenzylidene) indan-1-one, 3- (4-dimethylaminophenyl) -1-indan-5-ylpropenone, 3-phenylthiophthalimide, N- Mechi -3,5-di (ethylthio) phthalimide, N-methyl-3,5-di (ethylthio) phthalimide, phenothiazine, methylphenothiazine, amine, N-phenylglycine, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate It is possible to use butoxyethyl acid, 4-dimethylaminoacetophenone, triethanolamine, methyldiethanolamine, dimethylaminoethanol, 2- (dimethylamino) ethylbenzoate, poly (propylene glycol) -4- (dimethylamino) benzoate, etc. it can.

  Among the above, the photosensitizer or co-initiator (E) added to the photosensitive resin composition of the present invention is selected from benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, and coumarin derivatives. Preferred is at least one photosensitizer compound.

The (E) photosensitizer or co-initiator content in the photosensitive resin composition is 0.5 to 15 based on the total solid content excluding the solvent contained in the photosensitive resin composition. % By mass is preferable, more preferably 1 to 12% by mass, and particularly preferably 2 to 10% by mass.
Moreover, the sum total of the addition amount of (A) photoinitiator and (E) photosensitizer or co-initiator is 0.1-15.0 weight% in the total solid of the photosensitive resin composition. It is preferable that it is 0.1 to 12.0% by weight.

(Other ingredients)
Additives The photosensitive resin composition of the present invention includes, as necessary, a radical scavenger, a light stabilizer, a curing aid, a thermal polymerization initiator, a surfactant, an adhesion aid, a development accelerator, and a thermal polymerization inhibitor. Various additives such as an additive, a dispersant, and other additives (filler, ultraviolet absorber, anti-aggregation agent, etc.) can be contained.

Light Stabilizer Various light stabilizers may be added to the present invention to improve light resistance. Although it does not specifically limit about the kind of light stabilizer, From the surface of versatility, a hindered amine type light stabilizer; For example, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-tetraacrylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)- 1,2,3,4-tetraacrylate, hindered phenol light stabilizers; for example pentaerythritol-tetrakis (3- (3 ′, 5′-di-tert-butyl-4′- Hydroxyphenyl) propionate and the like are preferably used.

  About 0.1-5.0 mass% is preferable with respect to the total solid of the photosensitive resin composition, and, as for content of the light stabilizer in this invention, it is 0.2-4.0 mass%. More preferably, it is more preferable that it is 0.5-2.0 mass%. If it is 0.1% by mass or less, the desired light resistance cannot be obtained, and if it is 5.0% by mass or more, the sensitivity decreases, which is not preferable.

(Curing aid)
As a curing aid, a compound having an epoxy ring may be used in order to increase the strength of the formed coating film. The use of a compound having an epoxy ring is preferable because thermal polymerization proceeds, solvent resistance is improved, and ITO sputtering suitability is improved.

The compound having an epoxy ring is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) These similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

The cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl type As alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT- 302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (manufactured by Toto Kasei), Epilon 430, 673. 695, 850S, 4032 (above, manufactured by DIC And the like.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434, YH-434L (manufactured by Nagase Kasei Co., Ltd.), glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin, and the like can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage during curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is poor.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701 (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, 3, 5, 3 Examples include ', 5'-tetramethyl-4,4' diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, and EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.).

  The content of the curing aid in the present invention is preferably about 0.1 to 5.0% by mass, and preferably 0.2 to 4.0% by mass, based on the total solid content of the photosensitive resin composition. More preferably, it is more preferable that it is 0.5-2.0 mass%. If it is 0.1% by mass or less, the effect of promoting the curing cannot be obtained, and if it is 5.0% by mass or more, the light resistance is deteriorated, which is a problem.

Thermal polymerization initiator It is also effective to contain a thermal polymerization initiator in the photosensitive resin composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

Surfactant It is preferable that the photosensitive resin composition of the present invention is composed of various surfactants from the viewpoint of improving coatability. The surfactant can improve liquid properties (particularly fluidity) when used as a coating liquid, and can improve the uniformity of coating thickness and liquid-saving properties. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed. It is also effective in slit coating that easily causes liquid breakage.

  As the surfactant, various nonionic, cationic and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.

  The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F173, F177, F141, F142, F143, F144, R30, and F437 (above, manufactured by DIC Corporation), Fluorard FC430, FC431, FC171 (Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-10 381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), and the like.

  Examples of surfactants other than fluorine-based surfactants include phthalocyanine derivatives (commercial product EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) heavy Combined polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Paluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, manufactured by BASF Nonionic surfactants such as 150R1; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

  As for the addition amount of surfactant, 0.001-2.0 mass% is preferable with respect to the total mass of the photosensitive resin composition, More preferably, it is 0.005-1.0 mass%.

Adhesion aid An adhesion aid can be added to the photosensitive resin composition used in the present invention from the viewpoint of improving adhesion to the substrate. As the adhesion assistant, an alkoxysilane compound, especially a silane coupling agent can be used.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material as a substrate, and exhibits an affinity by interaction or bond formation with an organic resin (meta) Silane coupling agents having a group such as acryloyl group, phenyl group, secondary or tertiary mercapto group, epoxy group, aminosilane group are preferred, and among them, (meth) acryloylpropyltrimethoxysilane and epoxypropyltrimethoxysilane are preferred. Is more preferable. Examples of such materials include KBM-303, KBM-403, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.).
In the case of using a silane coupling agent, the addition amount is preferably in the range of 0.2% by mass to 5.0% by mass in the total solid content in the photosensitive resin composition of the present invention, 0.5 The mass% to 3.0 mass% is more preferable.

Development accelerator In addition, when the alkali solubility of the uncured portion of the photosensitive resin composition layer is promoted to further improve the developability of the photosensitive resin composition, the development accelerator is used as the photosensitive resin composition. Can be used for
As such a development accelerator, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is preferable. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

Thermal polymerization inhibitor It is preferable to add a thermal polymerization inhibitor to the photosensitive resin composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert -Butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful It is.

Other additives In addition to the above, fillers such as glass and alumina; ultraviolet absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and poly Examples thereof include an aggregation inhibitor such as sodium acrylate.

  The photosensitive resin composition of the present invention comprises the components described above, that is, (A) a photopolymerization initiator, (B) a solvent, (C) a polymerizable monomer, (D) an alkali-soluble resin, and (E ) It can be prepared by adding and mixing other additives such as photosensitizers or co-initiators. As for the photosensitive resin composition of this invention, it is preferable that the sum total of (A)-(E) component occupies 85 mass% or more of a composition.

The shape or the like of the photo spacer formed by the method of the present invention is not particularly defined, but is preferably a columnar shape or a truncated cone shape. Needless to say, these shapes include a strict columnar shape and a truncated cone shape, and also include errors within a range not departing from the gist of the present invention.
The photo spacer formed by the method of the present invention is preferably composed of two types of main PS and sub PS, and the height of the main PS is, for example, 5.0 to 1.5 μm. The height of PS can be set to 4.0 to 1.0 μm. Furthermore, the difference in height between the main PS and the sub-PS is preferably 0.2 to 1.5 μm, and more preferably 0.3 to 1.0 μm.

<Photospacer and manufacturing method thereof>
The photospacer of the present invention includes, for example, a step of applying a photosensitive resin composition on a substrate to form a photosensitive resin composition layer, and changing the exposure amount in a pattern with respect to the photosensitive resin composition layer. A pattern forming method comprising: an exposure step of exposing the exposed portion to cure the exposed portion; and a developing step of removing uncured portions of the photosensitive resin composition layer by development to form two or more independent patterns. To be manufactured.
As a method of performing exposure by changing the exposure amount, a method of performing halftone mask exposure for forming a semi-transmissive portion by laminating and patterning a film having an arbitrary transmittance, or a photosensitive resin composition layer In contrast, there is a method of exposing in a dot pattern manner.

  The photosensitive resin composition layer is applied to the substrate directly or via another layer. As a method for applying the photosensitive resin composition layer, spin coating, slit coating, casting coating, roll coating, ink jetting, etc. It is formed by a method such as coating or transfer. The formed photosensitive resin composition is exposed through a mask pattern or exposed in a pattern, and after the exposed portion is cured, the unexposed portion (uncured portion) is developed and removed with a developer. Thus, a photo spacer can be produced by forming a dot-shaped pattern.

  In this case, the radiation used for exposure includes ultraviolet rays such as g-line, h-line, i-line, and j-line. In view of the problems at the beginning, exposure with g-line and h-line is particularly preferable. As a result, the gh-ray exposure equipment can be effectively used and the production efficiency can be improved.

  Drying (prebaking) of the film with the photosensitive resin composition of the present invention applied (preferably applied) on the substrate is performed under conditions of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate, an oven or the like. Can be done.

In development, the uncured part after exposure is eluted in the developer, leaving only the cured part. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the film of the photosensitive resin composition in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  As said organic solvent, what was enumerated as the above-mentioned solvent which can be used when preparing the photosensitive resin composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide (TMAH), choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0 An alkaline aqueous solution dissolved so as to be 0.01 to 1% by mass is exemplified.
In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans (rinse) with water after image development.

After the development, excess developer is washed away, dried, and then generally heated (post-baked) at a temperature of 100 to 250 ° C.
Post-baking is heating after development for complete curing, and is usually performed at about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  When a film is formed by applying the photosensitive resin composition of the present invention on a substrate, the dry thickness of the film is generally 0.5 to 6.0 μm, preferably 1.0 to 5.0 μm, Most desirably, the thickness is 2.0 to 4.0 μm.

  As the substrate, for example, non-alkali glass, sodium glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached, a solid-state imaging device, and the like used for liquid crystal display devices and the like are used. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.

The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
In the case where the photosensitive resin composition is applied to the substrate through another layer, the other layers include an interlayer insulating film layer, a planarizing film layer, a SiNx layer, a gas barrier layer, and a solvent resistant layer. Can be mentioned.

The photo spacer of the present invention can also be formed after forming a color filter including a black shielding part such as a black matrix and a colored part such as a colored pixel.
The black shielding part and the colored part and the photo spacer are formed by arbitrarily combining a coating method for applying a photosensitive composition and a transfer method using a transfer material having a photosensitive resin layer made of the photosensitive composition. It is possible.
The black shielding part, the colored part, and the photospacer can each be formed from a photosensitive composition. Specifically, for example, a photosensitive resin layer is formed by directly applying the liquid photosensitive composition to a substrate. Later, exposure / development is performed to form the black shielding portion and the colored portion in a pattern, and then the photosensitive composition of another liquid is placed on another substrate (temporary support) different from the substrate. Then, using the transfer material produced by forming the photosensitive resin layer, the transfer material is brought into close contact with the black shielding portion or the substrate on which ITO or SiNx and the colored portion are formed to form the photosensitive resin layer. After the transfer, the photo spacer can be formed in a pattern by performing exposure and development. In this manner, a color filter provided with a photo spacer can be manufactured.

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention comprises a photospacer obtained by the method for producing a photospacer of the present invention. The photo spacer is preferably formed on a display light shielding part such as a black matrix formed on a support or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may exist between a light shielding portion for display such as a black matrix, a driving element such as TFT and a photo spacer. It is also preferable that a protective film is provided on the TFT as in COA (color filter on array) and formed thereon.

For example, when the photo spacer is provided on the display light-shielding part or the driving element, the display light-shielding part (black matrix or the like) or the driving element previously disposed on the support is covered with, for example, a photosensitive resin. The photosensitive resin layer of the transfer film is laminated on the surface of the support, peeled and transferred to form a photosensitive resin layer, and then subjected to exposure, development, heat treatment, etc. to form a photo spacer. A substrate for a liquid crystal display device can be manufactured.
The substrate for a liquid crystal display device of the present invention may further be provided with colored pixels of three colors such as red (R), blue (B), and green (G) as necessary.

<Liquid crystal display element>
A liquid crystal display element can be formed by providing the substrate for a liquid crystal display device of the present invention. As one of the liquid crystal display elements, a liquid crystal layer and liquid crystal driving means (simple matrix driving method and active matrix driving method) are provided between a pair of supports (including the substrate for a liquid crystal display device of the present invention) at least one of which is light transmissive. Including at least).

  In this case, the substrate for a liquid crystal display device of the present invention can be configured as a color filter substrate having a plurality of RGB pixel groups and each pixel constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a photo spacer having a uniform height and excellent deformation recovery properties, a liquid crystal display element including the color filter substrate has a cell gap unevenness (between the color filter substrate and the counter substrate ( Occurrence of cell thickness fluctuations) can be suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a vivid image.

As another aspect of the liquid crystal display element, at least one of the liquid crystal display elements includes a liquid crystal layer and a liquid crystal driving unit between a pair of light transmissive supports (including the liquid crystal display device substrate of the present invention), and the liquid crystal The driving means has an active element (for example, TFT), and is configured to be regulated to a predetermined width by a photo spacer having a uniform height between a pair of substrates and excellent deformation recovery.
Also in this case, the substrate for a liquid crystal display device of the present invention is configured as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a black matrix.

Examples of liquid crystals that can be used in the present invention include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.
In addition, the pixel group of the color filter substrate may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used. For producing the color filter substrate, for example, a black matrix may be formed as described above after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Good. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

<Liquid crystal display device>
The liquid crystal display device of the present invention is constituted by providing the liquid crystal display device substrate. The liquid crystal display device of the present invention is configured by providing the liquid crystal display element. That is, as described above, the space between a pair of substrates facing each other so as to face each other is regulated to a predetermined width by the photo spacer produced by the photo spacer production method of the present invention, and the liquid crystal material is placed in the regulated gap. The liquid crystal layer is configured to be sealed (the sealed portion is referred to as a liquid crystal layer), and the thickness (cell thickness) of the liquid crystal layer is maintained at a desired uniform thickness. The main photo spacer is mainly used as a cushion for attaching the CF substrate and the TFT side substrate, and the sub photo spacer is designed to make the liquid crystal uniform even at low temperatures (low temperature firing) and high temperatures (liquid crystal flow). It is structured.

  The liquid crystal display mode in the liquid crystal display device includes STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. Preferably mentioned. Among them, in the liquid crystal display device of the present invention, from the viewpoint of exhibiting the effect of the present invention most effectively, a display mode that easily causes display unevenness due to fluctuations in the cell thickness of the liquid crystal cell is desirable, and the cell thickness is 2 to 4 μm. The VA display mode, the IPS display mode, and the OCB display mode are preferably configured.

  The basic configuration of the liquid crystal display device of the present invention includes: (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged; and a counter electrode (conductive layer). And (b) a driving substrate and a counter substrate provided with a counter electrode (conductive layer). The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices, and the like. .

  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, published in 1994)”. The liquid crystal display device of the present invention is not particularly limited except that it includes the liquid crystal display element of the present invention. For example, the liquid crystal display device can be configured as various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”. . In particular, it is effective in constructing a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”.

  The liquid crystal display device of the present invention is an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, a light diffusion film, except that the liquid crystal display device of the present invention described above is provided. It can be generally configured using various members such as an antiglare film. Regarding these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

（Ａ１−２）下記化合物：ＩＲＧＡＣＵＲＥ ＯＸＥ−０１（ＢＡＳＦ社製）

（Ａ１−３）下記化合物：ＩＲＧＡＣＵＲＥ ＯＸＥ−０２（ＢＡＳＦ社製）

（Ａ１−４）下記化合物：３０４Ａ（常州強力電子製、ＴＲ−ＰＢＧ３０４）

（Ａ１−５）下記化合物：（富士フイルム製、ＺＳ５３９）

（Ａ１−６）下記化合物：Ｂ−ＣＩＭ（保土ヶ谷化学工業製）

In this example, the following compounds were employed.
(A1) Oxime polymerization initiator (A1-1) The following compound was synthesized by the method described in JP-A-2007-231000.

(A1-2) The following compound: IRGACURE OX-01 (manufactured by BASF)

(A1-3) The following compound: IRGACURE OXE-02 (manufactured by BASF)

(A1-4) The following compound: 304A (manufactured by Changzhou Strong Electronics Co., Ltd., TR-PBG304)

(A1-5) The following compound: (manufactured by Fuji Film, ZS539)

(A1-6) The following compound: B-CIM (manufactured by Hodogaya Chemical Co., Ltd.)

(A2) Polymerization initiator 2
(A2-1) The following compound: IRGACURE 379 (manufactured by BASF)

（Ｃ−２）下記重合性モノマー：東亜合成化学株式会社製、平均酸価：６７．０±２０ｍｇＫＯＨ／ｇ

（Ｃ−３）下記重合性モノマーの混合物：Ｍ−５１０（東亜合成化学株式会社製）（酸価：１００±２０ｍｇＫＯＨ／ｇ）

（Ｃ−４）ジペンタエリスリトール ヘキサアクリレート（ＤＰＨＡ）（日本化薬製、ＫＡＹＡＲＡＤ ＤＰＨＡ）（酸価：０ｍｇＫＯＨ／ｇ）
（Ｃ−５）ＰＥＴＡ（ペンタエリスリトールテトラアクリレートとペンタエリスリトールトリアクリレートの４０：６０（重量比）の混合物）（東亞合成製、ＫＡＹＡＲＡＤ Ｍ−３０５）（酸価：０ｍｇＫＯＨ／ｇ）

(C) Polymerizable monomer (C-1) The following polymerizable monomer: M-520 (manufactured by Toagosei Co., Ltd.), average acid value: 30 ± 10 mg KOH / g

(C-2) The following polymerizable monomer: manufactured by Toagosei Co., Ltd., average acid value: 67.0 ± 20 mg KOH / g

(C-3) Mixture of polymerizable monomers shown below: M-510 (manufactured by Toa Gosei Chemical Co., Ltd.) (acid value: 100 ± 20 mg KOH / g)

(C-4) Dipentaerythritol hexaacrylate (DPHA) (manufactured by Nippon Kayaku, KAYARAD DPHA) (acid value: 0 mgKOH / g)
(C-5) PETA (40:60 (weight ratio) mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate) (manufactured by Toagosei Co., Ltd., KAYARAD M-305) (acid value: 0 mgKOH / g)

(D) Alkali-soluble resin The binder which superposed | polymerized the following monomers in the ratio (mass ratio) as described in parenthesis was employ | adopted. Here, BzMA is benzyl methacrylate, MMA is methacrylic acid, AA is acrylic acid, CHMA is cyclohexyl methacrylate, GMA-MMA is glycidyl methacrylate, and AllylMA is allyl methacrylate.
The unit of the following acid value is mgKOH / g, the unit of the glass transition point (Tg) is ° C., and Mw indicates the weight average molecular weight.

(D1)
D1-1: BzMA (53) / MAA (47) (acid value: 195, Tg: 92, Mw 11000)
D1-2: BzMA (60) / AA (40) (acid value: 167, Tg: 63.9, Mw11000)
D1-3: BzMA (60) / MAA (40) (acid value: 160, Tg: 84.5, Mw 11000)
D1-4: BzMA (70) / MAA (30) (acid value: 113, Tg: 74.9, Mw 11000)
D1-5: BzMA (20) / MAA (80) (acid value: 483, Tg: 84.4, Mw 11000)
D1-6: BzMA (40) / MAA (60) (acid value: 275, Tg: 110, Mw 11000)
D1-7: BzMA40 / AA60 (acid value: 296, Tg: 72, Mw 11000)
D1-8: BzMA30 / AA70 (acid value: 380, Tg: 77.5, Mw 11000)
D1-9: Allyl MA (50) / MAA (50) (acid value: 264, Tg: 92, Mw 11000)
D1-10: MMA (100) (acid value: 651, Tg: 228, Mw 11000)
D1-11: BzMA40 / nBuA20 / AA40 (acid value: 179, Tg: 32.8, Mw11000)
D1-12: MMA70 / MAA30 (acid value: 175, Tg: 132, Mw 11000)

Ｄ２−４：ＡｌｌｙｌＭＡ（６９）／ＭＡＡ（３１）（酸価：１３０、Ｔｇ：６６、Ｍｗ３５０００）
Ｄ２−５：ＡｌｌｙｌＭＡ（８０）／ＭＡＡ（２０）（酸価：９５、Ｔｇ：５３、Ｍｗ３５０００ ）
Ｄ２−６：ＡｌｌｙｌＭＡ（６０）／ＡＡ（４０）（酸価：２１５、Ｔｇ：５２、Ｍｗ３００００）
Ｄ２−７：ＡｌｌｙｌＭＡ（５０）／ＡＡ（５０）（酸価：２８３、Ｔｇ：５８、Ｍｗ３００００）
Ｄ２−８：下記化合物(ダイセル・サイテック製、サイクロマーＰ ＡＣＡ２３０ＡＡ）（酸価：３０、Ｔｇ１２０、Ｍｗ１４０００）

(D2)
D2-1: CHMA (46) / MMA (2) / GMA-MMA (32) / MAA (20) (acid value: 66, Tg: 98), Mw 40000)
D2-2: CHMA (40) / MMA (2) / GMA-MMA (31) / MAA (27) (acid value: 91, Tg: 103, Mw 40000)
D2-3: The following compound (Showa High Polymer, SPCF-9X) (acid value: 36, Tg: 140, Mw 9000)

D2-4: Allyl MA (69) / MAA (31) (acid value: 130, Tg: 66, Mw 35000)
D2-5: Allyl MA (80) / MAA (20) (acid value: 95, Tg: 53, Mw 35000)
D2-6: Allyl MA (60) / AA (40) (acid value: 215, Tg: 52, Mw 30000)
D2-7: Allyl MA (50) / AA (50) (acid value: 283, Tg: 58, Mw 30000)
D2-8: The following compound (manufactured by Daicel Cytec, Cyclomer P ACA230AA) (acid value: 30, Tg120, Mw14000)

(E) Photosensitizer The following compound: (Nippon Kayaku, KAYACURE DETX-S)

Example 1
<Preparation of photosensitive resin composition>
The components shown in the following table were mixed in the proportions shown below and stirred to prepare a photosensitive resin composition. All the addition amounts shown below represent parts by mass.
(Composition 1)
-(A1) Photopolymerization initiator 0.36 parts-(A2) Photopolymerization initiator 0.72 parts-(B) Solvent: 44.8 parts of PGMEA-(B) Solvent: 3-ethoxyethyl propionate 19. 2 parts. (C) Polymerizable monomer: 19.4 parts. (D1) Alkali-soluble resin 1 12.75 parts. (E) Photosensitizer: 2.52 parts. Polymerization inhibitor: p-methoxyphenol. 03 parts ・ Adhesion aid: KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.18 parts ・ Surfactant: Megafac F781-F (manufactured by DIC Corporation, fluorine-based surfactant)
0.04 parts

<Formation of Photospacer Pattern Using Photosensitive Resin Composition>
Using the photosensitive resin composition obtained as described above, a pattern was formed on the substrate as follows.

-Formation of photosensitive resin composition layer-
The obtained photosensitive resin composition was applied to a glass substrate with ITO (N-07, 0.7 mm thickness manufactured by Nippon Sheet Glass Co., Ltd.). Specifically, the photosensitive resin composition layer after post-baking was applied by adjusting the interval between the slit nozzle and the substrate and the discharge amount so that the film thickness after drying was about 4.0 μm.

-Pre-baking process-
Next, the photosensitive resin composition layer was dried with a vacuum dryer until the degree of vacuum reached 66 Pa, and then heated (prebaked) at 80 ° C. for 120 seconds using a hot plate.

-Exposure process (proximity exposure)-
After the pre-bake treatment, a proximity exposure machine (Hitachi High-Technologies Corporation, LE5565A) is used, an i-line cut filter SC-39 (Fuji Film) is placed between the mask surface and the photosensitive resin layer surface, and a half-tone mask. 200 mJ / cm ² for the main photo spacers through, the sub photo spacers were exposed so that 40 mJ / cm ^2.

-Development process, baking (post-baking) process-
Then, using a developing device (manufactured by Hitachi High-Technologies Corporation), the shower pressure was reduced to 0 at 24 ° C. with a TMAH developer (FHD-5 pure water diluted product, 0.5% manufactured by Fuji Film Electronics Materials). Developed at 2 MPa for 60 seconds and washed with pure water.
After sufficiently drying, it was post-baked in an oven at 230 ° C. for 20 minutes to obtain a photospacer pattern.

  The resulting photospacer pattern was evaluated for halftone suitability, shape, mechanical properties, and poly and bake margin.

Examples 2-28, Comparative Examples 1-11
In composition 1 of Example 1, (A) Type of photopolymerization initiator, (C) Type of polymerizable monomer, (D) Type of alkali-soluble resin, and exposure wavelength were changed as described in Table 1. Otherwise, in the same manner as Example 1, photosensitive resin compositions of Examples 2 to 28 and Comparative Examples 1 to 11 were prepared. Here, when using alkali-soluble resin (D1) and (D2) together, the ratio of D1 and D2 was set to 50:50. Further, using each of the obtained photosensitive resin compositions, the halftone suitability, shape, mechanical properties, poly and bake margin were evaluated in the same manner as in Example 1.

(Halftone suitability)
The film thickness and shape of the obtained main photo spacer and sub photo spacer were observed, and the halftone suitability was evaluated. A non-contact surface shape measuring instrument NewView 7300 (manufactured by Zygo) was used for film thickness measurement and shape observation. The evaluation is in five stages, and a larger number indicates better performance.
5: The film thickness difference between the main photo spacer and the sub photo spacer is 0.5 μm or more, and the sub photo spacer has a trapezoidal shape. 4: The film thickness difference between the main photo spacer and the sub photo spacer is 0.4 μm or more. Less than 0.5 μm and the shape of the sub photo spacer is trapezoid 3: The difference in film thickness between the main photo spacer and the sub photo spacer is not less than 0.3 μm and less than 0.4 μm, and the shape of the sub photo spacer is trapezoidal. Shape 2: A difference in film thickness between the main photo spacer and the sub photo spacer is 0.3 μm or more, but the sub photo spacer is not trapezoidal 1: Not corresponding to the above 2-5

(shape)
The shape of the sub-photo spacer pattern of the photosensitive resin composition was observed with an optical microscope and evaluated. The evaluation is in five stages, and a larger number indicates better performance.
<Evaluation criteria for shape>
5: The shape is trapezoidal, and there is no chipping or peeling. 4: The shape of some patterns is dome-shaped, and there is no peeling or peeling. 3: The shape is dome-shaped, and there is no peeling or peeling. Some of them are scratched or peeled.

(Mechanical properties)
The obtained photo spacer was measured with a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows and evaluated as a deformation recovery rate. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following evaluation criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH. The evaluation is in five stages, and a larger number indicates better performance.
Deformation recovery rate (%)
= (Recovery amount after release of load [μm] / Deformation amount under load [μm]) × 100
5: Deformation recovery rate of 90% or more for both main photospacer and sub-photospacer 4: Not applicable to 5 above, Deformation recovery rate of main photospacer of 90% or more 3: Applicable to 4 and 5 above No, the main photo spacer has a deformation recovery rate of 85% or more 2: Does not correspond to the above 3-5, and the main photo spacer has a deformation recovery rate of 80% or more 1: Does not correspond to the above 2-5

(Post-bake margin (PB margin))
Among the pattern forming methods using the photosensitive resin composition, the post-baking temperature is 230 ° C. to 215 ° C. (−15 ° C.), 220 ° C. (−10 ° C.), 225 ° C. (−5 ° C.), 235 ° C. (+ 5 ° C.). ), 240 ° C. (+ 10 ° C.), and 245 ° C. (+ 15 ° C.). The post bake margin was evaluated for changes in shape and mechanical properties at this time. The evaluation is in five stages, and a larger number indicates better performance.
5: No change in shape and mechanical properties at post-bake temperature ± 15 ° C. 4: Not applicable to 5 above, No change in shape and mechanical properties at post-bake temperature ± 10 ° C. 3: Applicable to 4 and 5 above No change in shape and mechanical properties at post-baking temperature ± 5 ° C. 2: No change in shape or mechanical properties at post-baking temperature ± 5 ° C. not corresponding to 3-5 above 1: No. 2 above Not applicable to 5

The results are shown in the table below.

As is clear from the above table, each photospacer obtained using the photosensitive resin composition of the example had excellent halftone suitability and good shape, and excellent mechanical properties and post-bake margin. . From the comparison between Example 3 and Examples 9 to 14, 17, and 18, the effect of improving the mechanical properties and the post-bake margin was further obtained by using the alkali-soluble resin in combination. Moreover, from Examples 15 and 16, it was found that the same effect can be obtained even when an alkali-soluble resin having a crosslinkable group and having an appropriate acid value and Tg is used alone.
On the other hand, each photospacer obtained using the photosensitive resin compositions of Comparative Examples 1 to 11 could not achieve both halftone suitability, mechanical properties, and post-bake margin. When the acid value of the alkali-soluble resin is low or the Tg is high, the halftone suitability is insufficient. When the acid value of the alkali-soluble resin was high, the surface erosion by the developing solution progressed too much, causing chipping and peeling. When the Tg of the alkali-soluble resin was low, a halftone film thickness difference was obtained, but the shape was unstable or a post-bake margin could not be obtained.
Furthermore, from comparison between Examples 1 and 2, it was found that the photosensitive resin composition in the present invention can cope with not only gh-line exposure but also ghi-line exposure.
From the above, it has been found that by using an alkali-soluble resin having an acid value and Tg in an appropriate range, it is possible to realize a total performance of halftone suitability, mechanical properties, and post-bake margin.

  Since the PS pattern of the present invention can easily form a main PS and a sub PS in a shape close to a cylindrical shape, elements that require high definition such as a touch panel for in-vehicle navigation, a touch panel, a portable mobile device, and a smartphone. It can be used as PS.

Claims (15)

(A) a photopolymerization initiator, (B) a solvent, (C) a polymerizable monomer, and (D) an alkali-soluble resin, and (D) at least one of the alkali-soluble resins has an acid value of 150 to 400 mgKOH / g And a glass transition point (Tg) of 50 to 120 ° C., wherein two or more independent patterns can be simultaneously formed. The said (D) alkali-soluble resin contains a crosslinkable group, or contains the alkali-soluble resin (D2) which has a crosslinkable group in a side chain separately from the said (D) alkali-soluble resin. Photosensitive resin composition. The photosensitive resin composition of Claim 2 which has the weight ratio of the said alkali-soluble resin (D1) and the said alkali-soluble resin (D2) in the range of 5: 95-70: 30. (A) At least 2 or more types are used together as a photoinitiator, The photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned. (A) The photosensitive resin of any one of Claims 1-3 containing photoinitiators other than 1 or more types of oxime ester compounds and 1 or more types of oxime ester compounds as a photoinitiator. Composition. Furthermore, the photosensitive resin composition of any one of Claims 1-5 containing (E) photosensitizer or a co-initiator. The total addition amount of (A) photopolymerization initiator and (E) photosensitizer or co-initiator is 0.1 to 15.0% by weight in the total solid content. Item 7. The photosensitive resin composition according to any one of Items 1 to 6. (C) The photosensitive resin composition of any one of Claims 1-7 whose polymerizable monomer has an acid group and whose acid value is 20-150 mgKOH / g. (D) The photosensitive resin composition of any one of Claims 1-8 whose alkali-soluble resin is acrylic resin. The alkali-soluble resin (D2) is an acrylic resin having an acid value of 150 to 400 mgKOH / g and a glass transition point (Tg) of 50 to 120 ° C. The photosensitive resin composition as described. The photosensitive resin composition of any one of Claims 1-10 which is an object for gh line exposure. Applying the photosensitive resin composition according to any one of claims 1 to 11 on a substrate to form a photosensitive resin composition layer; and pattern-like with respect to the photosensitive resin composition layer An exposure step of performing exposure by changing the exposure amount and curing the exposed portion; and a developing step of removing uncured portions of the photosensitive resin composition layer by development to form two or more independent patterns. Pattern forming method. The manufacturing method of a photo spacer including the process of forming two or more types of independent photo spacer patterns on a board | substrate using the photosensitive resin composition of any one of Claims 1-11. A photospacer having two or more kinds of independent patterns manufactured by the manufacturing method according to claim 12. The display apparatus which has a photo spacer which has two or more types of independent patterns of Claim 14.