JP2009003442A - Photosensitive resin composition, liquid crystal alignment control rib, spacer, color filter and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which ensures moderate melt flow so that members, such as ribs, spacers and an overcoat adjacent to a liquid crystal located between electrodes in a color liquid crystal display, can be formed into desirable shapes, and which solves the problems, such as uneven displays and ghost images caused by image persistence, without adversely affecting the electrical properties, such as voltage retention of the liquid crystal. <P>SOLUTION: The photosensitive resin composition constitutes members located between electrodes, in a color liquid crystal display comprises (A) a resin, having carboxyl groups and/or hydroxyl groups, represented by formulae (1) and (B) a photopolymerization initiator and/or a photoacid generator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the color liquid crystal display device, a member positioned between the electrodes, for example, a liquid crystal alignment control protrusion (rib), a spacer, an overcoat, or a pixel layer or a black matrix formed on the electrode depending on the cell configuration. The present invention relates to a photosensitive resin composition for forming. Furthermore, it is related with the photosensitive resin composition for forming a spacer and a liquid crystal orientation control protrusion simultaneously. The present invention also relates to members such as liquid crystal alignment control protrusions and spacers formed using the photosensitive resin composition, and relates to a color filter and an image display device having these members.

  A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage to the liquid crystal. On the other hand, each member forming the LCD cell is often formed using a photosensitive resin composition typified by photolithography, which is easy to form a fine structure on a substrate for a large screen. From the reason that this treatment is easy, the range of application of the photosensitive resin composition tends to further expand in the future.

However, in an LCD using a photosensitive resin composition, the voltage applied to the liquid crystal may not be maintained due to the electrical characteristics of the photosensitive resin composition itself and the impurities contained in the photosensitive resin composition. Even if the power is turned off, the electric potential remains, causing problems such as display unevenness and afterimage. In particular, ribs, spacers, and overcoats disposed between the electrodes have a great influence.
For this reason, the photosensitive resin composition for forming a member located between the electrodes in the color liquid crystal display device such as a rib, a spacer, or an overcoat, that is, a member adjacent to the liquid crystal, has a voltage holding ratio of the liquid crystal. In order to improve the problems such as display unevenness and afterimage caused by burn-in and the like without adversely affecting the electrical characteristics such as, it is desirable to have excellent electrical characteristics such as voltage holding ratio.

  Furthermore, these ribs, spacers, and overcoat members, for example, ribs and spacers are required to secure the required shape, and overcoats are required to have smooth surface irregularities on the pixel surface for each RGB color. It is desired that the photosensitive resin composition for forming the member is adjusted to an appropriate melt flow (fluidity) in a curing process performed after exposure and development.

  In addition, the photosensitive resin composition of the present invention includes components (A) and (B) described later as constituent components, and particularly has component (A). Resins corresponding to (A) are also described in, for example, JP-B-1-54390, JP-A-10-114852, and JP-A-2004-117857. However, in these patent documents, this resin is mainly used for solder resists and electroless plating resists in the production of printed wiring boards, and is dilute alkali developability, solder heat resistance, and electroless plating resistance. Is a feature that is completely different from the present invention. Conventionally, the influence of these resins on liquid crystals has not been studied at all.

Examples of applying these resins to ribs include those described in Japanese Patent Application Laid-Open No. 2005-221947. However, simply applying these resins causes problems in image formation and is quite practical. It wasn't.
Japanese Patent Publication No. 1-54390 Japanese Patent Laid-Open No. 10-114852 JP 2004-117857 A JP 2005-221947 A

The present invention has been made in view of the above-described conventional situation, and a member such as a rib, a spacer, or an overcoat, which is located between electrodes in a color liquid crystal display device, that is, adjacent to a liquid crystal, is a liquid crystal. A photosensitive resin composition that does not adversely affect the electrical characteristics such as voltage holding ratio of the toner, improves the problems such as display unevenness and afterimage caused by image sticking, and can be formed into a preferable shape by a moderate melt flow. The purpose is to provide.
The present invention also provides a color filter having a member formed using the photosensitive resin composition and an image display device.

As a result of intensive studies on the above problems, the present inventor has found that the above problems can be solved by using a photosensitive resin composition containing the following (A) and (B) as constituent components.
Accordingly, the gist of the present invention is as follows.

[1] A photosensitive resin composition constituting a member located between electrodes in a color liquid crystal display device, comprising the following component (A) and component (B): .
(A) Resin having a carboxyl group and / or a hydroxyl group represented by the following formula (1) (B) Photopolymerization initiator and / or photoacid generator

〔式（１）中、Ｘは、水素原子、或いはカルボキシル基及び／又は水酸基を有しさらにその他の置換基を有していても良い炭化水素基であり、複数のＸは互いに同一であっても良く、異なっていても良いが、全てのＸが水素原子である場合は除く。
Ｗは、下記式（８）で表される２価の連結基である。
Ｐは水素原子、ハロゲン原子、炭素数１〜８のアルキル基、又はアリール基を表し、複数のＰは互いに同一であっても異なっていても良い。
ｎは平均値を表し、１〜２００である。

（式（８）中、ＵとＶは、それぞれ独立に、水素原子、或いは、置換基を有していても良い、炭素数１〜８のアルキル基、アリール基、又は複素環式化合物由来の基を表す。）〕

[In Formula (1), X is a hydrocarbon group which has a hydrogen atom or a carboxyl group and / or a hydroxyl group, and may have another substituent, and a plurality of X are the same as each other. Or may be different, except when all X are hydrogen atoms.
W is a divalent linking group represented by the following formula (8).
P represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and a plurality of P may be the same as or different from each other.
n represents an average value and is 1 to 200.

(In Formula (8), U and V are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group, or a heterocyclic compound which may have a substituent. Represents a group.)]

〔式（９）、（１０）中、Ｙは水素原子、又は置換基を有していても良く且つ不飽和基を含んでいても良い炭化水素基であり、成分（Ａ）の樹脂中に含まれる複数のＹは互いに同一であっても良く、異なっていても良い。式（９）中、Ｚは置換基を有していても良い２価の炭化水素基（連結基）であり、成分（Ａ）の樹脂中に含まれる複数のＺは互いに同一であっても良く、異なっていても良い。
なお、上記式（９）、（１０）、（１１）中、（*）は、式（１）におけるエーテル基への結合部位を表す。〕 [2] X in the formula (1) is selected from the following formulas (9), (10), and (11), and is included in the resin of the component (A) (9), (10), (11 ), When the average value of the content of each group is a, b, c, a, b, c are each independently 0-150, and a + b + c is 3-200, The photosensitive resin composition according to claim 1.

[In the formulas (9) and (10), Y is a hydrogen atom or a hydrocarbon group which may have a substituent and may contain an unsaturated group, and in the resin of the component (A) The plurality of Y included may be the same as or different from each other. In formula (9), Z is a divalent hydrocarbon group (linking group) which may have a substituent, and a plurality of Z contained in the resin of component (A) may be the same as each other It may be good or different.
In the above formulas (9), (10), and (11), (*) represents a bonding site to the ether group in the formula (1). ]

〔式（１２）、（１３）中、Ｑは水素原子、又はメチル基である。
Ｚは式（９）におけると同義である。
なお、上記式（１２）、（１３）中、（*）は、式（１）におけるエーテル基への結合部位を表す。〕 [3] The above formulas (9) and (10) are represented by the following formulas (12) and (13), respectively, and further contain an ethylenically unsaturated compound as the component (C) [2] The photosensitive resin composition as described in 2.

[In Formula (12) and (13), Q is a hydrogen atom or a methyl group.
Z has the same meaning as in formula (9).
In the above formulas (12) and (13), (*) represents the binding site to the ether group in formula (1). ]

[4] The photosensitive resin composition according to [2] or [3], wherein c / (a + b) is 0.2 to 9.

[5] The photosensitive resin composition according to any one of [1] to [4], further comprising a pigment.

[6] The photosensitive resin composition according to any one of [1] to [5], further comprising a substrate adhesion enhancer.

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) includes oxime derivatives.

[8] The photosensitive resin composition according to any one of [1] to [7], further comprising a crosslinking agent.

[9] The photosensitive resin composition according to any one of [1] to [8], wherein the resin contains a novolak resin and / or a hydroxystyrene resin in addition to the component (A). .

[10] In any one of [1] to [9], in the color liquid crystal display device, the members positioned between the electrodes are liquid crystal alignment control protrusions and spacers, and are used to form these simultaneously. The photosensitive resin composition as described in 2.

[11] A liquid crystal alignment control protrusion formed using the photosensitive resin composition according to any one of [1] to [10].

[12] A spacer formed using the photosensitive resin composition according to any one of [1] to [10].

[13] A color filter having a member formed using the photosensitive resin composition according to any one of [1] to [10] between electrodes.

[14] An image display device using a color filter having a member formed using the photosensitive resin composition according to any one of [1] to [10] between electrodes.

  According to the photosensitive resin composition of the present invention, a member located between electrodes in a color liquid crystal display device, that is, a rib, a spacer, or an overcoat, that is, a member adjacent to the liquid crystal, such as a voltage holding ratio of the liquid crystal. The electric characteristics are not adversely affected, and problems such as display unevenness and afterimages caused by image sticking or the like can be improved, and a preferable shape can be formed by a moderate melt flow.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. These contents are not specified.

In the present invention, “(meth) acrylic acid” means that both acrylic acid and methacrylic acid are included, and “(meth) acrylate”, “(meth) acryloyl” and the like have the same meaning. . Moreover, what added "(poly)" in front of the monomer name means including both the said monomer and its polymer, and "(acid) anhydride", "(anhydrous) ... acid" Means to include both acids and their anhydrides.
In the present invention, “total solid content” means all components except the solvent among the constituent components of the photosensitive resin composition of the present invention.

[Photosensitive resin composition]
First, the photosensitive resin composition of this invention is demonstrated in detail.
The photosensitive resin composition of the present invention is mainly for constituting members positioned between electrodes, such as ribs, spacers, and overcoats, in a color liquid crystal display device, and includes the following (A) and (B) is included as a constituent component.
(A) Resin having a carboxyl group and / or a hydroxyl group represented by the following formula (1) (B) Photopolymerization initiator and / or photoacid generator

（式（８）中、ＵとＶは、それぞれ独立に、水素原子、或いは、置換基を有していても良い、炭素数１〜８のアルキル基、アリール基、又は複素環式化合物由来の基を表す。）〕 [In Formula (1), X is a hydrocarbon group which has a hydrogen atom or a carboxyl group and / or a hydroxyl group, and may have another substituent, and a plurality of X are the same as each other. Or may be different, except when all X are hydrogen atoms.
W is a divalent linking group represented by the following formula (8).
P represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and a plurality of P may be the same as or different from each other.
n represents an average value and is 1 to 200.

(In Formula (8), U and V are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group, or a heterocyclic compound which may have a substituent. Represents a group.)]

<Component (A)>
A feature of the present invention is that the component (A) includes a resin having a carboxyl group and / or a hydroxyl group represented by the above formula (1).

In the above formula (1), preferred examples of X are as follows, but P is particularly preferably a hydrogen atom or a methyl group from the viewpoint of ease of production and cost.
In the formula (8) representing W, U and V are particularly a hydrogen atom, a methyl group, an ethyl group, a vinyl group, a phenyl group, a cinnamyl group, and a furfuryl group because of the ease of polycondensation of the skeleton resin. Among them, a hydrogen atom and a methyl group are particularly preferable.
From the viewpoint of image formation, n is preferably 10 to 90, particularly preferably 15 to 70.

  As an example of a preferable resin of the component (A), for example, X in the above formula (1) is selected from the following formulas (9), (10), and (11), and is included in the resin of the component (A) When the average value of the content of each group represented by (9), (10), (11) is a, b, c, a, b, c are each independently 0-150, and a + b + c Are those having 3 to 200. If the value of a + b + c is less than 3, image formation may be difficult, and if it exceeds 200, there is a possibility that developability cannot be ensured.

[In the formulas (9) and (10), Y is a hydrogen atom or a hydrocarbon group which may have a substituent and may contain an unsaturated group, and in the resin of the component (A) The plurality of Y included may be the same as or different from each other. In formula (9), Z is a divalent hydrocarbon group (linking group) which may have a substituent, and a plurality of Z contained in the resin of component (A) may be the same as each other It may be good or different.
In the above formulas (9), (10), and (11), (*) represents a bonding site to the ether group in the formula (1). ]

Preferred examples of Y in the groups represented by the above formulas (9) and (10) include alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; a vinyl group, an allyl group, Examples thereof include alkenyl groups having 2 to 8 carbon atoms such as propenyl group and isopropenyl group; aromatic groups such as phenyl group, styryl group and cinnamyl group.
Moreover, as a preferable example of Z in the said Formula (9), C2-C8 alkylene groups, such as a methylene group, ethylene group, a propylene group, cyclohexenylidene, etc .; Ethenylidene group, a propylidene group, etc., C2-C8 Alkenylidene group; aromatic groups such as phenylene group, methylphenylene group, dimethylphenylene group, trimethylphenylene group, naphthylene group, carboxylphenylene group, methoxyphenylene group and the like.

  Among them, in particular, Y is a vinyl group or an isopropenyl group, that is, formulas (9) and (10) are represented by the following formulas (12) and (13), respectively, and Z is an ethylene group. Or 4,5-cyclohexenylidene group or carboxylphenylene group, a: b: c of 10 to 100: 0 to 70: 0 to 70, and a + b + c of 2 to 100 are excellent in balance between sensitivity and developability. In addition, those having c / (a + b) of 0.2 to 9 are excellent in melt flow at the time of curing and easy to form a preferable shape.

〔式（１２）、（１３）中、Ｑは水素原子、又はメチル基である。
Ｚは式（９）におけると同義である。
なお、上記式（１２）、（１３）中、（*）は、式（１）におけるエーテル基への結合部位を表す。〕

[In Formula (12) and (13), Q is a hydrogen atom or a methyl group.
Z has the same meaning as in formula (9).
In the above formulas (12) and (13), (*) represents the binding site to the ether group in formula (1). ]

  In addition, when the photosensitive resin composition of the present invention is used for spacer applications, the spacer is required to have compression characteristics. Therefore, when the resin itself is formed by photopolymerization, the double bond equivalent must be controlled. It becomes. In that case, for example, it is possible to design a resin by mixing an ethylenically unsaturated group with Y in the above formulas (9) and (10) and a group that imparts elasticity to the resin. This is also a great difference from the resin disclosed in Kaihei 10-114852.

  A known method can be used for producing the resin in which X in the formula (1) is a group represented by the formulas (9), (10), and (11). For example, the following methods are listed. It is done.

  First, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance to a dissolved mixture of a novolak resin and an excess of epihalohydrin such as epichlorohydrin or epibromohydrin, or at a temperature of 20 to 120 ° C. with addition. The intermediate body which introduce | transduced the epoxy group is obtained by making it react for 1 to 10 hours.

  In the reaction for obtaining the intermediate having the epoxy group introduced therein, the alkali metal hydroxide may be used as an aqueous solution, in which case the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system. A method may be employed in which water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, followed by liquid separation, water removal, and epihalohydrin being continuously returned to the reaction system.

  Further, it is obtained by adding a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst to a dissolved mixture of novolak resin and epihalohydrin and reacting at 50 to 150 ° C. for 1 to 5 hours. Alternatively, a method of adding a solid or aqueous solution of an alkali metal hydroxide to a halohydrin etherified product of a novolak resin and reacting again at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used.

  The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, per 1 equivalent of the hydroxyl group of the novolak resin. Moreover, the usage-amount of an alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of a novolak resin, Preferably it is 0.9-11 mol.

Furthermore, in order to make the reaction proceed smoothly, the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol.
When alcohols are used, the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, the usage-amount is 5 to 100 weight% with respect to the quantity of an epihalohydrin, Preferably it is 10 to 90 weight%.

  After the reaction product of these epoxidation reactions is washed with water or without washing, epihalohydrin and other added solvents are removed under reduced pressure by heating at 110 to 250 ° C. and a pressure of 1.3 kPa (10 mmHg) or less. In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, particularly preferably 0.05 to 0.2 mol based on 1 equivalent of the hydroxyl group of the novolak resin for epoxidation. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours. After completion of the reaction, the produced salt is removed by filtration, washing with water and the like, and further, a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure.

  Next, the epoxy resin obtained by the above method is reacted with a carboxylic acid compound. For this reaction, for example, the above epoxy resin and carboxylic acid are combined with a tertiary amine such as triethylamine or benzylmethylamine, or dodecyltrimethyl. Reaction in quaternary ammonium salts such as ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours By doing so, a carboxylic acid can be added to the epoxy resin.

  The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (total of epoxy resin and carboxylic acid compound). In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 to 10 weight% with respect to a reaction raw material mixture, Most preferably, it is 0.1 to 5 weight%.

  The ratio of adding the carboxylic acid compound to the epoxy group of the epoxy resin is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects the storage stability, the carboxylic acid compound is usually 0.8 to 1.5 equivalents, particularly 0.9 to 1.1 equivalents per 1 equivalent of epoxy group of the epoxy resin. It is preferable to carry out the reaction.

  The carboxylic acid compounds used here are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, benzoic acid, cinnamic acid, amino acids, crotonic acid, lactic acid, o- , M-, p-vinyl benzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, monocarboxylic acid such as cyano substituent, 2- (meth) acryloyloxyethyl succinic acid, 2-acrylic acid Leuroxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acrylic acid Leuoxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxy Lopyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxy Butyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid and ε-caprolactone , Β-propiolactone, γ-butyrolactone, δ-valerolactone, and other lactones, or monomers of hydroxyalkyl (meth) acrylate and pentaerythritol tri (meth) acrylate (anhydrous) Add acid (anhydride) such as acid, (anhydrous) phthalic acid, (anhydrous) maleic acid And monomer, and (meth) acrylic acid dimer. These can be used alone or in combination of two or more.

  Next, by adding a polybasic acid and / or its anhydride to the hydroxyl group of the reaction product of the epoxy resin and the carboxylic acid compound, X in the formula (1) is represented by the formulas (9), (10), (11). The resin which is group represented by these can be obtained. As the polybasic acid and / or anhydride thereof used here, known ones can be used. Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Dibasic carboxylic acids such as chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid or their anhydrides; trimellitic acid, pyromellitic acid And polybasic carboxylic acids such as benzophenone tetracarboxylic acid and biphenyl tetracarboxylic acid, or anhydrides thereof. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone or in combination of two or more.

  The addition rate of the polybasic acid and / or anhydride thereof is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably of the hydroxyl group produced when the carboxylic acid compound is added to the epoxy resin. 30 to 100 mol%. If the addition rate is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient.

  As a method for adding a polybasic acid and / or an anhydride thereof to the hydroxyl group of the reaction product after adding a carboxylic acid compound to the above epoxy resin, a known method can be used. ) In which X is a group represented by the formulas (9), (10), and (11). When the average value of the content of each resin in which X in Formula (1) is a group represented by Formulas (9), (10), and (11) is a, b, c, a, b, c Can be adjusted by the amount of epihalohydrin reacted with a novolac resin and the amount of carboxylic acid compound reacted with an epoxy resin, but a: b: c is 10-100: 0 to 70: 0 to 70, a + b + c. Is preferably 2 to 100, and as described above, c / (a + b) is preferably added in the range of 0.2 to 9.

  As another method for producing a resin in which X in the formula (1) is a group represented by the formula (9), (10), or (11), there is a method of reacting a novolak resin and an unsaturated group-containing epoxy compound. is there. In this case, a polybasic acid and / or an anhydride thereof can be further added to the hydroxyl group of the reaction product.

Examples of the unsaturated group-containing epoxy compound include glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, glycidyloxy (poly) alkylene glycol (meth) acrylate, methyl glycidyl (meth) acrylate, ( 3,4-epoxycyclohexyl) vinyl and the like.
Of these, glycidyl methacrylate and (3,4-epoxycyclohexyl) methyl (meth) acrylate are particularly preferable.

  A known method can be used for the reaction of the novolak resin and the unsaturated group-containing epoxy compound. For example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc. in an organic solvent. By reacting at a reaction temperature of 50 to 150 ° C. for several to several tens of hours, an unsaturated group-containing epoxy compound can be added to the novolak resin.

  The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (the total of the novolak resin and the unsaturated group-containing epoxy compound). In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, dibutylhydroxytoluene, phenothiazine). The amount used is preferably 0.01 to 10% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.

  The ratio of adding the unsaturated group-containing epoxy compound to the phenolic hydroxyl group of the novolak resin is 1 to 100%. This ratio can be adjusted by the amount of the unsaturated group-containing epoxy compound added to the phenolic hydroxyl group. In particular, when Formula (9) is a group represented by Formula (12) and Formula (10) is a group represented by Formula (13), the average value of each content is a, b, When it is set as c, it is preferable to add so that c / (a + b) may be in the range of 0.2-9.

  A polybasic acid and / or an anhydride thereof can be further added to the hydroxyl group of the reaction product of the novolak resin and the unsaturated group-containing epoxy compound. As the polybasic acid and / or anhydride thereof used here, known ones can be used. Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, Dibasic carboxylic acids such as chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid or their anhydrides; trimellitic acid, pyromellitic acid And polybasic carboxylic acids such as benzophenone tetracarboxylic acid and biphenyl tetracarboxylic acid, or anhydrides thereof. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone or in combination of two or more.

  The addition rate of the polybasic acid and / or its anhydride is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 30 to the hydroxyl group of the reaction product of the novolak resin and the unsaturated group-containing epoxy compound. 100 mol%. If the addition rate is too small, the solubility may be insufficient or the adhesion to the substrate may be insufficient.

<Other resins>
In the photosensitive resin composition of the present invention, one or more kinds of other arbitrary resins can be mixed and used together with the resin of the component (A) as a resin. In this case, the resins used in combination include novolak resins, hydroxystyrene resins, epoxy acrylic resins, cardo resins, polyamides, polyesters, polyethers, polyurethanes, polyvinyl acetals, polyvinyl alcohols, polyvinyl pyrrolidones, acetyl celluloses, and (meta ) Acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, etc. Resins, hydroxystyrene resins, epoxy acrylic resins, cardo resins and the like are preferable, and novolak resins and hydroxystyrene resins are particularly preferable.

  As novolak resins, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propyl Phenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4'-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, benzoic acid , 4-hydroxyphenylacetic acid, salicylic acid, phloroglucinol and the like phenols in the presence of an acid catalyst, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, Aldehyde, salicylaldehyde, aldehydes such as furfural, or ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, a resin having engaged at least one and polycondensation of.

  The condensation reaction of the phenols with aldehydes or ketones is carried out in the absence of a solvent or in a solvent. A resole resin polycondensed in the same manner can be used except that an alkali catalyst is used instead of the acid catalyst in the polycondensation of the novolak resin.

  The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of novolak resins by gel permeation chromatography (GPC) is 1,000 to 20,000, preferably 1,000 to 10,000. Preferably it is 1,000-8,000. When Mw is less than 1,000, the electrical reliability is lowered, and when it exceeds 20,000, the developability may be lowered.

  In order to enhance alkali solubility in the novolak resins, a carboxylic acid may be added to a part of the phenolic hydroxyl group. Examples of the carboxylic acid include oxalic acid, maleic acid, itaconic acid, phthalic acid, Tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydro One type or two or more types of phthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and anhydrides thereof may be mentioned.

  Examples of the hydroxystyrene-based resin include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene, tetrahydroxystyrene, pentahydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy. Hydroxystyrenes such as -α-methylstyrene, p-hydroxy-α-methylstyrene, 2- (o-hydroxyphenyl) propylene, 2- (m-hydroxyphenyl) propylene, 2- (p-hydroxyphenyl) propylene ( These may have a halogen atom such as chlorine, bromine, iodine or fluorine, or an alkyl group having 1 to 4 carbon atoms as a substituent on the benzene ring. In addition, styrene, α-methylstyrene, etc. , (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, tricyclo [5.2.1.0] decan-8-yl (meth ) Polymerize one or more comonomers such as acrylate, glycidyl (meth) acrylate, and acrylic acid derivatives such as hydroxyphenyl (meth) acrylamide in the presence of a radical polymerization initiator or a cationic polymerization initiator. Examples thereof include homopolymers or copolymers of hydroxystyrenes.

  The weight average molecular weight (Mw) in terms of polystyrene by GPC of the hydroxystyrene resin is usually 2,000 to 50,000, preferably 2,000 to 20,000. If the Mw is less than 2,000, the electrical reliability may be lowered, and if it exceeds 50,000, the developability may be lowered.

  Also for hydroxystyrene resins, carboxylic acid may be added to a part of phenolic hydroxyl group in order to enhance alkali solubility. Examples of this carboxylic acid include oxalic acid, maleic acid, itaconic acid, phthalic acid. Acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methyl 1 type, or 2 or more types, such as hexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, and those anhydrides are mentioned.

In the photosensitive resin composition of the present invention, when the resin of component (A) is mixed with the above novolak resins or hydroxystyrene resins, the weight ratio is the resin of component (A): (novolak resins and / or Or hydroxystyrene-based resin) = 0.5: 9.5 to 9.5: 0.5 is preferable, and 2: 8 to 8: 2 is particularly preferable.
By mixing novolak resins and hydroxystyrene resins with the resin of component (A), the image sticking phenomenon can be further suppressed or the shape can be adjusted, but if the mixing ratio is too small The improvement effect cannot be obtained sufficiently, and if it is too much, effects such as electrical characteristics and plate-making property due to the use of the resin of the component (A) may not be sufficiently obtained in the present invention.

Moreover, alkali-soluble resin can also be used as resin other than resin of a component (A). The alkali-soluble resin is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, and examples thereof include acrylic resins, urethane resins, and epoxy acrylic resins. These alkali-soluble resins can be used singly or in combination of two or more.
When other alkali-soluble resins are used, the ratio of use is preferably a weight ratio of resin of component (A): other alkali-soluble resins = 2: 8 to 9.9: 0.1, particularly preferably 3: 7-9.5: 0.5. By using other alkali-soluble resins for the resin of component (A), the compatibility and dispersibility with other components can be further increased, and performance such as compression properties can be provided. If the amount of the resin is too much, the effect of melt flow for improving the electrical characteristics and securing the shape may not be sufficiently obtained by using the resin of the component (A) in the present invention.

<Component (B): Photopolymerization initiator>
The photopolymerization initiator in the component (B) according to the present invention is a compound capable of generating radicals that polymerize ethylenically unsaturated groups by ultraviolet rays or heat.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
Halomethylated oxadiazole derivatives;
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. An imidazole derivative of
Benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;

Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzanthrone derivatives;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p- Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1, -trichloromethyl Acetophenone derivatives such as-(p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluoro Feni-1-i , Di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as

  In addition, oxime derivatives (oxime compounds) are particularly effective in terms of sensitivity. When the photosensitive resin composition of the present invention contains a phenolic hydroxyl group, it may be disadvantageous in terms of sensitivity. Therefore, the use of oxime derivatives is particularly effective as a method for improving sensitivity in such a case. is there.

Examples of the oxime derivatives include a compound containing a structural moiety represented by the following general formula (3), and preferably an oxime ester compound represented by the following general formula (4).

[In Formula (3), R ² is a C2-C20 heteroaryl group, C2-C12 alkanoyl group, C3-C20 heteroarylalkanoyl group, carbon, which may be substituted, respectively. C3-C25 alkenoyl group, C4-C8 cycloalkanoyl group, C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C4-C20 heteroaryloxy Carbonylalkanoyl group, C2-C10 aminocarbonyl group, C7-C20 aryloyl group, C3-C20 heteroaryloyl group, C2-C10 alkoxycarbonyl group, or C7-C20 Of the aryloxycarbonyl group. ]

[In Formula (4), R ^1a is an optionally substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 3 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, C 8-20 phenoxycarbonylalkyl group, C 4-20 heteroaryloxycarbonylalkyl group, C 3-20 heteroarylthioalkyl group, C 0-20 amino group, C 1-20 Aminoalkyl group, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, heteroary having 3 to 20 carbon atoms Royle group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryl oxycarbonyl group having 7 to 20 carbon atoms, further ^{R 1a} is May form a ring with R ^1b, the linkage is respectively an alkylene group having 1 to 10 carbon atoms which may have a substituent group, polyethylene group _{(- (CH = CH) r} -), Poriechiniren group (— (C≡C) _r —) or a combination thereof (r is an integer of 0 to 3), and R ^1b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ² has the same meaning as in general formula (3). ]

  Specific examples of the oxime derivatives include the following, but are not limited to these compounds.

  These oxime derivatives are known compounds per se, and are, for example, one of a series of compounds described in JP-A No. 2000-80068 and JP-A No. 2006-36750.

  When using a photoinitiator as a component (B), the sensitizing dye according to the wavelength of an image exposure light source can be mix | blended as needed for the purpose of improving a sensitivity. As these sensitizing dyes, for example, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc., complex described in JP-A-3-239703, JP-A-5-289335, etc. Coumarin dyes having a ring, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335 and the like, pyromethene dyes described in JP-A-6-19240, and others, JP-A-47. -2528, JP 54-155292, JP 45-37377, JP 48-84183, JP 52-112681, JP 58-15503, JP JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5 107761, JP-A No. 5-210240, JP-can be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818 Patent Publication. These can be used alone or in combination of two or more.

<Component (B): Photoacid generator>
As the component (B) according to the present invention, a photoacid generator can also be used. The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and a crosslinking reaction of a crosslinking agent such as a melamine compound can be advanced by the action of an acid generated upon exposure.

  Among such photoacid generators, those having high solubility, particularly solubility in a solvent are preferable. For example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis ( Diaryl iodonium such as p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium Or triarylsulfonium chloride, bromide, borofluoride, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic sulfonate salt, tetrakis Tafluorophenyl) borate salts, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, 2-methyl-4,6-bistrichloromethyltriazine, 2- (4-methoxy Examples thereof include, but are not limited to, triazine compounds such as phenyl) -4,6-bistrichloromethyltriazine.

  A crosslinking agent can be further added to the photosensitive resin composition of the present invention. Particularly when a photoacid generator is used as the component (B), the incorporation of the crosslinking agent is effective. Examples of the crosslinking agent include melamine or guanamine compounds, and more specifically, for example, melamine or guanamine compounds represented by the following formula (14).

〔式中、Ｒ^１１は基−ＮＲ^１６Ｒ^１７又はアリール基を表し、Ｒ^１１が基−ＮＲ^１６Ｒ^１７の場合はＲ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７の一つが、そしてＲ^１１がアリール基の場合はＲ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５の一つが、基−ＣＨ_２ＯＲ^１８を表し、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７の残りは互いに独立に、水素原子又は基−ＣＨ_２ＯＲ^１８を表す。ここで、Ｒ^１８は水素原子又はアルキル基を表す。〕

[Wherein R ¹¹ represents a group —NR ¹⁶ R ¹⁷ or an aryl group, and when R ¹¹ is a group —NR ¹⁶ R ¹⁷ , one of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ And when R ¹¹ is an aryl group, one of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represents the group —CH ₂ OR ¹⁸ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and The remainder of R ¹⁷ independently of one another represents a hydrogen atom or a group —CH ₂ OR ¹⁸ . Here, R ¹⁸ represents a hydrogen atom or an alkyl group. ]

Here, the aryl group of R ¹¹ is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl group and naphthyl group have substituents such as an alkyl group, an alkoxy group and a halogen. It may be bonded. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ¹⁸ is generally an alkyl group having 1 to 6 carbon atoms, particularly a methyl group or an ethyl group, particularly a methyl group.

  Among the compounds represented by the above formula (14), melamine compounds, that is, compounds represented by the following formula (15) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxy. Examples include methyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine and the like.

〔式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７は互いに独立に、水素原子又は基−ＣＨ_２ＯＲ^１８を表す。ここで、Ｒ^１８は水素原子又はアルキル基を表す。〕

Wherein ^{represents R 12, R 13, R 14} , R 15, R 16 and ^{R 17} independently of one another, a hydrogen atom or a group _-CH 2 ^{OR 18.} Here, R ¹⁸ represents a hydrogen atom or an alkyl group. ]

Among the compounds represented by formula (14), guanamine compounds, that is, compounds in which R ¹¹ in formula (14) is an aryl group include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, Tetraethoxymethylbenzoguanamine and the like are included.

Furthermore, the following compounds are also included in the crosslinking agent having a methylol group or a methylol alkyl ether group, and these can also be used.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.

  These crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.

<Ratio of component (A) and component (B) / content of other combined components>
In the photosensitive resin composition of the present invention, the blending ratio of the component (A) and the component (B) varies depending on the type of the component used, but is preferably the following blending ratio by weight.
When component (B) is a photopolymerization initiator such as oxime derivatives, component (A): component (B) is usually 99.9: 0.1-60: 40, preferably 99: 1-65: 35. When a resin other than component (A) is used in combination, (component (A) + resin other than component (A)): component (B) is 99.9: 0.1 to 65:35, preferably 99: 1 to 75:25. If the amount of the component (B) is too small, sufficient sensitivity may not be obtained. If the amount is too large, problems may occur in developability and storage stability.
When component (B) is a photoacid generator, component (A): component (B) is usually 97: 3 to 30:70, preferably 90:10 to 50:50. If the component (B) is too small, the effect may not be obtained, and if it is too large, the plate-making property may be lowered.

  When a photopolymerization initiator such as oxime derivatives and a photoacid generator are used in combination as component (B), component (A): component (B) is usually 99: 1 to 50:50, preferably 98: 2-60: 40. When a resin other than component (A) is used in combination, (component (A) + resin other than component (A)): component (B) is 99: 1 to 50:50, preferably 98: 2 60:40. If the amount of the component (B) is too small, sufficient sensitivity may not be obtained. If the amount is too large, problems may occur in developability, storage stability and plate making. In this case, the weight ratio of the photopolymerization initiator as the component (B) to the photoacid generator is as follows: photopolymerization initiator: photoacid generator = 99: 1 to 1:99, particularly 90:10 to 10 : 90 is preferable. If the amount of photopolymerization initiator is larger than this range and the amount of photoacid generator is small, the voltage holding ratio may be insufficient. If the amount of photopolymerization initiator is small and the amount of photoacid generator is large, sufficient sensitivity cannot be secured. there is a possibility.

When using a sensitizing dye, the content of the sensitizing dye in the photosensitive resin composition is 0.1 to 10% by weight, preferably 0.2 to 0.2%, based on the total solid content in the photosensitive resin composition. 5% by weight. If the amount of the sensitizing dye is less than this, the sensitizing effect is not obtained, and if it is too much, the developability may be lowered.
Moreover, when using a crosslinking agent, the quantity is 0.1-20 weight part with respect to 100 weight part of total solids of the photosensitive resin composition, Especially preferably, it is 1-10 weight part. If the amount of the cross-linking agent is less than this, the sensitivity is insufficient, or it is disadvantageous for electric characteristics, and if it is too much, the developability is deteriorated, the melt flow becomes difficult, and it may be disadvantageous for securing the shape. .

<Ingredient (C)>
The said photoinitiator is normally used with the ethylenically unsaturated compound which is a component (C). As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith. From the standpoint that the difference in solubility can be expanded, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group (meta ) Acrylate compounds are more preferred.

  Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.

  Typically, compounds having two or more ethylenically unsaturated bonds include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

Specific examples of esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
Reaction product of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; Examples of sugar alcohol include those described above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.

Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, etc.

  In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts These reactants can be mentioned. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate, tri (meth) acrylate, etc. of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.

  As the (meth) acryloyloxy group-containing phosphates, those represented by the following general formulas (5), (6) and (7) are preferable.

〔式（５）、（６）及び（７）中、Ｒ^１０は水素原子又はメチル基を示し、ｐ及びｐ’は１〜２５の整数、ｑは１、２、又は３である。〕

[In the formulas (5), (6) and (7), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3. ]

  As will be described later, these compounds are mainly used as a substrate adhesion enhancer, but since they have an ethylenically unsaturated bond in the molecule, they can also be used as an ethylenically unsaturated compound.

  Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, Examples include (meth) acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

Examples of urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate. ) Acrylate compound, aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tris Aromatic polyisocyanates such as isocyanate phenyl) thiophosphate, a reaction product of a polyisocyanate compound heterocyclic polyisocyanates such as isocyanurate.
Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

  Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol As a compound having two or more hydroxyl groups in one molecule, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, etc. manufactured by Asahi Kasei Corporation Biuret type, same A compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted. The compound obtained, or a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as Asahi Kasei Kogyo “Duranate ME20-100”, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. 1 or more hydroxyl groups and 2 in one molecule Above, can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.

  Examples of epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds such as, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds, etc. And a reaction product with a polyepoxy compound such as a heterocyclic polyepoxy compound such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.

  Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds whose crosslinking rate has been improved by sulfurizing the ether bonds of the ethylenically unsaturated compound with phosphorous pentasulfide and changing to thioether bonds, and for example, Japanese Patent No. 3164407 and JP-A-9- The polyfunctional (meth) acrylate compound and silica sol having a particle diameter of 5 to 30 nm (for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.)), methyl ethyl ketone-dispersed organosilica sol (Nissan Chemical) "MEK-S" ”), Methyl isobutyl ketone-dispersed organosilica sol (“ MIBK-ST ”manufactured by Nissan Chemical Co., Ltd.), etc.] and the like, and the like, and the like, by using an isocyanate group or a mercapto group-containing silane coupling agent. Examples thereof include compounds having improved strength and heat resistance as a cured product by reacting and bonding silica sol through a silane coupling agent.

  The above ethylenically unsaturated compounds may be used alone or in combination of two or more.

  In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Those having 5 or more functional groups are particularly preferred.

  When using the ethylenically unsaturated compound of component (C), the content of the ethylenically unsaturated compound in the photosensitive resin composition is 5 to 80% by weight based on the total solid content in the photosensitive resin composition. Preferably, it is 10 to 70% by weight. If the amount of the ethylenically unsaturated compound is less than this, sufficient sensitivity may not be ensured, and if it is too much, it may be difficult to form an appropriate shape.

<Board adhesion enhancer>
The photosensitive resin composition of the present invention preferably contains a substrate adhesion enhancer in order to sufficiently adhere fine lines and dots.
As the substrate adhesion enhancer, a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent or the like is preferable. Examples of the compound containing a nitrogen atom include diamines (described in JP-A No. 11-184080) Adhesion enhancers, others) and azoles are preferred. Among them, azoles are preferable, and in particular, imidazoles (adhesion enhancers described in JP-A-9-236923, etc.), benzimidazoles, benzotriazoles (adhesion enhancers described in JP-A-2000-171968, etc.). Are preferred, and imidazoles and benzimidazoles are most preferred. Among these, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve adhesion. -Aminoimidazole is preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferable.

  As the phosphoric acid group-containing compound, (meth) acryloyloxy group-containing phosphates that also function as an ethylenically unsaturated compound are preferable, and those represented by the following general formulas (5), (6), and (7) are preferable. .

〔式（５）、（６）及び（７）中、Ｒ^１０は水素原子又はメチル基を示し、ｐ及びｐ’は１〜２５の整数、ｑは１、２、又は３である。〕

[In the formulas (5), (6) and (7), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3. ]

  Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4, and specific examples thereof include (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, Examples include (meth) acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

  Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.

  When these substrate adhesion enhancers are blended, the blending ratio varies depending on the type of substrate adhesion enhancer used, but is 0.05 to 10% by weight, particularly 0, based on the total solid content of the photosensitive resin composition. It is preferable to set it as 5 to 5 weight%.

<Color material>
The photosensitive resin composition of the present invention may contain a coloring material such as a pigment. In that case, the resin of the component (A) according to the present invention can also function as a dispersion resin. That is, the photosensitive resin composition of the present invention may contain an ink using a resin having a carboxyl group and / or a hydroxyl group represented by the formula (1) as a pigment dispersion resin.
In that case, as the resin of the component (A), one having an acid value of 100 to 200 mg-KOH / g is particularly preferable in terms of dispersibility.
The dispersion resin is not limited to the resin of the component (A), and can be appropriately used as necessary.

  When the coloring material such as a pigment is mixed and used in the photosensitive resin composition of the present invention, the pigment includes various pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment. Colors of pigments can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. And CI pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  The black color material may be a single black color material, or may be a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  Among these, carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

  Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, C lor Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

  Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

  As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

  These various pigments can also be used in combination of, for example, chromaticity adjustment.

  The average particle size of these various inorganic and organic pigments is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

  Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  The use of the coloring material in the photosensitive resin composition of the present invention is for ribs (light-shielding ribs) of large-screen high-definition televisions that mainly require contrast, and when the spacers are formed together with the ribs, It will also be used for spacers. In addition, for example, when the composition of the present invention is used for a pixel layer or a black matrix depending on the cell configuration, a color material is usually used.

  In the case of using a color material, the ratio of the color material such as a pigment can be selected in the range of 1 to 50% by weight in the total solid content of the photosensitive resin composition. In this range, 10 to 40% by weight is more preferable, and 20 to 40% by weight is particularly preferable. If the proportion of the color material is too small, the required light shielding properties cannot be ensured in the case of a light shielding rib or the like. Conversely, if the proportion of the color material is too large, a sufficient rib shape may not be obtained.

  In addition, when the photosensitive resin composition of this invention contains a pigment, you may add a pigment derivative etc. for the improvement of the dispersibility of a pigment, and the improvement of dispersion stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable, among which quinophthalone is preferable. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These pigment derivatives can be used alone or in combination of two or more.

  The addition amount of the pigment derivative is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, still more preferably 0.1 to 5% by weight based on the pigment. % Or less.

  When the photosensitive resin composition of the present invention contains a pigment, it is preferable to use a pigment dispersant and / or a dispersion aid together in order to improve the dispersibility and dispersion stability of the pigment. Among them, it is particularly preferable to use a polymer dispersant as the pigment dispersant because it is excellent in dispersion stability with time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. And the like, and the like. Specific examples of such a dispersant are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol) , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These dispersants can be used singly or in combination of two or more.

  The content of the pigment dispersant and / or the dispersion aid is usually 50% by weight or less, preferably 30% by weight or less in the total solid content of the photosensitive resin composition.

<Other ingredients>
Although it will not specifically limit if the photosensitive resin composition of this invention contains the photoinitiator and / or photoacid generator of said resin (A) and (B) as a structural component, It mentions above. In addition to the above components, a surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, a development improver and the like may be further contained.

Various types of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but nonionic surfactants are used because they are unlikely to adversely affect various properties. It is preferable to use it.
The blending ratio of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, and more preferably 0.01 to 0. 0% with respect to the total solid content in the photosensitive resin composition. It is in the range of 5% by weight, most preferably 0.03-0.3% by weight.

As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used.
The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight with respect to the total solid content in the photosensitive resin composition.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin.
The blending ratio of these plasticizers is preferably in the range of 5% by weight or less with respect to the total solid content in the photosensitive resin composition.

<Solvent>
Each component contained in the above-described photosensitive resin composition of the present invention is usually dissolved or dispersed in a solvent and referred to as a photosensitive resin composition solution (hereinafter referred to as “photosensitive resin composition solution of the present invention”). May be used).

  Examples of the solvent used here include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropion Acid, 3-e Methyl toxipropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, Examples include butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate. These solvents may be used alone or in combination of two or more.

  In the photosensitive resin composition solution of the present invention, the content of the solvent is 90% by weight or less, 60% by weight or more, particularly 70% by weight or more, from the viewpoint of easy application during coating film formation and film thickness control. It is preferable that

[Use of photosensitive resin composition of the present invention]
A voltage is applied to the liquid crystal layer by ON / OFF of an applied signal, and it is required to hold the applied voltage until the next writing. This voltage holding capability is generally expressed as a voltage holding rate. However, when there is a problem with the voltage holding capability of the liquid crystal layer, display failure such as flickering occurs in the displayed image.
In general, the deterioration of the voltage holding ratio is caused by the entry of mobile ions into the liquid crystal layer or the low resistance of the members surrounding the liquid crystal layer. A particularly severe electrical property is required for a contact or extremely adjacent member.

Since the photosensitive resin composition of the present invention has excellent electrical characteristics, it is useful as a material for forming a member positioned between electrodes.
Here, the electrodes are a pair of electrodes for applying a voltage to the liquid crystal, and “between the electrodes” in the present invention means between the pair of electrodes.

  Examples of the general configuration of the liquid crystal display device include those shown in FIG. 1 as described in detail later, and the photosensitive resin composition of the present invention can be used as a member positioned between electrodes, for example, It is preferably used for forming liquid crystal alignment control protrusions (ribs), spacers, overcoats and the like. In addition, the liquid crystal display device may have a configuration in which a pixel layer, a black matrix, or the like is formed on an electrode. In that case, the composition of the present invention can also be used to form a pixel layer or a black matrix.

[Liquid Crystal Display (Panel)]
Below, the method to manufacture a liquid crystal display device (panel) using the photosensitive resin composition of this invention is demonstrated.

  In a typical configuration of a liquid crystal display device, for example, a pixel layer is formed on a substrate such as a glass plate, the pixel layer is covered with an overcoat layer as necessary, a transparent electrode is applied, and liquid crystal alignment is performed as necessary. After forming control protrusions (ribs) and spacers, and further forming an alignment film, a cell is formed by bonding to a counter substrate, liquid crystal is injected into the formed cell, and the counter electrode is connected.

  FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of such a liquid crystal display device, in which 1 is a glass plate, 2 is a black matrix, and 3 is a pixel layer (green filter, blue filter, red). Filter), 4 is an overcoat layer, 5 is an ITO transparent electrode, 6 is an alignment film, 7 is a liquid crystal alignment control protrusion (rib), 8 is a spacer, 9 is a liquid crystal, 10 is an insulating film, and 11 is a TFT.

  In such a liquid crystal display device, liquid crystal alignment control protrusions (ribs) and / or spacers can be formed using the photosensitive resin composition of the present invention. In the case where a bead type spacer is used as the spacer, it is applied at the time of liquid crystal injection after forming the alignment film. Here, the alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and a curing process is performed by thermal baking. The thickness of the alignment film is usually several tens of nm.

  Formation of the liquid crystal alignment control protrusion (rib) using the photosensitive resin composition of the present invention is performed, for example, as follows.

  In forming the liquid crystal alignment control protrusion (rib), first, a black matrix obtained by a method described in JP-A-2003-33011 and the like, and a red, blue, and green pixel layer (a color filter in a narrow sense) are provided. Further, an electrode, for example, a 150 nm thick ITO is deposited (the electrode is not limited thereto), and a transparent substrate having a thickness of usually 0.1 to 2 mm is prepared. The resin composition solution is applied, then dried and then image-exposed.

  In addition, the spacer is formed in the same manner as the rib formation, for example, by the method described in JP-A-2007-119718.

  The above-described photosensitive resin composition solution of the present invention can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering to the spin coating method, and the generation of foreign matter is suppressed. To preferred.

  The coating film after the photosensitive resin composition solution is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying conditions are usually selected in the range of 15 to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

  The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

  Image exposure is performed by superimposing a matrix pattern on the coating film of the photosensitive resin composition of the present invention and irradiating an ultraviolet light source or a visible light source through this matrix risk pattern. Examples of the light source used for the above image exposure include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a lamp light source such as a carbon arc, a fluorescent lamp, Examples thereof include laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When irradiating and using light of a specific wavelength, an optical filter can be used.

  After the exposure, an unexposed uncured portion is removed by development to form an image. Development can be performed using an aqueous solution of an alkaline compound that may contain an organic solvent or a surfactant. This developer may contain a buffering agent and a complexing agent.

  Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, phosphorus Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or Such as trimethylamine, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be used as a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzenes. Examples thereof include anionic surfactants such as sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate salts, and amphoteric surfactants such as alkylbetaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used by mixing with water.

  The temperature of development processing is 10-50 degreeC normally, Preferably it is 15-45 degreeC, More preferably, it is 20-40 degreeC. Further, the developing method may be any of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like. Usually, an image obtained after development is required to have a fine line reproducibility with a width of 5 to 20 μm, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display.

  The photosensitive resin composition of the present invention is usually 150 ° C. or higher for the purpose of obtaining necessary shapes such as liquid crystal alignment control protrusions, spacers, and overcoats after development, and obtaining sufficient electrical reliability. , Preferably 180 ° C. or higher, more preferably 200 ° C. or higher, usually 400 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and usually 10 minutes or longer, preferably 15 minutes or longer, more preferably 20 The heat treatment is performed for at least minutes, usually at most 120 minutes, preferably at most 60 minutes, more preferably at most 40 minutes.

The liquid crystal alignment control protrusion formed as described above has an arch shape with a bottom width of usually 0.5 to 20 μm, preferably 3 to 17 μm, and a height of usually 0.2 to 5 μm, preferably 0.5 to 3 μm. The dome shape is preferable, and the angle with the substrate surface is usually 10 to 40 °, preferably 15 to 35 °. Meanwhile, the spacer height is usually 0.5 to 10 [mu] m, preferably 1 to 9 m, the bottom area is usually 10 to 300 [mu] m ^2, preferably columnar shape of 40 to 200 [mu] m ^2, the angle between the substrate surface normal 15 It is -110 degrees, Preferably it is 20-90 degrees.

  Even if the overcoat is applied on a pixel layer having a step, the surface is preferably smooth.

  In the case of batch formation in which the liquid crystal alignment control protrusions and spacers are simultaneously formed with the same photosensitive resin composition, it is necessary to form different heights with a single coating (with the same coating film thickness). is there. For this purpose, various methods as proposed so far can be used. For example, a photomask used for exposure has a pattern with different transmittance and transmission wavelength, a step in exposure illuminance is made by adjusting the opening width of the mask, exposure is performed from both front and back, and a mask with different patterns multiple times The method of exposing using, etc. is mentioned.

  Further, the liquid crystal alignment control protrusions (ribs) and spacers thus obtained may be transparent or colored depending on the application, but when high contrast is required, the ribs are preferably shielded from light. . When such a light-shielding rib is formed, a coloring material such as the aforementioned pigment is mixed with the photosensitive resin composition.

On the other hand, as the spacer of the liquid crystal display device, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and usually a spacer of 2 to 8 μm is preferable.
In recent years, the use of a photo spacer formed by a photolithographic method using a photosensitive resin composition has increased, but this spacer (photo spacer) and rib are formed of the same photosensitive resin composition, By forming them simultaneously at the same time, significant rationalization of materials and processes (processing time and place) can be expected. The photosensitive resin composition of the present invention is also in view of it, and in particular, since the spacer is required to have compression characteristics, it is necessary to control the double bond equivalent when the resin itself is formed or formed by photopolymerization. It becomes. In that case, for example, a design in which an ethylenically unsaturated group and a highly elastic group are introduced into Y of the group X represented by the formulas (1) and (10) of the resin represented by the formula (1). It becomes possible.

As the counter substrate of the liquid crystal display device, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable. The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed. The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  When the photosensitive resin composition of the present invention is used for a rib application, the rib is used for an MVA method using a vertical alignment type liquid crystal, but the type of liquid crystal is not particularly limited, and an aromatic type, Conventionally known liquid crystals such as aliphatic and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
The structural components of the photosensitive resin compositions used in the following examples and comparative examples are as follows.

<Photopolymerization initiator>

<Photo acid generator>

<Board adhesion enhancer>

<Crosslinking agent>

<Ink-1>
A reaction vessel was charged with 35 parts by weight of propylene glycol monomethyl ether acetate, 8.8 parts by weight of 1-methoxy-2-propanol, and 1.5 parts by weight of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.). In a nitrogen atmosphere, the temperature was raised to 80 ° C., 10.5 parts by weight of benzyl methacrylate, 7.5 parts by weight of methyl methacrylate, and 11.9 parts by weight of methacrylic acid were added dropwise over 2 hours, and further 4 hours. Stirring was performed to obtain Dispersing Resin-1. The average molecular weight (Mw) by GPC of Dispersing Resin-1 was 12000 in terms of polystyrene, and neutralization titration with KOH gave an acid value of 120 mg-KOH / g.
Next, C.I. I. Pigment Red 254, 52 parts by weight, C.I. I. Pigment Blue 156, 37 parts by weight, C.I. I. 11 parts by weight of Pigment Violet 23, 25 parts by weight of a dispersant “DisperBYK-161” (manufactured by Big Chemie), 30 parts by weight of the above-mentioned Dispersing Resin-1 in solids, and a dispersant of propylene glycol monomethyl ether acetate And 620 parts by weight including those derived from the dispersion resin. Here, zirconia beads (0.5 mm diameter) of 3 times the total weight were mixed, filled in a stainless steel container, and dispersed for 6 hours with a paint shaker to prepare ink-1.

<Resin-1>
“CCR-1171H” manufactured by Nippon Kayaku Co., Ltd. (Mw = 4000 to 5000, acid value = 100 mg-KOH / g)

<Synthesis of Resin-2>
120 g of m-cresol novolak resin having an Mw of 4000 and 71 g of glycidyl methacrylate were dissolved in 191 g of propylene glycol monomethyl ether acetate, 0.19 g of paramethoxyphenol and 1.9 g of tetraethylammonium chloride were added, and the mixture was reacted at 90 ° C. for 13 hours. After confirming that the glycidyl methacrylate was 1% or less by gas chromatographic analysis, 45.6 g of tetrahydrophthalic anhydride and 45.6 g of propylene glycol monomethyl ether acetate were added, and the mixture was further reacted at 95 ° C. for 5 hours. It was confirmed by IR that there was no acid anhydride, and a resin-2 solution was obtained. The Mw of this resin was 7500.

<Synthesis of Resin-3>
284 g of m / p-cresol novolak resin (m / p = 6/4, Mw = 4000) and 205.7 g of propylene glycol monomethyl ether acetate were placed in a reaction vessel and dissolved at 100 ° C. in a nitrogen atmosphere. Subsequently, 47.3 g of succinic anhydride and 7.1 g of diethylaniline were added and reacted at 100 ° C. for 10 hours. After confirming that succinic anhydride disappeared by FT-IR, the reaction was completed. To this, 440 g of propylene glycol monomethyl ether acetate was added, and the reaction solution was cooled. Mw of the obtained resin was 4000.

<Resin-4>
m / p-cresol novolak resin (m / p = 6/4, Mw = 5000)

<Synthesis of Resin-5>
A reaction vessel was charged with 130 parts by weight of propylene glycol monomethyl ether acetate and heated to 90 ° C. While maintaining the container temperature at 90 ° C. with stirring, 5 parts by weight of styrene, 32 parts by weight of tricyclodecanyl methacrylate, 42 parts by weight of glycidyl methacrylate, 7 parts by weight of 2,2′-azobisisobutyronitrile, propylene glycol A mixed solution of 20 parts by weight of monomethyl ether acetate was added dropwise over 3 hours. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the internal temperature of the reaction vessel at 90 ° C, and then reacted at 110 ° C for 1 hour. Next, the internal temperature of the reaction vessel is lowered to 90 ° C., 0.05 part by weight of paramethoxyphenol and 1 part by weight of tetraethylammonium chloride are added, and 21 parts by weight of acrylic acid is added dropwise over 30 minutes. The reaction was continued until the value was 3 mg-KOH / g or less. Next, 8.7 parts by weight of 1,2,3,6-tetrahydrophthalic acid was added and reacted at 90 ° C. for 4 hours to obtain a resin solution. Mw of this resin was 8000, and the acid value was 30 mg-KOH / g.

<Resin-6>
ZAR-1035 manufactured by Nippon Kayaku Co., Ltd. (Special bis A-type acid-modified epoxy acrylate resin Mw = 13,000, acid value = 101 mg-KOH / g)

<Synthesis of Resin-7>
In a reaction vessel, 230 parts by weight of an epoxy resin (Nippon Kayaku Co., Ltd. NC-7000H, epoxy equivalent 230) 230 parts by weight, 86 parts by weight of methacrylic acid, 3 parts by weight of tetraethylammonium chloride, 316 parts by weight of propylene glycol monomethyl ether acetate And dissolved. The internal temperature of the reaction vessel was raised to 90 ° C., and the reaction was carried out at 90 ° C. until the acid value of the solution became 2 mg-KOH / g or less. Next, 117 parts by weight of 1,2,3,6-tetrahydrophthalic acid was added and reacted at 90 ° C. for 4 hours to obtain a resin solution. This resin was represented by the following structural formula, Mw was 2000, and the acid value was 100 mg-KOH / g.

<Ethylenically unsaturated compound>

<Surfactant>
"Megafuck F-475" made by DIC

<Solvent>
Propylene glycol monomethyl ether acetate (PGMEA)

[Examples 1 to 4, Comparative Examples 1 to 6]
The components shown in Table 1 are mixed well in the formulation shown in Table 1, photosensitive resin composition solutions 1 to 10 are prepared, voltage holding ratio (VHR) and shape are evaluated by the following methods, and the results are obtained. It is shown in Table 1.

<Evaluation of voltage holding ratio (VHR)>
An electrode substrate A in which an ITO film is formed on one entire surface of a 2.5 cm square alkali-free glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.) and a 2 mm width at the center of one surface of the 2.5 cm square glass substrate. An electrode substrate B on which a 1 cm square ITO film with a lead-out electrode connected was prepared.
Each photosensitive resin composition solution was applied onto the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked on a hot plate at 80 ° C. for 3 minutes to obtain a coating film having a dry film thickness of 1.8 μm. Thereafter, the entire surface was subjected to image exposure using 3 kW high-pressure mercury under exposure conditions of 80 mJ / cm ² . Next, 0.16% by weight sodium carbonate, 0.046% by weight sodium hydrogen carbonate, 0.4% by weight nonionic surfactant (“Adecatol PC-8” manufactured by Adeka), and 0.1% by weight Using a developer composed of an aqueous solution containing 1% propylene glycol, after performing shower development at 26 ° C. with a water pressure of 0.1 MPa, the development was stopped with pure water and rinsed with a water spray. The development time was determined by measuring the time (break time) required to remove the coating film of the sample that was not exposed and multiplying that time by 1.2. The thus-formed glass substrate was post-baked at 230 ° C. for 30 minutes to obtain a glass substrate having a thermosetting film on the entire surface.
On the other hand, after applying an epoxy resin sealant containing silica beads having a diameter of 5 μm on the outer periphery of the electrode substrate B using a dispenser, the surface of the electrode substrate A on which each photosensitive resin composition solution was applied The outer edge portions were arranged so as to be shifted by 3 mm, and heated at 180 ° C. for 2 hours in a hot air circulating furnace while being crimped.
Liquid crystal (MLC-6846-000 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the periphery was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.
After annealing the liquid crystal cell (heating at 105 ° C. for 2.5 hours in a hot air circulating furnace), a pulse voltage having the frequency shown in Table 1 is applied to the electrode substrates A and B at a voltage of 5 V and an application time of 16.67 msec, The voltage was applied under the condition of a span of 500 msec, and the voltage holding ratio was measured with “VHR-1” manufactured by Toyo Corporation.

<Evaluation of shape>
Each photosensitive resin composition solution was applied onto an electrode substrate C on which an ITO film was formed on one whole surface of a 5 cm square alkali-free glass substrate (AN-100 manufactured by Asahi Glass Co., Ltd.), and after vacuum drying for 1 minute, Prebaking was performed at 80 ° C. for 3 minutes on a hot plate to obtain a coating film having a dry film thickness of 1.8 μm. Thereafter, the entire surface was subjected to image exposure with 3 kW high-pressure mercury under an exposure condition of 80 mJ / cm ² using a mask having lines with opening widths of 5, 6, 7, 8, 9, 10, 11, and 12 μm. did. Next, development processing and post-baking were performed under the same conditions as in the evaluation of the VHR to obtain a glass substrate on which a resist was applied in a line shape. The line width of the resist on the glass substrate was measured with an optical microscope, the cross-sectional shape of the line was observed with an SEM for each sample having a line width closest to 10 μm, and the evaluation results are shown in Table 1. .
In addition, the evaluation of the shape was ◯ for an arch shape with a smooth line, and “X” for a flat, rounded, or loose surface.

  From Table 1, it can be seen that the resist layer formed using the photosensitive resin composition of the present invention has almost no adverse effect on the voltage holding ratio of the liquid crystal even in the state where the liquid crystal is in direct contact. In addition, since it has an appropriate melt flow, it can be a composition that is very suitable for forming ribs that require a smooth shape without corners and an overcoat that needs to make the underlying unevenness smooth. I understand.

It is typical sectional drawing which shows an example of the laminated constitution of a liquid crystal display device.

Explanation of symbols

1 Glass plate 2 Black matrix 3 Pixel layer (green filter, blue filter, red filter)
4 Overcoat layer 5 ITO transparent electrode 6 Alignment film 7 Liquid crystal alignment control protrusion (rib)
8 Spacer 9 Liquid crystal 10 Insulating film 11 TFT

Claims (14)

A photosensitive resin composition constituting a member located between electrodes in a color liquid crystal display device, comprising the following component (A) and component (B).
(A) Resin having a carboxyl group and / or a hydroxyl group represented by the following formula (1) (B) Photopolymerization initiator and / or photoacid generator

[In Formula (1), X is a hydrocarbon group which has a hydrogen atom or a carboxyl group and / or a hydroxyl group, and may have another substituent, and a plurality of X are the same as each other. Or may be different, except when all X are hydrogen atoms.
W is a divalent linking group represented by the following formula (8).
P represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and a plurality of P may be the same as or different from each other.
n represents an average value and is 1 to 200.

(In Formula (8), U and V are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group, or a heterocyclic compound which may have a substituent. Represents a group.)] X in the formula (1) is selected from the following formulas (9), (10), and (11), and is represented by the formulas (9), (10), and (11) included in the resin of the component (A). And a, b, c are each independently 0-150, and a + b + c is 3-200, wherein the average value of the content of each group is a, b, c. 2. The photosensitive resin composition according to 1.

[In the formulas (9) and (10), Y is a hydrogen atom or a hydrocarbon group which may have a substituent and may contain an unsaturated group, and in the resin of the component (A) The plurality of Y included may be the same as or different from each other. In formula (9), Z is a divalent hydrocarbon group (linking group) which may have a substituent, and a plurality of Z contained in the resin of component (A) may be the same as each other It may be good or different.
In the above formulas (9), (10), and (11), (*) represents a bonding site to the ether group in the formula (1). ] The formulas (9) and (10) are represented by the following formulas (12) and (13), respectively, and further contain an ethylenically unsaturated compound as the component (C). Photosensitive resin composition.

[In Formula (12) and (13), Q is a hydrogen atom or a methyl group.
Z has the same meaning as in formula (9).
In the above formulas (12) and (13), (*) represents the binding site to the ether group in formula (1). ]   c / (a + b) is 0.2-9, The photosensitive resin composition of Claim 2 or 3 characterized by the above-mentioned.   The photosensitive resin composition according to claim 1, further comprising a pigment.   The photosensitive resin composition according to any one of claims 1 to 5, further comprising a substrate adhesion enhancer.   Component (B) contains oxime derivatives, The photosensitive resin composition of any one of Claim 1 thru | or 6 characterized by the above-mentioned.   The photosensitive resin composition according to claim 1, further comprising a crosslinking agent.   The photosensitive resin composition according to any one of claims 1 to 8, wherein the resin contains a novolak resin and / or a hydroxystyrene resin in addition to the component (A).   10. The color liquid crystal display device according to claim 1, wherein the members positioned between the electrodes are liquid crystal alignment control protrusions and spacers, and are used to form these simultaneously. Photosensitive resin composition.   Liquid crystal alignment control protrusion formed using the photosensitive resin composition of any one of Claims 1 thru | or 10.   The spacer formed using the photosensitive resin composition of any one of Claim 1 thru | or 10.   A color filter comprising a member formed using the photosensitive resin composition according to claim 1 between electrodes.   An image display device comprising a color filter having a member formed using the photosensitive resin composition according to any one of claims 1 to 10 between electrodes.

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