JP2007065640A - Photocurable composition and photospacer for liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable composition which has high sensitivity and high solubility, suppresses occurrence of residue on development, reduces image thickening, and allows reproduction of a desired image pattern. <P>SOLUTION: The photocurable composition contains an alkali-soluble resin, a photopolymerizable compound, a trihalomethane triazine compound and a coumarin-based ultraviolet absorber, wherein at least one of the alkali-soluble resin and the photopolymerizable compound has an alkylene oxide chain. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photocurable composition and a photospacer for a liquid crystal display device, and more particularly, light suitable for forming a structure such as a photospacer for regulating the cell thickness of a cell in which liquid crystal is provided between substrates. The present invention relates to a curable composition and a photospacer for a liquid crystal display device using the same.

  Conventionally, a liquid crystal display (LCD) has been widely used for display devices that display high-quality images. In general, a liquid crystal display device is provided with a liquid crystal layer capable of displaying an image with a predetermined orientation between a pair of substrates, and maintaining the distance between the substrates, that is, the thickness of the liquid crystal layer, determines the image quality. Therefore, a spacer for maintaining a constant thickness is provided. The thickness between the substrates is generally referred to as “cell thickness”, and the cell thickness usually indicates the thickness of the liquid crystal layer, that is, the distance between two electrodes applying an electric field to the liquid crystal in the display area. It is.

  As the spacer, resin fine particles having a particle size of about 5 μm in diameter are used for a long time, and this is dispersed between electrodes to form a spacer (called a ball spacer or pearl material). It was. However, in recent years, the ball spacer using the fine particles cannot specify the spraying position, and the particles are present on the colored pixels constituting the color filter, contributing to pixel defects, Since the spraying position is not fixed, there is a particular problem such as uneven distribution on the screen as the screen becomes larger.

  In recent years, a spacer formed using a photosensitive resin composition called a photospacer has become mainstream. The photo spacer is formed by optically patterning the surface shape of the spacer by a photolithography method using a photosensitive resin composition, and has an advantage that the formation position can be specified with respect to the ball spacer. That is, it can be selectively formed at a position overlapping with the black stripe and can be configured so as not to hinder the image quality.

  On the other hand, in recent liquid crystal display devices, in order to improve the display speed, it has been attempted to improve the response speed of the liquid crystal itself and reduce the distance between opposing electrodes, that is, the cell thickness. The cell thickness has been about 5 μm in the past, but recently, it has been formed into a thin form of 2 μm or less.

  The spacer is formed by, for example, applying a photosensitive resin composition for forming a spacer on a substrate having an electrode (the surface on which the photo spacer is in direct contact is a flattened film, a transparent electrode, or an alignment film). It can be performed by drying to form a resin film, placing an exposure mask above the formed resin film, exposing in a pattern, and developing. In this case, it is difficult to avoid the influence of lateral propagation of light in the film during exposure while maintaining good exposure sensitivity. In addition, if the solubility during development processing is poor, a development residue will be formed and high-resolution pattern formation will not be possible. As a way to improve solubility during development, acidic groups (such as carboxyl groups) are introduced. A method has been proposed.

In relation to the formation of the above-mentioned photospacer, there is a disclosure relating to a photocurable composition containing an alkali-soluble resin having an alkylene oxide chain and a polymerizable double bond, which is said to be excellent in photocurability and developability. (For example, refer to Patent Document 1). Further, a resin composition for spacers containing a resin having an allyl group as a binder is disclosed, and it is said that the compressive strength is strong and plastic deformation hardly occurs during panel formation (see, for example, Patent Document 2). Further, in relation to the above, a single spacer at a sealing temperature at the time of liquid crystal preparation is provided for a spacer resin composition for forming a spacer pixel pattern disposed on a substrate in order to keep the thickness of the liquid crystal layer constant. There is a disclosure relating to a technique for setting the amount of plastic deformation with respect to a load of 1 gf to 0.03 to 0.3 μm (see, for example, Patent Document 3).
JP 2004-109989 A JP 2003-207787 A JP 2003-302039 A

  However, when the thickness of the resin film for constituting the spacer is reduced, it is inevitably affected by the propagation of light in the lateral direction in the resin film, and the shape according to the mask pattern shape is not formed. In other words, only a thicker line pattern can be obtained. That is, the irradiated light spreads further in the lateral direction from the opening end of the mask, and as a result of causing multiple reflections between the light mask and the resin film, a curing reaction proceeds in the lateral direction from the opening end of the mask, The mask pattern becomes thicker and larger than the intended thickness and size.

  In addition, by introducing acidic groups as described above, it is not always possible to ensure sufficient solubility, but conversely, by introducing acidic groups, development residues on a flattened film, a transparent electrode, an alignment film, etc. There is a problem that it tends to be.

  The present invention has been made in view of the above, and has a high sensitivity, a high solubility, a small amount of development residue, a photocurable composition that can reproduce an intended image pattern by reducing image thickness. Another object of the present invention is to provide a spacer for a liquid crystal display device in which variation in the shape of the pattern is suppressed to be small and uniform in shape, and to achieve the object.

Specific means for achieving the above object are as follows.
<1> In a photocurable composition containing an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, the photopolymerization initiator is a trihalomethane triazine compound, and further includes a coumarin ultraviolet absorber. The photocurable composition is characterized in that at least one of the alkali-soluble resin and the photopolymerizable compound has an alkylene oxide chain.

  <2> The photocurable composition according to <1>, wherein the coumarin ultraviolet absorber is a compound represented by the following general formula (I).

In the general formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Represents. X represents a hydrogen atom, a halogen atom, or an alkyl oxide group. n represents an integer of 0 to 4.

  <3> The above-mentioned <1> or <2>, wherein the trihalomethanetriazine compound is at least one selected from the group consisting of compounds represented by any one of the following general formulas (II) to (V). It is a photocurable composition.

In the general formula (II), R ⁴ represents a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R ⁵ and R ⁶ each independently represent a -CH ₂ COOR ^7, R ⁷ represents a hydrocarbon group having 1 to 4 carbon atoms. n represents an integer of 0 to 4. X represents a halogen atom.

In the general formula (III), R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, or a hydrocarbon group having 1 to 4 carbon atoms. X represents a halogen atom.

In the general formula (IV), R ¹⁰ represents a halogen atom or an alkoxy group, and X represents a halogen atom. n represents an integer of 0 to 4.

In the general formula (V), R ¹¹ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and R ¹² and R ¹³ each independently represent a halogen atom, a hydroxyl group, an alkoxy group, or 1 to 3 carbon atoms. Represents a hydrocarbon group. X represents a halogen atom. n represents an integer of 0 to 4.

<4> The alkali-soluble resin is the photocurable composition according to any one of <1> to <3>, wherein the side chain in the molecule has a polymerizable unsaturated group.
<5> Any of the above <1> to <4>, wherein the photopolymerizable compound is at least one selected from the group consisting of compounds represented by any one of the following general formulas (VI) to (VIII): It is a photocurable composition as described in one.

In the general formula (VI), R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group. m represents an integer of 2 to 6, n represents an integer of 1 to 3, and a and b satisfy a + b = 3.

In the general formula (VII), R ²³ , R ²⁴ , and R ²⁵ each independently represent a hydrogen atom or a methyl group. s, t, and u each independently represent 2 or 3, and p, q, and r satisfy 1 ≦ p + q + r ≦ 3.

  In the general formula (VIII), R represents a hydrogen atom or a methyl group. w represents an integer of 2 to 6, x represents an integer of 1 to 3, y represents an integer of 2 to 4, and z represents an integer of 0 to 2.

<6> A photospacer for a liquid crystal display device comprising the photocurable composition according to any one of <1> to <5>.
<7> A photospacer for a liquid crystal display device for regulating a cell thickness between substrates provided to sandwich a liquid crystal, wherein the cell thickness is 3 μm or less. Photo spacer.

  According to the present invention, a photocurable composition that has high sensitivity, high solubility, little development residue, can reduce image thickness, and can reproduce an intended image pattern, and pattern shape variation A spacer for a liquid crystal display device that is suppressed to a small size and has a uniform shape can be provided.

  Hereinafter, the photocurable composition of the present invention will be described in detail, and the liquid crystal display spacer of the present invention will be described in detail through the description.

The photocurable composition of the present invention has a configuration using an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and further contains a coumarin-based ultraviolet absorber, and the photopolymerization start. A trihalomethane triazine compound is used as an agent, and at least one of the alkali-soluble resin and the photopolymerizable compound has an alkylene oxide chain.
Hereinafter, each component which comprises the photocurable composition of this invention is explained in full detail.

-Alkali-soluble resin-
The photocurable composition of the present invention contains at least one alkali-soluble resin. This alkali-soluble resin is a binder component containing an alkylene oxide chain, if necessary, when the photopolymerizable compound described later does not contain an alkylene oxide chain, and when it contains an alkylene oxide chain, and is unexposed during development. This is effective for forming a sharp pattern in which the solubility of the portion in the developer is enhanced and development residues are prevented.

  As the alkali-soluble resin according to the present invention, those having an acidic functional group having alkali developability (for example, carboxyl group, phenolic hydroxyl group, etc.) are suitable.

  As a specific example, a linear organic polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. In addition, a polymer having a hydroxyl group with an acid anhydride added, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.

The alkali-soluble resin may be copolymerized with a hydrophilic monomer. Examples of the monomer include hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, 2 Tertiary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, Examples thereof include branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.
As other hydrophilic monomers, tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salts, monomers containing morpholinoethyl group, etc. are also useful. is there.

In the present invention, a polymer having a molecular chain having a polymerizable unsaturated group (polymerizable double bond) in the molecule is particularly suitable. The polymer containing a molecular chain having a polymerizable double bond in the molecule can be used as long as it is alkali-soluble and has a polymerizable unsaturated group such as an ethylenically unsaturated bond. Examples thereof include a polymer having a polymerizable unsaturated group.
As the polymerizable unsaturated group, for example, an acryloyl group, a methacryloyl group, and an allyl group are preferable, and those having a polymerizable unsaturated group in the side chain in the molecule are particularly preferable.

In this case, the proportion of the “polymer containing a molecular chain having an unsaturated group in the molecule” in the total amount of the alkali-soluble resin is preferably 10% by mass or more, more preferably 20% by mass or more, and 30 A mass% or more is particularly preferred. If the ratio is less than 10% by mass, the pixel pattern profile may deviate from the rectangle.
Moreover, as an equivalent of the unsaturated group which occupies in alkali-soluble resin, the inside of the range of 0.1-5.0 meq / gr is preferable, and the inside of the range of 0.5-3.0 meq / gr is more preferable.

  Among the above, as the alkali-soluble resin according to the present invention, at least one kind of co-polymer selected from the compound (1-1), the compound (1-2), and the compound (1-3) containing the following structural units: It is preferably a coalescence.

Compound (1-1): The following structural units (a1), (a2), (b1), (b2), (c1), and (d)
Compound (1-2): The following structural units (a1), (a2), (b1), (b2), (c2), and (d)
Compound (1-3): Structural units (a1), (a2), (b1), (b2), (c3), (c4), and (d) below

The constituent ratios of the respective structural units in the compounds (1-1) to (1-3) are molar ratios, and a1 and a2 are 10 to 70% in total, and b1 and b2 are 5 to 40% in total. , C1 is 5 to 40%, c2 is 5 to 40%, c3 and c4 are 5 to 40% in total, and d is 5 to 30%. R represents a hydrogen atom or a methyl group, and R ¹ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, a “phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxyl group”, 7 carbon atoms. Represents an aryl group having 12 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and R ² and R ⁴ are each independently an alkylene group having 1 to 18 carbon atoms, “an alkyl group having 1 to 4 carbon atoms as a substituent Or a carbamate having an alicyclic group having ³ to 18 carbon atoms, R ³ represents a linear or branched alkylene group having 2 to 16 carbon atoms, and R ⁵ is Represents an alkyl group having 1 to 4 carbon atoms. X represents a group selected from the following structural formulas (1) to (9). l represents an integer of 2 to 30, m represents an integer of 0 or 1 to 20, and n represents an integer of 2 to 20.

  Regarding the compound (1-1), the compound (1-2), and the compound (1-3), part of the structural units (a1), (a2), (b1), (b2), and (d) ) Is subjected to an addition reaction after copolymerization to complete a part of the structural unit (b2) as structural units (c1) to (c4).

  For example, in the case of the compound (1-1), after synthesizing the copolymers of the structural units (a1), (a2), (b1), (b2), and (d), the structural unit ( It can be obtained by adding an acrylate compound having an isocyanate group to a part of the component b2).

  In the case of the compound (1-2), after synthesizing the copolymers of the structural units (a1), (a2), (b1), (b2), and (d), the structural unit ( It can be obtained by adding an acrylate compound having an epoxy group to a part of the component b2).

  In the case of the compound (1-3), after synthesizing the copolymers of the structural units (a1), (a2), (b1), (b2), and (d), the structural unit (b2) It is obtained by adding a group selected from the structural formulas (1) to (9) to a part of the component.

Hereinafter, each structural unit will be described in detail.
R ¹ is an alkyl group having 1 to 18 carbon atoms, a phenyl group, a “phenyl group substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms”, or an aryl group having 7 to 12 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms.

The alkyl group having 1 to 18 carbon atoms represented by R ¹ may be linear, branched or cyclic, for example, methyl group, ethyl group, propyl group, i-propyl group, butyl Group, i-butyl group, t-butyl group, amyl group, i-amyl group, t-amyl group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group and the like. Preferably it is a C1-C8 alkyl group.

In the “phenyl group substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms” represented by R ¹ , the “alkyl group having 1 to 4 carbon atoms” as a substituent is as follows. Examples include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, and the like, and a “C1-C4 alkoxyl group” which is a substituent. Examples thereof include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, butoxy group, i-butoxy group, t-butoxy group and the like.

The “aryl group having 7 to 12 carbon atoms” represented by R ¹ may have a substituent, for example, a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group. And a naphthyl group.
The “aralkyl group having 7 to 12 carbon atoms” represented by R ¹ may have a substituent, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

R ² and R ⁴ are each independently an alkylene group having 1 to 18 carbon atoms, a phenylcarbamic acid ester containing an alkyl group having 1 to 4 carbon atoms as a substituent, or an alicyclic group having 3 to 18 carbon atoms. It represents a carbamate having a group.

Examples of the “C1-C18 alkylene group” represented by R ² or R ⁴ include linear or branched alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, A hexylene group, an octylene group, etc. are mentioned. Preferably, it is a C4-C8 alkylene group.

Each of “phenylcarbamic acid ester containing a C 1-4 alkyl group as a substituent” represented by R ² or R ⁴ or “carbamic acid ester having a C 3-18 alicyclic group” Examples of the ester include alkyl esters having 1 to 6 carbon atoms.

R ³ represents a linear or branched alkylene group having 2 to 16 carbon atoms. Examples of the “linear or branched alkylene group having 2 to 16 carbon atoms” represented by R ³ include a linear or branched alkylene group, such as a methylene group, an ethylene group, a propylene group, and a butylene group. Hexylene group, octylene group and the like. Preferably, it is a C4-C8 alkylene group.

R ⁵ represents an alkyl group having 1 to 4 carbon atoms. Examples of the “alkyl group having 1 to 4 carbon atoms” represented by R ⁵ include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, and a t-butyl group. It is done.

Said l represents the integer of 2-30, Preferably it is an integer of 2-10. The m represents 0 or an integer of 1 to 20, preferably 0 or an integer of 1 to 2. Said n represents the integer of 2-20, Preferably it is an integer of 2-6.
X represents a group selected from the structural formulas (1) to (9), and among them, a group represented by the structural formula (1) or a group represented by the structural formula (2) is preferable.

  In the present invention, the structural ratio of each structural unit in the compounds (1-1) to (1-3) is mol%, and a1 and a2 are 10 to 70% in total, preferably 15 to 60%. , B1 and b2 are 5 to 40% in total, preferably 15 to 30%, c1 is 5 to 40%, preferably 10 to 20%, c2 is 5 to 40%, preferably 10 to 20%, c3 and c4 Is 5 to 40% in total, preferably 10 to 20%, d is 5 to 30%, preferably 10 to 20%.

  Among the above, as the alkali-soluble resin according to the present invention, a (meth) acryloyl group is preferably 0.1 to 5.0 meq / g, more preferably 0.5 to 3.0 meq / g, and particularly preferably 0. Those containing 0.8 to 2.0 meq / g are preferred. The acid value of the alkali-soluble resin is preferably in the range of 20 to 200, more preferably 25 to 100, and particularly preferably 30 to 80.

  The mass average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 30,000, more preferably 7,000 to 15,000, and particularly preferably 8,000 to 12,000.

  The content of the alkali-soluble resin in the photocurable composition is not particularly limited, and when it contains a colorant described later, it is preferably 5 to 55% by mass with respect to the total solid content. Preferably it is 15-45 mass%, and when it does not contain a coloring agent, 20-70 mass% is preferable with respect to the total solid, More preferably, it is 30-60 mass%.

-Photopolymerizable compound-
The photocurable composition of the present invention contains at least one photopolymerizable compound. This photopolymerizable compound is a curable component containing an alkylene oxide chain, if necessary, when the alkali-soluble resin does not contain an alkylene oxide chain and when it contains an alkylene oxide chain. This is effective for forming a sharp pattern in which the solubility of the portion in the developer is enhanced and development residues are prevented.

  As the photopolymerizable compound according to the present invention, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. More preferred.

  Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher under normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B-49-43191 and JP-B-52-30490 Can be mentioned. Furthermore, what is introduced as a photocurable compound and an oligomer in the Japan Adhesive Association magazine Vol.20, No.7, p.300-308 can also be used.

  Further, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol described above and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can also be used as photocurable compounds.

  Among the above, at least one selected from the group consisting of compounds represented by any one of the following general formulas (VI) to (VIII) is preferable.

In the general formula (VI), R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group. m represents an integer of 2 to 6, n represents an integer of 1 to 3, and a and b satisfy a + b = 3.

Of the above, preferably R ²¹ is a hydrogen atom, R ²² is a hydrogen atom, m is 5, n is 1, a is 3, and b is 3. Those are preferred.

In the general formula (VII), R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group. s, t, and u each independently represent 2 or 3, and p, q, and r satisfy 1 ≦ p + q + r ≦ 3.

Of the above, preferably R ²³ is a hydrogen atom, R ²⁴ is a hydrogen atom, R ²⁵ is a hydrogen atom, s is 2, t is 2, and u is 2 It is preferable that p is 1, q is 1, and r is 1.

  In the general formula (VIII), R represents a hydrogen atom or a methyl group. w represents an integer of 2 to 6, x represents an integer of 1 to 3, y represents an integer of 2 to 4, and z represents an integer of 0 to 2.

  Of the above, preferably, R is a hydrogen atom, w is 2, x is 1, y is 4, and z is 0.

Examples suitable as the photopolymerizable compound according to the present invention will be listed below. However, the present invention is not limited to these.

A photocurable compound can be used in combination of 2 or more types in addition to being used alone.
As content in the photocurable composition of a photocurable compound, 20-200 mass% is preferable with respect to the total solid of this composition, More preferably, it is 50-120 mass%.

-Trihalomethane triazine compounds-
The photocurable composition of the present invention contains at least one trihalomethane triazine compound as a photopolymerization initiator. This trihalomethane triazine-based compound can be used with a coumarin-based ultraviolet absorber described later to increase the sensitivity, increase the light absorption during pattern exposure, and change the size of the image pattern (for example, the line portion). Line width and the like) can be effectively suppressed.

  The trihalomethane triazine compound can be appropriately selected from conventionally known compounds. In the present invention, it is particularly preferable to be composed of at least one selected from the group consisting of compounds represented by any one of the following general formulas (II) to (V).

In the general formula (II), R ⁴ represents a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
Examples of the halogen atom represented by R ⁴ include a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom and a bromine atom are preferable.

Examples of the hydrocarbon group having 1 to 4 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, and a propyl group. Among them, a methyl group and an ethyl group are preferable.

R ⁵ and R ⁶ each independently represent —CH ₂ COOR ⁷ , and R ⁷ represents a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group having 1 to 4 carbon atoms represented by R ⁷ include a methyl group, an ethyl group, a propyl group, and a butyl group. Among them, a methyl group and an ethyl group are preferable.

  Moreover, said X represents a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom etc. are mentioned, A chlorine atom is especially preferable. Said n represents the integer of 0-4, Preferably it is 1.

Of the compounds represented by the general formula (II), R ⁴ is a bromine atom, R ⁵ and R ⁶ are both —CH ₂ COO—C ₂ H ₅ , and R ⁷ is an ethyl group. A compound in which X is a chlorine atom and n is 1 is particularly preferable.

In the general formula (III), R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, or a hydrocarbon group having 1 to 4 carbon atoms.
Examples of the halogen atom represented by R ⁸ or R ⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferable.

As the alkoxy group represented by R ⁸ or R ⁹ , an alkoxy group having 1 to 4 carbon atoms is preferable, and among them, a methoxy group and an ethoxy group are preferable.

As a C1-C4 hydrocarbon group represented by said R < ⁸ > or R < ⁹ >, a methyl group and an ethyl group are preferable.

  X in the general formula (III) represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable.

Of the compounds represented by the general formula (III), a compound in which R ⁸ and R ⁹ are hydrogen atoms and X is a chlorine atom is particularly preferable.

In the general formula (IV), R ¹⁰ represents a halogen atom or an alkoxy group.
Examples of the halogen atom represented by R ¹⁰ include a fluorine atom, a chlorine atom, and a bromine atom, and a chlorine atom and a bromine atom are preferable.

As the alkoxy group represented by R ¹⁰ , an alkoxy group having 1 to 4 carbon atoms is preferable, and among them, a methoxy group and an ethoxy group are preferable.

X in the general formula (IV) represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, etc. Among them, a chlorine atom and a bromine atom are preferable.
Said n represents the integer of 0-4, Preferably it is 1.

Of the compounds represented by the general formula (IV), a compound in which R ¹⁰ is a methoxy group, X is a chlorine atom, and n is 1 is particularly preferable.

In the general formula (V), R ¹¹ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms.
The alkoxy group having 1 to 3 carbon atoms represented by R ^11, a methoxy group is preferable.

R ¹² and R ¹³ each independently represents a halogen atom, a hydroxyl group, an alkoxy group, or a hydrocarbon group having 1 to 3 carbon atoms.
Examples of the halogen atom represented by R ¹² or R ¹³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom and an iodine atom are preferable.

The alkoxy group represented by R ¹² or R ¹³ is preferably a methoxy group or an ethoxy group.
As a C1-C3 hydrocarbon group represented by said R < ¹² > or R < ¹³ >, a methyl group is preferable.

X in the said general formula (V) represents a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A bromine atom and a chlorine atom are preferable.
The n represents an integer of 0 to 4, and is preferably 1 or 2.

Of the compounds represented by the general formula (V), particularly those compounds in which R ¹¹ is a hydroxyl group, R ¹² and R ¹³ are both hydrogen atoms, that is, n is 0 and X is a chlorine atom. preferable.

  Hereinafter, preferred specific examples of the trihalomethane triazine compound will be shown. However, the present invention is not limited to these.

Preferred examples include the following compounds:

Among these, the following compounds are more preferable,

More preferably, they are the following compounds.

As content in the photocurable composition of a trihalomethane triazine type compound, 0.1-10 mass% is preferable with respect to the total mass of the non-volatile component of this composition, 2-7 mass% is more preferable, 3 ˜6% by weight is particularly preferred. When the content is within the above range, light is absorbed at the time of pattern exposure while maintaining high sensitivity, and it is effective in suppressing fluctuations in the size of the image pattern such as, for example, thickening of the line width.
Here, the “nonvolatile component” is a component that remains on the substrate by drying. Specifically, when applied to the substrate with a thickness of 10 μm, the composition is subjected to a drying treatment at 160 ° C. for 1 hour. A component that remains on the substrate without being lost due to evaporation or volatilization. The same applies hereinafter.

In this invention, you may use together other well-known photoinitiators other than said trihalomethane triazine type compound. Examples of other known photopolymerization initiators include active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, 3-aryl substituted coumarin compounds, and at least one kind of lophine dimer. . Regarding these details, reference can be made to the description in JP-A No. 2004-109989.
When the other photopolymerization initiator is used in combination, the ratio of the “trihalomethanetriazine compound” according to the present invention in the total amount of the photopolymerization initiator is preferably 50% by mass or more from the viewpoint of the effect of the present invention, 75 The mass% or more is more preferable.

-Coumarin UV absorber-
The photocurable composition of the present invention contains at least one coumarin-based ultraviolet absorber. This coumarin-based UV absorber can be used with the aforementioned trihalomethane triazine-based compound to increase the sensitivity, increase the light absorption during pattern exposure, and change the size of the image pattern (for example, the line portion). It is effective to effectively suppress the line width of the line).

  As a coumarin type ultraviolet absorber, it can select suitably from conventionally well-known things, and especially the compound represented with the following general formula (I) in this invention is preferable.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
As a C1-C4 hydrocarbon group represented by said R < ¹ > or R < ² >, a methyl group and an ethyl group are preferable, for example, and an ethyl group is more preferable especially.

R ³ represents a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
Examples of the halogen atom represented by R ³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom and a chlorine atom are preferable.

As a C1-C4 hydrocarbon group represented by said R < ³ >, a methyl group, an ethyl group, etc. are mentioned suitably, for example, Among these, an ethyl group is preferable.

  X in the general formula (I) represents a hydrogen atom, a halogen atom, or an alkyl oxide group. Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.

As the alkyl oxide group represented by X, an alkyl oxide group having 1 to 4 carbon atoms is preferable, and examples thereof include a methoxy group and an ethoxy group, and among them, a methoxy group is preferable.
N represents an integer of 0 to 4, preferably 1.

Among the coumarin ultraviolet absorbers represented by the general formula (I), R ¹ and R ² are both ethyl groups, R ³ is a hydrogen atom, that is, n is 0, and X is a chlorine atom. Certain compounds are particularly preferred.

  Hereinafter, the preferable specific example of the said coumarin type ultraviolet absorber is shown. However, the present invention is not limited to these.

In this invention, you may use together well-known ultraviolet absorbers other than a coumarin type ultraviolet absorber with said coumarin type ultraviolet absorber. Examples of other known ultraviolet absorbers include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.
When the other ultraviolet absorber is used in combination, the ratio of the “coumarin ultraviolet absorber” according to the present invention in the total amount of the ultraviolet absorber is preferably 50% by mass or more from the viewpoint of the effect of the present invention, and 75% by mass. % Or more is more preferable.

  As content in the photocurable composition of a coumarin type ultraviolet absorber, 0.1-10 mass% is preferable with respect to the total mass of the non-volatile component of this composition, 4-8 mass% is more preferable, 5-7 mass% is especially preferable. When the content is within the above range, light is absorbed at the time of pattern exposure while maintaining high sensitivity, and it is effective in suppressing fluctuations in the size of the image pattern such as, for example, thickening of the line width.

-Colorant-
The photocurable composition of the present invention can suitably contain at least one colorant and can be configured to form a colored visible image, such as a liquid crystal display (LCD) or a solid. A photocured film of a color filter for an image sensor (image sensor) can be formed.

  Colorants include pigments, dyes and the like. A pigment and dye can be used individually by 1 type or in mixture of 2 or more types. Hereinafter, the pigments and dyes suitable for the present invention will be mainly described.

  As the pigment, conventionally known various inorganic pigments or organic pigments can be used. In addition, regardless of whether the pigment is an inorganic pigment or an organic pigment, it is preferable to use a fine particle as much as possible considering that high transmittance is preferable, and considering the handling property, the average particle size of the pigment is 0.01 μm to 0.00. 1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

As the organic pigment,
CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
CIPigment Orange 36, 38, 43, 71;
CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
CIPigment Violet 19, 23, 32, 39;
CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Green 7, 36, 37;
CIPigment Brown 25, 28;
CIPigment Black 1, 7;
And carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause has not been fully elucidated, it is presumed that the good affinity between the photocurable monomer and the pigment has an influence.

Among the above, preferable pigments include the following. However, it is not limited to these.
CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CIPigment Orange 36, 71,
CIPigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CIPigment Violet 19, 23, 32,
CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CIPigment Black 1, 7,
CIPigment Green 7, 36;

The organic pigments can be used alone or in combination of two or more kinds in order to increase color purity. Specific examples are shown below.
Examples of red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments, and perylene red pigments. A mixture of these is used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it exceeds 100: 5, the light transmittance of 400 to 500 nm can be suppressed, and the color purity can be increased. On the other hand, when the ratio is less than 100: 50, the dominant wavelength is shorter than the short wavelength, and deviation from the NTSC target hue is hardly observed. In particular, the range of 100: 10 to 100: 30 is optimal. In the case of a combination of red pigments, it is adjusted according to the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment is used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. If it exceeds 100: 5, the light transmittance of 400 to 450 nm can be suppressed, and the color purity can be increased. On the other hand, when the ratio is less than 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue is hardly observed. A more preferable mass ratio is in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment alone or a mixture thereof with a dioxazine purple pigment is used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, a photosensitive resin having good dispersibility and dispersion stability is obtained by using a powdered processed pigment in which a pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, or an ethyl cellulose resin. A composition can be obtained.

  As a pigment for constituting the black matrix, carbon black, titanium carbon, iron oxide and the like can be used alone or in combination. Among these, carbon black and titanium carbon can be mixed and used. In this case, the mixing ratio is within the range of 100: 0 to 100: 60 in terms of dispersion stability. preferable.

Hereinafter, a method for treating a pigment will be described.
Generally, these pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization for drying, a large amount of heat energy is given to dry it to form a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.

Since it is not easy to disperse the pigment forming such an aggregate in the fine particles, it is preferable to treat the pigment with various resins in advance. Examples of the resin include the alkali-soluble resins described above.
Examples of the treatment method include a flushing treatment and a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, and the like. Among these, a flushing process or a kneading method using two or three roll mills is preferable in terms of atomization.

  The flushing treatment is usually a method in which an aqueous dispersion of pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with a resin. According to this method, since the pigment is not dried, the aggregation of the pigment can be prevented and the dispersion becomes easy. In kneading with a two or three roll mill, the pigment and resin or resin solution are mixed, and then the pigment and resin are kneaded while applying a high shear (shearing force), thereby coating the pigment surface with the resin. , A method for treating pigments. The pigment particles aggregated in this process are dispersed from the lower order aggregates to the primary particles.

In the present invention, processed pigments previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be suitably used. As the form of the processed pigment treated with the above-mentioned various resins, a powder, a pellet, and a paste in which the resin and the pigment are uniformly dispersed are preferable.
Further, a non-uniform lump in which the resin is gelled is not preferable. The colored dispersion thus obtained is mixed with a photocurable monomer and provided as a photocurable composition.

  When the colorant is contained, the content of the colorant in the photocurable composition is not particularly limited, but is preferably 30 to 60% by mass with respect to the total solid content.

  For the purpose of improving the dispersibility of the pigment, conventionally known pigment dispersants and surfactants can be added. As the dispersant, many kinds of compounds are used. For example, a phthalocyanine derivative (EFKA-745 manufactured by Efka), Solsperse 5000 (manufactured by Geneca), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), ( Cationic surfactants such as (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho); polyoxyethylene lauryl ether Nonionic surfactants such as polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (more, Morishita industry) ), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, Various Solsperse dispersants (manufactured by Zeneca) such as 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, 103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonetto S-20 (manufactured by Sanyo Chemical Co., Ltd.).

  When using dye, there is no restriction | limiting in particular in this dye, A well-known dye can be used for conventional color filters. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-94821, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215. JP, 11-343437, JP 8-62416, JP 2002-14220, JP 2002-14221, JP 2002-14222, JP 2002-14223, The dyes disclosed in JP-A-8-302224, JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

  In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used from the viewpoint of completely removing the binder and / or dye by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

  The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, photocurability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

  As the derivative of the acid dye, an inorganic salt of an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, etc. can be used, and a curable composition solution Is not particularly limited as long as it can be dissolved, but it requires solubility in organic solvents and developer, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. It is selected considering all of the performance.

The method for forming the “salt of an acid dye and a nitrogen-containing compound” may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.
The nitrogen-containing compound that forms a salt with the acidic dye and the nitrogen-containing compound that forms an amide bond with the acidic dye will be described. Nitrogen-containing compounds are the solubility of salts or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, interaction with other components in the curable composition, and heat resistance as a colorant. And light resistance. When selected only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible, preferably has a molecular weight of 300 or less, more preferably has a molecular weight of 280 or less, and has a molecular weight of 250 or less. Particularly preferred.

  The molar ratio of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound (hereinafter referred to as n) is a value that determines the molar ratio between the acid dye molecule and the amine compound that is a counter ion. It can be freely selected according to the salt-forming conditions of the dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selected from the standpoint of absorbance only, n is preferably a numerical value between 0 <n ≦ 4.5, more preferably a numerical value between 0 <n ≦ 4, and a numerical value between 0 <n ≦ 3.5. Particularly preferred.

  The concentration in the photocurable composition when using a dye varies depending on the dye with respect to the total solid components, but is preferably 0.5 to 80% by mass, more preferably 0.5 to 60% by mass, and 0 0.5 to 50% by mass is particularly preferable.

-Solvent-
A solvent can be used when preparing the photocurable composition of the present invention.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropionate Ethyl acetate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.
You may use a solvent in combination of 2 or more types besides using independently.

-Other components-
In the photocurable composition of the present invention, various additives as necessary, for example, a filler, a polymer compound other than the alkali-soluble resin, a surfactant, an adhesion promoter, an antioxidant, an anti-aggregation agent, etc. Can be blended.

  Specific examples of additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, polymer having hydroxyl group Alkali-soluble resins such as alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; nonionic, kachin, anionic surfactants; vinyltrimethoxysilane Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypro Rutrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl Adhesion promoters such as trimethoxysilane and 3-mercaptopropyltrimethoxysilane; antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; 2 There may be mentioned UV absorbers such as-(3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

  In addition, when the alkali solubility of the uncured part is promoted and the developability of the composition of the present invention is further improved, the composition of the present invention is an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl. Catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful. .

  The photocurable composition of the present invention comprises an alkali-soluble resin, a photocurable compound, a trihalomethanetriazine compound (photopolymerization initiator), and a coumarin ultraviolet absorber, together with other additives as necessary. Can be prepared by mixing and dispersing using an appropriately selected mixer or disperser.

  The photocurable composition of the present invention is applied to a substrate by a coating method such as spin coating, cast coating, slit coating, roll coating, and the like to form a radiation sensitive layer, and is exposed through a predetermined mask pattern. Then, a colored pattern is formed by developing with a developer. Among them, the slit coating has an advantage that it can be applied to a large area to be coated at a high speed. The photocurable composition of the present invention is excellent in suitability for slit coating, and a coating film having a uniform film thickness can be obtained in a large area without causing liquid breakage even when applied at high speed.

  In the slit coating, the gap between the substrate (slit head) having a width (several tens to several hundreds of microns) and a length (one side of the coating region) and the substrate is several tens to several tens. This is a method of applying a resist to the substrate by moving the slit head or the substrate by moving the slit head or the substrate and forming the desired coating film with a small amount of coating solution compared to the above-mentioned spin coating. In addition, the film thickness distribution is characterized by having performance equivalent to that of spin coating. Since the amount of the coating solution is small, the manufacturing cost can be reduced. Further, slit coating has an advantage not found in other coating methods such as spin coating, in which a uniform coating film can be obtained even at the central portion of the substrate.

The photocurable composition of the present invention is suitable for production of LCD components or members and components or members for solid-state imaging device (image sensor) components.
Examples of the LCD component or member include a spacer, a contact hole forming layer, an interlayer insulating film, a planarizing layer, a scattering layer, and the like, and an LCD spacer is preferable.
The solid-state image sensor component or member includes a color filter, a transparent resin undercoat layer (spacer) provided to improve the adhesion of the color filter on the silicon wafer, and the surface of the color filter applied to the surface. A flattening layer (protective layer) for flattening can be used.

The photospacer for a liquid crystal display device of the present invention is a method comprising at least a step of applying the above-described photocurable composition by, for example, slit coating, and a step of irradiating the applied coating film in a pattern. It can form suitably.
In the light irradiation, ultraviolet rays such as g-line, h-line, and i-line can be suitably used as a light source.
Preferably, at least after the step of slit-coating the above-mentioned photocurable composition and the step of irradiating the applied coating film with light in a pattern, the step of developing with a developer is performed to form a (colored) pattern. It is a method of forming.

  When the photocurable composition of the present invention is used for forming an LCD spacer, it can be provided between an array substrate and a color filter substrate. Specifically, (1) When provided on the ITO electrode layer of the array substrate, (2) When provided on the colored layer of the color filter substrate, (3) From both the array substrate side and the color filter substrate side May be provided. It can also be provided on an alignment film such as polyimide (the alignment film is provided on the color filter colored layer).

When the photocurable composition of the present invention is used for forming a flattening layer of an LCD, it is provided as a protective layer for the color filter on the colored layer constituting the color filter. It can also be provided on the ITO film.
There is a system that requires opening a hole in a protective layer in order to impart conductivity to a part of an LCD array substrate or CF substrate. In that case, after forming a layer using the photocurable composition of the present invention, the portion corresponding to the hole is unexposed in the exposure step, and the non-exposed portion is removed by development processing. In this case, the exposure is preferably stepper exposure, but may be proximity exposure. By doing so, it is possible to form a hole having a slope that is gentler than that of a resist for semiconductors, and to smoothly inject liquid crystal by forming a panel.

As a component for solid-state imaging devices, it is applied to the surface of a transparent resin undercoat layer, a photo spacer, or a color filter for improving the adhesion of a color filter (colored layer) on a silicon wafer to flatten the surface. A flattening layer (protective layer) or the like can be provided. The photocurable composition of the present invention can be used for these undercoat layer or planarizing layer.
The photocurable composition of the present invention can be cured by irradiation with radiation such as i-line and h-line, and can be used as an undercoat layer or a flattening layer for improving the adhesion of a color filter (colored layer). .

  In the present invention, the dry layer thickness of the layer formed using the photocurable composition is preferably 1 to 50 μm, more preferably 1.0 to 20 μm, still more preferably 1. In the case of forming a planarizing layer, the thickness is preferably 0.1 to 3 μm, more preferably 0.2 to 1.5 μm. In the case of a contact hole, 0.1 to 6 μm. The thickness is preferably 0.0 μm, more preferably 0.2 to 3.0 μm.

  Examples of the pattern form of the photo spacer include a dot shape, a stripe shape, and a grid pattern. The pitch is reasonable according to the color filter, and this integer multiple is preferable. The shape may be a quadrangular prism, a cylinder, an elliptical cylinder, a quadrangular pyramid, a quadrangular trapezoidal cross section, or a polygon thereof.

  Examples of the substrate include a color filter substrate, soda glass, non-alkali glass, Pyrex (registered trademark) glass, quartz glass, and the like, for example, used in liquid crystal display devices, and those having a transparent conductive film attached thereto, a solid-state imaging device, etc. Examples of the photoelectric conversion element substrate used in the present invention include a silicon substrate. These substrates are generally formed with black stripes that isolate pixels.

Any developer can be used as long as it dissolves the uncured portion of the layer (film) made of the photocurable composition and does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
As said organic solvent, the above-mentioned solvent which can be used when preparing the photocurable composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. An alkaline aqueous solution in which an alkaline compound such as choline, pyrrole or piperidine is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.
In the case where a developer composed of an alkaline aqueous solution is used, washing with water is generally performed after development.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

<Synthesis of alkali-soluble resin (1)>
In a five-necked flask equipped with reflux cooling air, a thermometer, a nitrogen gas inlet tube and a stirrer, 45 parts of benzyl methacrylate, 27 parts of styrene, 18 parts of methacrylic acid, 63 parts of hydroxyethyl methacrylate, 27 parts of methoxypolyethylene glycol monomethacrylate 280 parts of ethyl ethoxypropionate and 140 parts of cyclohexanone. Furthermore, azoisobutyronitrile was added as a polymerization initiator, and the polymerization reaction was completed by heating and stirring at 80 ° C. for 8 hours.
Subsequently, 64 parts of a monoadduct of hexamethylene diisocyanate hydroxyethyl acrylate was added and stirred at 60 ° C. for 8 hours to obtain an alkali-soluble resin (1) having photocurability. The obtained alkali-soluble resin (1) had a (meth) acryloyl group equivalent of 1.73 meq / g, an acid value of 51, and a weight average molecular weight Mw of 11,500.

<Synthesis of alkali-soluble resin (2)>
In a five-necked flask equipped with reflux cooling air, a thermometer, a nitrogen gas inlet tube and a stirrer, 45 parts of benzyl methacrylate, 27 parts of styrene, 18 parts of methacrylic acid, 63 parts of hydroxyethyl methacrylate, 280 parts of ethyl ethoxypropionate, And 140 parts of cyclohexanone. Further, azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 12 hours to complete the polymerization.
The obtained alkali-soluble resin had no (meth) acryloyl group equivalent, an acid value of 80, and a mass average molecular weight Mw of 45,000.

Example 1
<Preparation of photocurable composition>
The following components were stirred and mixed using a magnetic stirrer to prepare a photocurable composition for LCD (resist liquid) of the present invention.
・ Alkali-soluble resin (1) 24 parts ・ Dipentaerythritol pentahexaacrylate 14 parts (monomer 1; photopolymerizable compound)
・ Ethylene oxide modified pentaerythritol tetraacrylate (monomer 2; photopolymerizable compound) 4 parts 7-{[4-chloro-6- (diethylamino) -5-triazin-2-yl] amino} -3-phenylcoumarin ... 2.4 parts (coumarin ultraviolet absorber represented by the general formula (I) described above; hereinafter abbreviated as UV absorber a)
Trihalomethanetriazine compound 3.2 parts (photopolymerization initiator [X: Cl, R ⁸ , R ⁹ : H] represented by the aforementioned general formula (III); hereinafter abbreviated as initiator A) )
Ethyl ethoxy bropionate / cyclohexanone: 150 parts (= 60/10 (mass ratio); solvent)
・ MegaFack F-144: 0.01 part (manufactured by DIC Corporation; fluorosurfactant)

(Examples 2 to 7)
Example 1 except that the type and content of the trihalomethanetriazine compound (photopolymerization initiator), the content of the UV absorber a, and the photopolymerizable compound were changed as shown in Table 1 below. In the same manner as above, a photocurable composition for LCD of the present invention was prepared. Initiator B is shown below.
Initiator B: Photopolymerization initiator represented by the general formula (IV) described above [X: Cl, R ¹⁰ : H, n = 1; trihalomethanetriazine compound]

(Comparative Example 1)
Comparative photocurability for LCD in the same manner as in Example 1 except that UV absorber a in Example 1 was replaced with 2 (2′hydroxy-5′methylphenyl) benzotriazole (UV absorber b). Prepared the composition

(Comparative Example 2)
A comparative photocurable composition for LCD was prepared in the same manner as in Example 1 except that the initiator A (trihalomethanetriazine compound) was replaced with the following photopolymerization initiator C in Example 1.

(Comparative Example 3)
A comparative photocurable composition was prepared in the same manner as in Example 1 except that the amount of the photopolymerizable compound and the type of the alkali-soluble resin were changed as shown in Table 1 below.

(Evaluation)
The following evaluation was performed about each photocurable composition obtained in Examples 1-7 and Comparative Examples 1-3. The evaluation results are shown in Table 2 below.
-1. Evaluation of development latitude and thickness of mask
Using each photocurable composition, the width of width and mechanical strength with respect to the mask dimensions were evaluated as follows.
The prepared photocurable composition was spin-coated on a glass substrate (Corning 1737) so that the film thickness after drying was 2.0 μm, prebaked at 100 ° C. for 120 seconds using an oven, and then 10 μm on a side. The exposure was performed at 100 mj / cm ² with a square mask having a width mask dimension (illuminance was 20 mW / cm ² ). Then, it developed at 26 degreeC using the 20% dilution liquid of alkali developing solution CD-2000 (made by Fuji Film Electronics Materials Co., Ltd.). Development was carried out with development times ranging from 10 to 100 seconds in increments of 10 seconds. After development, it was post-baked at 230 ° C. for 30 minutes in a clean oven. Then, the horizontal width of the lower bottom of the pattern was measured, and the amount of weight (vs. mask thickness) with respect to the mask (10 μm width) was measured by the following formula. Moreover, the pattern shape at that time was observed with a scanning electron microscope.
Mask thickness (one side) = (Pattern bottom base dimension-Mask dimension) / 2

-2. Evaluation of mechanical properties
Each of the prepared photocurable compositions was spin-coated on a glass substrate (Corning 1737) so that the film thickness after drying was 2.0 μm, prebaked at 100 ° C. for 120 seconds using an oven, and then 10 μm on each side. The exposure was performed at 100 mj / cm ² (illuminance is 20 mW / cm ² ) using a square mask having a mask size of 1 mm. Then, it developed at 26 degreeC using the 20% dilution liquid of alkali developing solution CD-2000 (made by Fuji Film Electronics Materials Co., Ltd.). Development was carried out with development times ranging from 10 to 100 seconds in increments of 10 seconds. After development, it was post-baked at 230 ° C. for 30 minutes in a clean oven. Then, a load of 50 mN was applied to the obtained pattern with an ultra-micro hardness tester (manufactured by Shimadzu Corporation), the deformation amount at the maximum load (compression deformation amount; μm), and the recovery amount after pulling (μm ) Was measured. A smaller value for the amount of compressive deformation and a larger value for the amount of recovery indicate superior mechanical properties.

-3. Evaluation of pixel cross-sectional shape (pattern profile)
Each of the prepared photocurable compositions was spin-coated on a glass substrate (Corning 1737) so that the film thickness after drying was 2.0 μm, prebaked at 100 ° C. for 120 seconds using an oven, and then 10 μm on each side. The exposure was performed at 100 mj / cm ² (illuminance is 20 mW / cm ² ) using a square mask having a mask size of 1 mm. Then, it developed at 26 degreeC using the 20% dilution liquid of alkali developing solution CD-2000 (made by Fuji Film Electronics Materials Co., Ltd.). Development was carried out with development times ranging from 10 to 100 seconds in increments of 10 seconds. After development, it was post-baked at 230 ° C. for 30 minutes in a clean oven. And about the obtained pattern, it divides | segments so that the cross section of one pattern can be observed, respectively, produces a sample, observes a shape using SEM (S-7800H, Hitachi Ltd. make), photography did.

  As shown in Table 2, the embodiment has a wide development latitude and maintains high sensitivity and good developability compared to the comparative example. A pattern with excellent mechanical properties could be formed.

Claims (7)

In a photocurable composition containing an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator,
The photopolymerization initiator, wherein the photopolymerization initiator is a trihalomethane triazine compound, further includes a coumarin ultraviolet absorber, and at least one of the alkali-soluble resin and the photopolymerizable compound has an alkylene oxide chain. Sex composition. The photocurable composition according to claim 1, wherein the coumarin ultraviolet absorber is a compound represented by the following general formula (I).

[In General Formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Represents. X represents a hydrogen atom, a halogen atom, or an alkyl oxide group. n represents an integer of 0 to 4. ] The photocurable composition according to claim 1 or 2, wherein the trihalomethanetriazine compound is at least one selected from the group consisting of compounds represented by any one of the following general formulas (II) to (V).

[In the general formula (II), R ⁴ is, represents a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms. R ⁵ and R ⁶ each independently represent —CH ₂ COOR ⁷ , and R ⁷ represents a hydrocarbon group having 1 to 4 carbon atoms. n represents an integer of 0 to 4. X represents a halogen atom. ]

[In General Formula (III), R ⁸ and R ⁹ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, or a hydrocarbon group having 1 to 4 carbon atoms. X represents a halogen atom. ]

[In General Formula (IV), R ¹⁰ represents a halogen atom or an alkoxy group, and X represents a halogen atom. n represents an integer of 0 to 4. ]

[In General Formula (V), R ¹¹ represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and R ¹² and R ¹³ each independently represent a halogen atom, a hydroxyl group, an alkoxy group, or 1 to 3 carbon atoms. Represents a hydrocarbon group. X represents a halogen atom. n represents an integer of 0 to 4. ]   The photocurable composition according to claim 1, wherein the alkali-soluble resin has a polymerizable unsaturated group in a side chain in the molecule. The light according to any one of claims 1 to 4, wherein the photopolymerizable compound is at least one selected from the group consisting of compounds represented by any one of the following general formulas (VI) to (VIII). Curable composition.

[In General Formula (VI), R ²¹ and R ²² each independently represents a hydrogen atom or a methyl group. m represents an integer of 2 to 6, n represents an integer of 1 to 3, and a and b satisfy a + b = 3. ]

[In General Formula (VII), R ²³ , R ²⁴ and R ²⁵ each independently represents a hydrogen atom or a methyl group. s, t, and u each independently represent 2 or 3, and p, q, and r satisfy 1 ≦ p + q + r ≦ 3. ]

[In general formula (VIII), R represents a hydrogen atom or a methyl group. w represents an integer of 2 to 6, x represents an integer of 1 to 3, y represents an integer of 2 to 4, and z represents an integer of 0 to 2. ]   A photospacer for a liquid crystal display device comprising the photocurable composition according to any one of claims 1 to 5.   The photospacer for a liquid crystal display device for regulating a cell thickness between substrates provided so as to sandwich the liquid crystal, wherein the cell thickness is 3 μm or less.