JP5546801B2 - Photosensitive resin composition for ultraviolet light laser exposure, pattern forming method, color filter produced using the method, method for producing color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition for ultraviolet laser exposure, a pattern forming method, a color filter produced using the method, a method for producing a color filter, and a liquid crystal display device using the same.

  Color filters are indispensable components for liquid crystal displays. The liquid crystal display is compact compared to the CRT as a display device, and can save power, and has become more than equivalent in terms of performance due to technological advancement. Therefore, TV screens, personal computer screens, and other display devices It is being replaced by CRT.

In recent years, the development of liquid crystal displays has been expanded from the use of personal computers and monitors having a relatively small screen area to TV applications that require a large screen and high image quality.
In TV applications, higher image quality, that is, improvement in contrast and color purity is required compared to conventional monitor applications. In order to improve contrast, a finer particle size of a colorant (such as an organic pigment) used in a photosensitive resin composition used for forming a color filter is required. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of this photosensitive resin composition for color purity improvement.

  In response to the above requirements, a pigment dispersion composition having a finer particle diameter and higher dispersibility is required. In order to improve the dispersibility of the pigment, for example, the surface of the phthalocyanine pigment is usually modified with the derivative compound thereof, and the dispersion of a low molecular weight resin having a polar functional group that is easily adsorbed on the modified surface. A pigment dispersion composition containing a pigment, a surface modifier, and a dispersant is obtained while dispersing or stabilizing the pigment using the agent. Then, the obtained pigment dispersion composition further contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and other components to form a photosensitive composition, and a color filter is obtained by using this to obtain a color filter. ing.

If the pigment is made finer and the pigment content is increased, there is a problem that the stability of the line width is impaired when an image pattern is formed by the photolithography method. For TV applications, it is particularly required to provide a color filter at a low cost. However, the above-described problems centered on the development process have been required to be improved because the yield is lowered and the productivity is deteriorated.
In order to solve the above problems, many attempts have been made to improve the sensitivity by improving the photopolymerization initiator used in the photocurable composition for color filters. For example, a photopolymerizable composition using a triazine compound having a specific structure (see, for example, Patent Document 1), or a photo filter for a color filter using a mixture of one or more benzophenone, acetophenone, and thioxanthone compounds. A resist (see, for example, Patent Document 2) is disclosed.

As another proposal, by defining the average double bond equivalent in the organic compound formed by summing the binder resin and the polymerizable monomer in the photosensitive composition, and further specifying the molecular weight of the binder resin, A technique for forming a forward tapered shape is disclosed (see Patent Document 3).
However, these techniques are inferior in productivity in the exposure process and the development process, cannot secure sufficient productivity, and therefore cannot reduce the price of the color filter.

In order to increase the productivity of the exposure process and the development process, it has been proposed to perform pattern formation by exposing with laser light (see Patent Document 4). However, although a semiconductor laser has an advantage that a mask is unnecessary, the laser output is small and insufficient to improve productivity. Therefore, a method for manufacturing a color filter using a high-power ultraviolet laser has been proposed (see Patent Document 5). However, even with the above-described prior art, the characteristics required for the color filter, such as a roughened pixel surface in the development process and insufficient line width stability of the pattern, are not satisfied.
Also, an exposure apparatus that does not use a large photomask has been proposed in terms of reducing the total cost of the color filter. (See Patent Documents 6 and 7) However, there is no presentation of a specific photosensitive resin composition, and a proposal of a photosensitive resin composition suitable for these apparatuses has been desired.

JP-A-6-289611 Japanese Patent Laid-Open No. 9-80225 JP 2007-93811 A JP 2007-156011 A JP 2003-278614 A JP 2008-76709 A JP 2008-51866 A

The present invention relates to a photosensitive resin composition for ultraviolet laser exposure and a pattern forming method capable of forming a pattern having a high line width stability in a development process and a smooth surface on a substrate, in particular, a colored pixel of a color filter, etc. It is an object of the present invention to provide a photosensitive resin composition for ultraviolet laser exposure and a pattern forming method that are suitable for the formation of the above.
A further object of the present invention is to provide a color filter obtained by the pattern forming method, having colored pixels having high line width stability in the developing process and smooth surface roughness, good color characteristics, and high productivity. Another object of the present invention is to provide a display device having high image quality with high contrast and color purity provided with the color filter.

As a result of intensive studies, the present inventor has found that the above problems can be solved by the following method.
<1> (A) a resin, (B) an ethylenically unsaturated compound, (C) a photopolymerization initiator containing at least one oxime ester compound represented by the following general formula (2) or (3) , and (D) The photosensitive resin composition for ultraviolet laser exposure containing the thiol compound of the content of the range of 0.2 mass%-4 mass% with respect to solid content of the photosensitive resin composition.
<2> The photosensitive resin composition for ultraviolet laser exposure according to <1>, wherein the photosensitive resin composition further contains (E) a colorant.

<3> The photosensitive resin composition for ultraviolet laser exposure according to <1> or <2>, wherein the (D) thiol compound is a compound represented by the following general formula (1).

In general formula (1), Q represents NR, a sulfur atom, or an oxygen atom. R represents a hydrogen atom, an alkyl group, or an aryl group. A ¹ represents an atomic group that forms a heterocycle with N═C—X.

<4> The photosensitive resin composition for ultraviolet laser exposure according to any one of <1> to <3>, further including at least one biimidazole compound as the (C) photopolymerization initiator.
<5> The ultraviolet laser exposure sensitivity according to < 2>, wherein the content of the (E) colorant is in the range of 25% by mass to 75% by mass with respect to the total solid content of the photosensitive resin composition. Resin composition.
< 6 > The photosensitive resin composition for ultraviolet laser exposure according to any one of <1> to < 5 >, wherein the ultraviolet laser is a solid laser or a gas laser.
< 7 > The photosensitive resin composition for ultraviolet laser exposure according to any one of <1> to < 6 >, wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm.

< 8 > A pattern forming method in which the photosensitive resin composition for ultraviolet light laser exposure according to any one of <1> to <8> is exposed in a pattern with an ultraviolet light laser to cure an exposed region.
< 9 > A color filter having a pattern formed by the pattern forming method according to < 8 >.
<1 0 > A method for producing a color filter, wherein a color filter is formed by the pattern forming method according to < 8 >.
<1 1 > A liquid crystal display device comprising the color filter according to < 9 >.

In the present invention, an ultraviolet laser is used as the exposure light. Since the output of the ultraviolet laser is high, the productivity is improved. However, there is a problem that the surface of the exposed portion is roughened. The reason for this is presumed that the decomposition of the surface layer is accelerated by exposure light in addition to the inhibition of polymerization by oxygen in the air.
In the present invention, by adding (D) a thiol compound to the photosensitive resin composition used for pattern formation, surface roughness can be prevented and line width stability against development can be further improved.
Although this action is not clear, (D) the thiol compound has promoted chain transfer in radical polymerization, polymerization of the exposed area has progressed, and the film property of the exposed area has been improved. It is presumed that the line width stability in the development process can be improved by improving the adhesion between the resin composition layer and the substrate.

According to the present invention, a photosensitive resin composition for ultraviolet light laser exposure and a pattern forming method capable of forming a pattern having a high line width stability in a development process and a smooth surface on a substrate, in particular, coloring of a color filter. A photosensitive resin composition for ultraviolet laser exposure and a pattern forming method that are suitable for forming pixels and the like can be provided.
The present invention further includes a color filter that is obtained by the pattern forming method, includes a colored pixel having high line width stability in a development process and having a smooth surface roughness, good color characteristics, and high productivity. In addition, it is possible to provide a display device having the image quality with high contrast and color purity provided with the color filter.

Hereinafter, the best mode for carrying out the invention will be described in detail.
The pattern forming method of the present invention, (A) resin, (B) a ethylenically unsaturated compound, (C) a photopolymerization initiator, and (D) a photosensitive resin composition containing a thiol compound (ultraviolet present invention described later The photosensitive resin composition for optical laser exposure ) is exposed in a pattern with an ultraviolet laser, and the exposed region is cured.

[Pattern formation method]
In the pattern formation method of this invention, it has the exposure process exposed to a pattern shape with an ultraviolet light laser. By this exposure step, (B) the polymerization curing reaction of the ethylenically unsaturated compound occurs and proceeds by the initiation species generated from the (C) photopolymerization initiator in the patterned exposure region in the photosensitive resin composition. When the region is cured, a pattern including a cured region and an uncured region is formed. After this exposure step, a development step may be performed as desired to remove the uncured region and form a pattern.

(Exposure process)
In the exposure method of the present invention, an ultraviolet laser is used as a light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  The wavelength that can be used in the present invention is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm is the photosensitive wavelength of the resist. It is preferable in that it matches.

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
Illuminance preferable in the present invention is preferably 10 W / cm ² or more, and more preferably 100 W / cm ² or more.
As the exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available devices such as EGIS (buoy technology) or DF2200G (Dainippon Screen Co., Ltd.) can be used. Other devices are also preferably used.

In the present invention, a pattern having a smooth surface can be formed by exposing a specific photosensitive resin composition by the exposure method described above. The preferable surface roughness of the pattern varies depending on the field to which the present invention is applied, but when applied to a color filter, the surface roughness (Ra value: centerline average roughness) is in the range of 2 nm to 12 nm. More preferably, it is the range of 2 nm-10 nm.
The Ra value can be measured using an AFM (atomic force microscope).
By setting the surface roughness within the above range, various patterns with smooth surfaces can be formed. In addition, since the colored pattern formed thereby has a smooth surface, the contrast, transmittance, etc. of the obtained color filter are improved, and a good image display device can be obtained by including it. .

  The ultraviolet laser has good light parallelism, and pattern exposure can be performed without using a mask during exposure, but the pattern shape is affected by the shape and profile of the output light. Therefore, it is preferable to expose the pattern using a mask because the linearity of the pattern becomes high.

  One feature of the ultraviolet laser is that the illuminance is high, and heat is generated in the exposure process, and the colored pixels may cause uneven curing. In order to control the temperature of the exposure object on which the colored pixels are provided, it is preferable to keep the exposure stage at a constant temperature, and it is necessary to consider the shape of the exposure stage. In addition, since the parallelism of light is high, the influence of the distance to the base material is small, and it is also preferable that the exposure is carried out while being floated by air.

<Photosensitive resin composition>
The photosensitive resin composition for ultraviolet laser exposure of the present invention comprises (A) a resin, (B) an ethylenically unsaturated compound, (C) an oxime ester compound represented by the following general formula (2) or (3) And (D) a photosensitive resin composition containing a thiol compound having a content in the range of 0.2% by mass to 4% by mass with respect to the solid content of the photosensitive resin composition. Yes, preferably (E) a photosensitive resin composition containing a colorant. The photosensitive resin composition will be described in detail below.
The photosensitive resin composition of the present invention may further contain other additives such as a polymer dispersant and a surfactant as desired.

[(A) Resin]
The photosensitive resin composition used in the present invention contains a resin for the purpose of improving film properties and imparting development properties. Here, examples of the resin include alkali-soluble resins, epoxy resins, pigment coating resins, and polymer compounds such as polymer dispersants. In consideration of development with an alkali, it is preferable to include at least an alkali-soluble resin. These resins are described in detail below.

  The alkali-soluble resin used in the present invention is a linear organic polymer, and at least one molecule in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

  More preferable as the alkali-soluble resin are polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, croton as described in JP-A Nos. 59-53836 and 59-71048. Acrylic polymers such as acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added The thing of a copolymer is mentioned.

  The acid value is preferably in the range of 10 mgKOH / g to 200 mgKOH / g, preferably 30 mgKOH / g to 180 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Examples of the alkyl (meth) acrylates and aryl (meth) ^{_{acrylate, CH 2 = C (R 11}} ) (COOR 13) ^{[wherein, R 11} represents a hydrogen atom or an alkyl group of 1 to 5 carbon ^{atoms, R 13} Represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferable. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. A compound in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. is used as a copolymerization component. Acrylic copolymer.

As the vinyl compound, CH ₂ = CR ¹¹ R ¹² [wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. . Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
Other monomers that can be copolymerized can be used singly or in combination of two or more. Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

As described above, the acrylic resin has an acid value in the range of 20 mgKOH / g to 200 mgKOH / g. If the acid value is 200 mgKOH / g or less, the acrylic resin does not become too soluble in alkali, and the appropriate development range (development latitude) can be prevented from becoming narrow. On the other hand, if it is 20 mgKOH / g or more, the solubility in alkali is unlikely to be reduced, so that it is possible to prevent the development time from being prolonged.
In addition, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used to realize a viscosity range that is easy to use in the process of applying the photosensitive resin composition, and to ensure the film strength. Therefore, it is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

  Moreover, in order to improve the crosslinking efficiency of the photosensitive resin composition usable in the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin having no polymerizable group. A polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting. Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as each molecule contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond. .

(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group A polymerizable double bond-containing acrylic resin, (2) an unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule,
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyurethane acrylic oligomer, Diamond Shamrock Co.). Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).
As addition amount of alkali-soluble resin, it is preferable that it is the range of 3-30 mass% in the total solid of the photosensitive resin composition, and 5-20 mass% is more preferable.

In preparing the photosensitive resin composition, it is preferable to add the following epoxy resin in addition to the alkali-soluble resin. Examples of the epoxy resin include compounds having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolak type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Toto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103, etc. (above, manufactured by Nagase Kasei Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (above, Daicel) In addition, bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.

  Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC Corporation) can also be used. Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Toto Kasei Co., Ltd.), Denacol EM-125, etc. As the biphenyl type, 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl and the like, and as the alicyclic epoxy compound, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT -302, GT-401, GT-403, EHPE-3150 (above, manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. (above, Toto Kasei Co., Ltd.) ), Epiclon 430, 673, 695, 850S, 4032 Or more, manufactured by DIC (Ltd.)), and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is deteriorated.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl. -4,4 'diglycidyl biphenyl, celoxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

In the present invention, the resin having an epoxy ring in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin not having an epoxy ring without adding an epoxy resin separately as described above. The alkali-soluble resin having an epoxy ring can be developed with an alkali developer and further has thermosetting properties.
Such a resin is obtained, for example, by copolymerizing methacrylic acid, glycidyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and styrene.

[(B) ethylenically unsaturated compound]
The photosensitive resin composition used in the present invention contains (B) an ethylenically unsaturated compound.
The ethylenically unsaturated compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one, preferably two or more terminal ethylenically unsaturated bonds. Selected from compounds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (V)
(However, R ⁴ and R ⁵ each independently represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these ethylenically unsaturated compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final photosensitive material. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the colored image portion, that is, the photosensitive resin composition layer, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic ester, methacrylic ester, A method of adjusting both sensitivity and strength by using a styrene compound or a vinyl ether compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection and use method of the addition polymerization compound is also an important factor for the compatibility with other components in the photosensitive resin composition layer (for example, an alkali-soluble resin and an initiator). The compatibility may be improved by using a combination of two or more, and a specific structure may be selected for the purpose of improving the adhesion to the substrate.

  From the above viewpoints, bisphenol A di (meth) acrylate, bisphenol A di (meth) acrylate EO modified product, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylolethane Tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (Meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO Modified products and the like are mentioned as preferable ones, and as commercially available products, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-TMMT, NK ester A-TMPT, NK ester A-TMM-3 (made by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronic M-402 (above, manufactured by Toagosei Co., Ltd.), V # 802 (Osaka Organic Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (above, Kyoeisha) is preferred.

  Among them, modified bisphenol A di (meth) acrylate EO, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ( (Meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc. are commercially available products such as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), NK ester A-TMMT, NK ester A-TMPT, NK ester A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronic M-309, Aronix M-450, Aronix M-402 (manufactured by Toagosei Co., Ltd.), (manufactured by Osaka Organic Chemical Industry Co., Ltd.) V # 802 is more preferable.

  (B) The content of the ethylenically unsaturated compound is preferably 5% by mass to 55% by mass in the total solid content in the photosensitive resin composition layer of the present invention, and is 10% by mass to 50% by mass. More preferably, it is more preferably 15% by mass to 45% by mass.

[(C) Photopolymerization initiator]
The photosensitive resin composition of the present invention contains (C) a photopolymerization initiator, and particularly needs to contain at least one oxime ester compound represented by the following general formula (2) or (3). .
The photopolymerization initiator is a compound that is decomposed by light and initiates and accelerates the polymerization of the (B) ethylenically unsaturated compound, and preferably has sensitivity to the wavelength of an ultraviolet laser.
The photopolymerization initiator preferably has absorption at the exposure wavelength of the laser, and even when there is no absorption at the wavelength of the ultraviolet laser, it can be adjusted to the wavelength of the ultraviolet laser by using in combination with a sensitizing dye described later. It is possible to have sensitivity. Moreover, the said photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-3070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241. JP, 62-21401, JP 63-70243, 63-298339, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. It is done.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol Forinophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino- Acetophenone derivatives such as 4-morpholinobutyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone And benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl dimethyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4- Di (9-acridinyl) butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di ( 9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9- Acridinyl) dodecane and other di (9-acridinyl) alkanes.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, oxalic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 -Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), And carbonyldi (t-hexylperoxydihydrogen diphthalate).

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include, for example, JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, and JP-A-9-188710. Publications, JP 2000-131837 A, JP 2002-107916 A, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin “Rad Tech '98. Proceeding April 19 -22, 1998, Chicago ”etc., organic boron sulfonium complexes or organic boron described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561. Oxosulfonium complex, JP-A-6-175554 JP, JP-A-6-175553, organoboron iodonium complex, JP-A-9-188710, organoboron phosphonium complex, JP-A-6-348011, JP-A-7-128785, JP Specific examples include organoboron transition metal coordination complexes such as 7-140589, JP-A-7-306527, and JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797 And the compounds described. As commercially available products, Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals are suitable.

  In the present invention, an oxime ester compound represented by the following general formula (2) or (3) is also suitable.

In the general formulas (2) and (3), R ₁ and R ₂ each independently represent a monovalent substituent, X represents a monovalent substituent or a hydrogen atom, and A represents a divalent organic group. Ar represents an aryl group.
Preferred specific examples of the oxime ester compound represented by the above general formula are shown below.

  Among these, the following are particularly preferable from the viewpoint of being easily dissolved in a solvent at the stage of preparing the photosensitive resin composition and having good productivity.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055, 4,069,056, phosphonium salts described in European Patent Nos. 104,143, U.S. Pat. Nos. 339,049, 410,201. And iodonium salts described in JP-A-2-150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297. 442, U.S. Pat. Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013 No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604 Examples thereof include sulfonium salts described in each specification of No. 581. From the viewpoint of stability, it is preferably substituted with an electron-withdrawing group. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As photopolymerization initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oximes Compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl substitution Compounds selected from the group consisting of coumarin compounds are preferred.

  More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  (C) It is preferable that content of a photoinitiator is the range of 0.1 mass%-20 mass% with respect to the total solid in a photosensitive resin composition layer, More preferably, it is 0.5 mass%. It is -15 mass%, Most preferably, it is the range of 1 mass%-10 mass%. Within this range, good sensitivity and pattern formability can be obtained.

[Sensitizing dye]
From the viewpoint of improving sensitivity, it is preferable to add a sensitizing dye to the photosensitive resin composition used in the present invention. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the polymerization initiator component and polymerization reaction of the polymerizable compound thereby.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

  Preferred spectral sensitizing dyes or dyes that can be used in the present invention include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose bengal), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, Chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyllin) Phil, chlorophyllin, center metal-substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

[(D) Thiol Compound]
The thiol compound in the present invention also acts as a co-sensitizer and has an effect of improving adhesion with the substrate. The co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation, or suppressing polymerization inhibition by oxygen of the ethylenically unsaturated compound.
Specific examples of the thiol compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate ( PETP), mercaptopropionic acid derivatives such as THEIC-BMPA represented by the following formula; ethylene glycol bisthioglycolate (EGTG), butanediol bisthioglycolate (BDTG), hexanediol bisthioglycolate (HDTG), triglyceride Thioglycolic acid derivatives such as methylolpropane tristhioglycolate (TMTG) and pentaerythritol tetrakisthioglycolate (PETG); 1,2-benzenedithiol, 1,3-benzene Thiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2 ′-(ethylenedithio) diethanethiol, meso-2,3-dimercaptosuccinic acid, p- Examples include thiols such as xylenedithiol and m-xylenedithiol; mercaptoethers such as di (mercaptoethyl) ether. These can be used alone or in combination of two or more.

  As for the thiol compound used by this invention, what is represented by the following general formula (I) is more preferable.

In general formula (I), R represents a hydrogen atom, an alkyl group, or an aryl group, and A ² represents an atomic group that forms a heterocycle with N═C—N.

In general formula (I), R represents an alkyl group or an aryl group.
Examples of the alkyl group include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, linear groups having 1 to 12 carbon atoms, and 3 to 12 carbon atoms. More preferred are branched alkyl groups and cyclic alkyl groups having 5 to 10 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like.

  Examples of the aryl group include a monocyclic structure, one to three benzene rings forming a condensed ring, and a benzene ring and a five-membered unsaturated ring forming a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable.

  These alkyl groups and aryl groups may further have a substituent. Examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and the number of carbon atoms. A linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, and 2 carbon atoms -20 alkoxycarbonyloxy group, aryloxycarbonyloxy group having 7-20 carbon atoms, carbamoyloxy group having 1-20 carbon atoms, carbonamido group having 1-20 carbon atoms, 1-20 carbon atoms Sulfonamide group, carbamoyl group having 1 to 20 carbon atoms, sulfamoyl group, substituted sulfamoyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon atom An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an N-acylsulfamoyl group having 1 to 20 carbon atoms, and 1 carbon atom -20 N-sulfamoylcarbamoyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C2-C20 alkoxycarbonylamino group, C7-20 Aryloxycarbonylamino group, amino group, substituted amino group having 1 to 20 carbon atoms, imino group having 1 to 20 carbon atoms, ammonio group having 3 to 20 carbon atoms, carboxyl group, sulfo group, oxy group, Mercapto group, alkylsulfinyl group having 1 to 20 carbon atoms, arylsulfinyl group having 6 to 20 carbon atoms, and 1-2 carbon atoms Alkylthio group, arylthio group having 6 to 20 carbon atoms, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, sulfamoylamino group A substituted sulfamoylamino group having 1 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms, an isocyanate group, an isocyanide group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, A nitro group, an onium group, etc. are mentioned.

In General Formula (I), A ² represents an atomic group that forms a heterocycle with N═C—N.
Examples of atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
The heterocyclic ring formed by A ² and N═C—N may further have a substituent, and the substituent that can be introduced is a substituent that can be introduced into the alkyl group or aryl group. The same thing is mentioned.

  Moreover, as a thiol compound, More preferably, it is represented by the following general formula (II) or general formula (III).

In general formula (II), R ¹ represents an aryl group, and X ¹ represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

In the general formula (III), ^{R 2} represents an alkyl group, or aryl group, ^{X 1} has the same meaning as ^{X 1} in the general formula (II).

  As a halogen atom in general formula (II) and (III), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

  As the alkoxy group in the general formulas (II) and (III), methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group Phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, ant Loxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group Group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group and the like.

The alkyl group in general formula (II) and (III) is synonymous with the alkyl group represented by R of general formula (I), and its preferable range is also the same.
Moreover, the aryl group in general formula (II) and (III) is synonymous with the aryl group represented by R of general formula (I), The preferable range is also the same.

  Each group in the general formulas (II) and (III) may further have a substituent, and the substituent can be introduced into the alkyl group or aryl group represented by R in the general formula (I). These are the same as those listed as examples of the substituent.

In general formulas (II) and (III), X ¹ is more preferably a hydrogen atom from the viewpoint of solubility in propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA as appropriate).
In general formula (II), R ¹ is most preferably a phenyl group from the viewpoints of sensitivity and PGMEA solubility.
In general formula (III), R ² is more preferably a methyl group, an ethyl group, a phenyl group, or a benzyl group from the viewpoints of sensitivity and PGMEA solubility.

  Of the general formulas (II) and (III), the compound represented by the general formula (III) is most preferable from the viewpoint of PGMEA solubility.

  These thiol compounds are described in J. Org. Appl. Chem. , 34, 2203-2207 (1961).

  In the photosensitive resin composition of the present invention, the compound represented by the general formula (I) may be used singly or in combination of two or more, or represented by the general formula (II). A compound selected from the following compounds may be used in combination with a compound selected from the compounds represented by formula (III):

In the present invention, the content of the thiol compound in the photosensitive resin composition is 0. 0 to the solid content of the photosensitive resin composition. Ru 2 to 4% by mass. Within this range, the polymerizability is not impaired, which is preferable.

[(E) Colorant]
When forming a coloring pattern with the photosensitive resin composition of this invention, it is preferable that a coloring agent is contained in the photosensitive resin composition.
As the colorant, dyes and pigments can be appropriately selected and used. From the viewpoint of heat resistance and the like, a pigment is more preferable.

The pigment used as the colorant may be an inorganic pigment or an organic pigment, but it is preferable to use a pigment having a particle size as small as possible from the viewpoint of high transmittance. The average particle size is preferably 10 nm to 100 nm, and more preferably 10 nm to 50 nm.
In the photosensitive resin composition used in the present invention, by using a polymer dispersant described later, the pigment dispersibility and dispersion stability are improved even when the pigment size is small. A colored pixel having excellent color purity can be formed even if it is thin.

  Furthermore, in the present invention, among the pigments contained in the photosensitive resin composition, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% in the total amount of the pigment, and the primary particles. The proportion of the pigment having a diameter exceeding 0.08 μm is preferably less than 5% in the total amount of the pigment.

When the ratio of the pigment having a primary particle diameter of less than 0.02 μm is less than 10%, the heat resistance and chromaticity change can be prevented, and the ratio of the pigment having a primary particle diameter exceeding 0.08 μm is 5 When it is less than%, the contrast is good, the temporal stability of the photosensitive resin composition is good, and further, foreign matter failure can be prevented.
The proportion of the pigment having a primary particle size of less than 0.02 μm is preferably less than 5% from the viewpoints of heat resistance and chromaticity change prevention.
The proportion of the pigment having a primary particle diameter exceeding 0.08 μm is preferably less than 3% from the viewpoint of improving the contrast.

  The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, the TEM photograph is subjected to image analysis to examine the particle size distribution. For example, the particle size distribution can be grasped by measuring the total number of particles in the observation sample at 3 to 100,000 times and the number of pigment particles less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder is observed with a transmission electron microscope at 3 to 100,000 times, photographed, the major axis of 1000 primary particles is measured, less than 0.02 μm, and more than 0.08 μm Calculate the percentage of primary particles. This operation was performed for a total of three locations by changing the location of the pigment powder, and the results were averaged.

  Examples of the inorganic pigment that can be used as a colorant for forming a colored pattern (colored pixel) include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium And metal oxides such as lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

  C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 4, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a pigment for the red phase (R), an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment A pigment or a mixture with a perylene red pigment, an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be 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 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is less than 100: 4, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  In addition, as a pigment for the green phase (G), a halogenated phthalocyanine pigment alone or a mixture thereof with a bisazo yellow pigment, quinophthalone yellow pigment, azomethine yellow pigment or isoindoline yellow pigment may be used. Can be used. For example, C.I. I. Pigment Green 7, 36, 37, 58 and 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 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the pigment for the blue phase (B), a phthalocyanine pigment can be used alone or a mixture thereof with a dioxazine purple pigment can be 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 and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  In the present invention, a light shielding layer can be provided. In this case, carbon black, titanium black, metal fine particles, metal oxide, sulfide fine particles, and the like can be used as the (E) colorant. In the color filter, the light shielding layer preferably has an optical density (OD value) of 3.5 or more.

As a material for the light shielding layer, conventionally, as a black colorant, at least two kinds of pigments have been used in combination so as to shield the visible light region. Examples of these pigments include the pigments described in JP 2005-17716 A [0038] to [0040] and JP 2005-17521 A [0080] to [0088]. The formation of the used light shielding layer is disclosed in JP-A-7-271020.
In order to further increase the light shielding effect, in Japanese Patent Laid-Open No. 2000-147240, Japanese Patent Laid-Open No. 2000-143985, Japanese Patent Laid-Open No. 2005-338328, Japanese Patent Laid-Open No. 2006-154849, etc., carbon black, titanium black, graphite or the like is a suitable light shielding material. Has been developed as. From the viewpoint of light shielding properties and cost, carbon black is preferable as one of the light shielding materials.

As an example of carbon black, pigment black 7 (carbon black) is preferable. Examples of the carbon black include carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, #M manufactured by Mitsubishi Chemical Corporation. 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 , Diamond black SH, diamond black SHA, diamond black LH, diamond black H, diamond black HA, diamond black SF, diamond black N550M, diamond black E, diamond black G, diamond black R, diamond black N760M, diamond black LP; company made of carbon black Color black FW200, Color black FW2, Color black FW1, Color black FW18, Color black S170, Color black S160, Special Black6, Special Black5, Special Black4, Special Black4A, Printex U, PrintexV, Printex 140U, Printex 140V, rintex 35; carbon black REGAL 400, REGAL 400R, REGAL XC72, VULCAN XC72R, MOGUL L, MONARCH 1400, MONARCH 1000, BLACK PEARLS 1400, carbon black SUNBLACK900, 3010, manufactured by Asahi Carbon Co., Ltd. 970, etc. can be mentioned. Also preferred are those coated with a polymer compound in order to increase the electric resistance. The preferred single particle size of these carbon blacks is 10 to 100 nm, more preferably 10 to 50 nm.
These are used singly or in combination as required. For example, carbon black alone, a mixture of organic pigments, combined use of carbon black and organic pigments, carbon black and titanium black, and the like.

  As content of (E) coloring agent in the photosensitive resin composition used for this invention, 25 mass%-75 mass% are preferable with respect to the total solid (mass) of this composition, and 32 mass%. -70 mass% is more preferable. When the content of the colorant is within the above range, the color density is sufficient to ensure excellent color characteristics.

  In the present invention, it is particularly preferable to use an organic pigment as a colorant and to coat the pigment with a polymer compound in the pigment miniaturization step or dispersion step. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles Further, it is possible to use a coated pigment excellent in dispersion stability in which primary particles are stably maintained.

  A coated pigment which is a preferred embodiment in the present invention is a pigment coated with a polymer compound, but the coating is a new interface of a highly active pigment formed by miniaturization, and a heterocyclic ring is present in the side chain. It is considered that a coating pigment having higher dispersion stability can be obtained because a strong coating layer of the polymer compound is formed by a strong electrostatic action with the polymer compound having the above. That is, in the present invention, the coated polymer compound is hardly liberated even when the pigment after coating treatment is washed with an organic solvent that dissolves the polymer compound.

  The coated pigment as used in the present invention is one in which pigment particles such as organic pigments are coated with a polymer compound having a polar group such as a heterocyclic ring in the side chain, and the polymer compound is a part of the pigment particle surface or By being firmly coated all over, a higher dispersion stability effect can be obtained, which is different from that obtained by adsorbing a general polymer dispersant to a pigment. This covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent described below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a surface-coated pigment as in the present invention, the liberation rate Is very small, 30% or less.

  The pigment after the coating treatment is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours using a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. And calculated as “mass of the polymer compound used in the initial treatment”. Separately, the pigment is washed with 1-methoxy-2-propanol, and the obtained liberation amount is divided by the “mass of the polymer compound used in the initial treatment” to obtain the liberation rate (%). .
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. A preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The coating treatment is preferably performed at the same time in the step of refining the pigment. Specifically, i) the pigment, ii) the water-soluble inorganic salt, and iii) a small amount of water-soluble that does not substantially dissolve ii). An organic solvent, and iv) a step of adding a polymer compound and mechanically kneading with a kneader or the like (referred to as a salt milling step), adding this mixture into water, stirring the mixture with a high-speed mixer or the like to form a slurry, The slurry is filtered, washed with water, and dried if necessary.

  The salt milling described above will be described more specifically. First, a small amount of iii) a water-soluble organic solvent is added as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is poured into water. Stir with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. When dispersed in an oily varnish, the treated pigment before drying (referred to as a filter cake) can be dispersed in the oily varnish while removing water by a method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

During salt milling, iii) by using an organic solvent in combination with iv) at least partly soluble resin, the pigment is agglomerated during drying, and the surface is further coated with iv) at least partly soluble resin. Can be obtained.
Note that iv) the polymer compound may be added at the initial stage of the salt milling process, or may be added separately. It is also possible to add in the dispersion step.

  The polymer compound used for coating the pigment may be anything as long as it has an adsorptive group for the pigment. In particular, those coated with a polymer compound having a heterocyclic ring in the side chain are preferred. Such a polymer compound is preferably a monomer represented by the following general formula (IV) or a polymer containing a polymer unit derived from a monomer comprising a maleimide or a maleimide derivative. A polymer containing a polymer unit derived from the monomer represented by formula (IV) is particularly preferable.

In the general formula (IV), R ⁶ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁷ represents a single bond or a divalent linking group. Y ¹ represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Z ¹ represents a group having a nitrogen-containing heterocyclic structure.

As the alkyl group for R ⁶ , an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group represented by R ⁶ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific preferred alkyl groups represented by R ⁶ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ⁶ is most preferably a hydrogen atom or a methyl group.

In general formula (IV), R ⁷ represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
The alkylene group represented by R ⁷ may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ⁷ include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ⁷ has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ⁷ include —O—, —S—, —C (═O) O—, —CONH—, and —C (═O) S at the terminal of the above alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z ¹ via the heteroatom or a partial structure containing a heteroatom.

In the general formula (IV), Z ¹ represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

Z ¹ is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formulas (2), (3), and (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  Specific examples of these compounds include the following MA-1 to MA-13 and the following M-1 to M-33, but the present invention is not limited thereto.

  In addition to the MA-1 to MA-13 and M-1 to M-33, the following compounds can be exemplified.

Even in the case of using the above-described coated pigment, it is more preferable to disperse the pigment using at least one dispersant and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101,103,106,108,109,111,112,116,130,140,142,162 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

  A pigment derivative is added to the above-described pigment dispersion composition as necessary. The pigment is introduced into the curable composition as fine particles by adsorbing a pigment derivative having a part having affinity for the dispersant or a polar group to the pigment surface and using it as an adsorption point of the dispersant. The re-aggregation can be prevented, and it is effective for constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, the dispersion can be favorably performed while the viscosity is kept low, the dispersion stability after dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The dispersion method can be performed, for example, by finely dispersing a pigment and a dispersant previously mixed with a homogenizer or the like using a bead disperser using zirconia beads or the like.

In the present invention, when a dye is used as the colorant, a photocurable composition that is uniformly dissolved is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. 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-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

〔solvent〕
The photosensitive resin composition used in the present invention can generally be prepared using a solvent. The pigment dispersion composition described above is also prepared using a solvent.
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, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, -2-oxypropionic acid alkyl esters such as ethyl oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropion) Acid methyl, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methyl Ethyl propionate, etc.), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butanediol diacetate 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, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n -Propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether Acetate, tripropylene glycol mono n-butyl ether, tripropylene glycol methyl ether acetate and the like;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether,
Aromatic hydrocarbons such as toluene and xylene are exemplified.

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, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently.

[Other additives]
In addition to the above components, various known additives can be used in the photosensitive resin composition used in the present invention depending on the purpose.
Hereinafter, such additives will be described.

(Surfactant)
When the pigment concentration is increased, the thixotropy of the coating solution generally increases, so film thickness unevenness after the photosensitive resin composition is applied or transferred onto the substrate to form the photosensitive resin composition layer (colored layer coating film). It is easy to produce. In particular, in the formation of the photosensitive resin composition layer (colored layer coating film) by the slit coating method, the coating liquid for forming the photosensitive resin composition layer is leveled before drying to form a uniform thickness coating film. is important. For this reason, it is preferable to contain an appropriate surfactant in the photosensitive resin composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acid ester There are nonionic surfactants such as stealth and polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, Adeka Pluronic series, Adecanol series i, Tetronic series (above ADEKA Co., Ltd.), Emulgen series, Rheodor series (above Kao Co., Ltd.), Eleminor series, Nonipol Series, Octapole series, Dodecapole series, New Pole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.), etc. is there. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, F780F, F781F, R30, R08, F482, F554 (DIC Corporation) ), FLORARD FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351 352, 801, 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.).

  These surfactants are preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the coating liquid for forming the photosensitive resin composition layer. When the amount of the surfactant exceeds 5 parts by mass, surface roughness due to coating and drying tends to occur, and smoothness tends to deteriorate.

  Further, in order to promote the alkali solubility of the uncured part and further improve the developability of the photosensitive resin composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. be able to. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

(Alkoxysilane compound)
In the photosensitive resin composition used in the present invention, an alkoxysilane compound, particularly a silane coupling agent, can be used from the viewpoint of improving adhesion to the substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material, and (meth) acryloyl or phenyl that exhibits affinity by interacting or forming a bond with an organic resin. , Mercapto, epoxy, and aminosilane are preferable, and (meth) acryloylpropyltrimethoxysilane is more preferable among them. Examples of such materials include KBM-303, KBM-402, KBM-403, KBM-502, KBM-503, KBM-802, KBM-803, and KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can do.
The addition amount in the case of using a silane coupling agent is preferably in the range of 0.2% by mass to 5.0% by mass in the total solid content in the photosensitive resin composition used in the present invention. More preferably, it is 5 mass%-3.0 mass%.

(Co-sensitizer)
The photosensitive resin composition used in the present invention preferably contains a co-sensitizer other than the above-described (D) thiol compound as desired. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation, or suppressing the inhibition of polymerization of the ethylenically unsaturated compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Another example of the co-sensitizer includes sulfides such as disulfide compounds disclosed in JP-A-56-75643, and specifically includes 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is in the range of 0.1% by mass to 30% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. Is preferable, the range of 0.1% by mass to 25% by mass is more preferable, and the range of 0.5% by mass to 20% by mass is still more preferable.

(Polymerization inhibitor)
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive resin composition.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, phenoxazine, phenothiazine and the like.

  The addition amount of the thermal polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the photosensitive resin composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide can be added to prevent polymerization inhibition due to oxygen and can be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . As for the addition amount of a higher fatty acid derivative, 0.5 mass%-10 mass% are preferable with respect to solid content of the photosensitive resin composition.

(Plasticizer)
Furthermore, in this invention, in order to improve the physical property of the photosensitive resin composition, you may add an inorganic filler, a plasticizer, etc.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. 10 mass% or less can be added with respect to the total mass of.

  By using the components described above, the photosensitive resin composition in the present invention is cured with high sensitivity by exposure to an ultraviolet laser, and exhibits high adhesion to the substrate. Furthermore, since the film is formed with high sensitivity, the smoothness of the surface is maintained even by high-power exposure with an ultraviolet laser. Therefore, the photosensitive resin composition containing the various components can be preferably used for forming a colored pattern of a color filter by applying it to the method of the present invention.

The photosensitive resin composition for ultraviolet laser exposure and the pattern forming method of the present invention are suitable for a color filter for liquid crystal display devices. Hereinafter, the photosensitive resin composition for ultraviolet laser exposure and the pattern forming method of the present invention will be described as a colored pattern forming composition and a forming method in a method for producing a color filter for a liquid crystal display device. The method is not limited.
<Method for producing color filter for liquid crystal display element>
Although it manufactures by forming a colored pattern using a photosensitive resin composition on a light-transmitting board | substrate, another process can also be provided as needed.

[Pattern formation process]
In the present invention, the colored pattern is formed by forming a photosensitive resin composition layer using a photosensitive resin composition on a light-transmitting substrate (photosensitive resin composition layer forming step), and the photosensitive resin composition layer. Is exposed to a pattern with an ultraviolet laser (exposure process), the exposed photosensitive resin composition layer is developed to remove an uncured region (development process), and the developed photosensitive resin is developed as desired. The composition layer can be formed by baking (baking step). In addition to the above steps, the pattern forming step may further include other steps such as a pre-baking step as necessary.

-Photosensitive resin composition layer forming step-
Examples of the light-transmitting substrate (hereinafter also simply referred to as “substrate”) include, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and transparent conductive films used in liquid crystal display devices and the like. And a photoelectric conversion element substrate used for a solid-state imaging device or the like. Furthermore, a plastic substrate is also possible. In these substrates, a black matrix is formed in a lattice shape or the like, and a colored pattern is formed in an empty portion of the lattice.

  Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface. It is preferable that the substrate is large (generally 1 m or more per side) from the standpoint of achieving the effects of the present invention.

As a method for forming the photosensitive resin composition layer on the substrate, various application methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied. . Of these, slit coating is preferred from the viewpoints of accuracy and speed.
Moreover, the method of transferring on the board | substrate the coating film previously provided and formed by the said application | coating method on the temporary support body can also be applied.
Regarding the transfer method, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 are used. It can be suitably used in the present invention.

The thickness of the photosensitive resin composition layer (for example, coating thickness) is 0.5 μm to 3.0 μm after drying in order to obtain a sufficient color reproduction region and sufficient panel brightness. It is preferable to form so that it may become, and it is more preferable to set it as 1.5 micrometers-2.5 micrometers.
Although the present invention can also be applied to a light shielding layer, the film thickness of the light shielding layer (black matrix) in that case is preferably 0.2 μm to 2.2 μm after drying, preferably 0.8 μm to More preferably, it is 1.5 μm.

-Exposure process-
In the pattern formation method of this invention, the said photosensitive resin composition layer is exposed using an ultraviolet laser as a light source at an exposure process. In this case, pattern exposure may be performed through a mask, or exposure may be performed in a pattern with the focus of exposure light being reduced. From the viewpoint of the pattern shape, it is preferable to perform exposure using a mask. Preferred illuminance and exposure amount are as described above.

-Development process-
In the development step, the photosensitive resin composition layer after exposure is developed. The exposed area is cured in a pattern shape, and in the development process, the unexposed part (uncured part) in the above exposure process is removed by elution into an alkaline aqueous solution and photocured by performing an alkali development process. By leaving only the part, a pattern can be formed.

As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is used.
Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkali compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline compounds is 0.001 to 0.001. An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

The development temperature is preferably 20 ° C to 35 ° C, more preferably 23 ° C to 30 ° C. The development time is preferably 30 seconds to 120 seconds, and more preferably 40 seconds to 90 seconds. Among these, a preferable combination of the development temperature and the development time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C. and 40 seconds to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and preferably 0.1 MPa to 0.3 MPa. By selecting these conditions, it is possible to arbitrarily design the pattern shape to be rectangular or forward tapered.

-Baking process-
In the baking process, the developed photosensitive resin composition layer is baked in order to complete the curing of the photosensitive resin composition. The baking method is a continuous or batch-wise process using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., on the substrate having the photosensitive resin composition pattern layer after development and rinsing. This can be done by heating with the formula.
As conditions for baking, the temperature is preferably 150 ° C to 260 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 ° C to 240 ° C. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 30 minutes to 90 minutes.

  In addition, when forming a colored pattern of a plurality of hues such as RGB three hues, a light-shielding layer, etc., the formation, exposure, development, and baking cycles of the photosensitive resin composition layer may be repeated as many times as desired. The formation, exposure, and development of the photosensitive resin composition layer may be performed for each hue, and finally baking may be performed for all hues. As a result, a color filter including colored pixels having a desired hue is produced.

-Other processes-
Before the exposure step, a prebaking step may be provided in order to dry the photosensitive resin composition layer formed by coating or the like.
The prebake temperature of the photosensitive resin composition layer is preferably 60 ° C to 140 ° C, and more preferably 80 ° C to 120 ° C. The pre-bake time is preferably 30 seconds to 300 seconds, and more preferably 80 seconds to 200 seconds.

<Liquid crystal display device>
A color filter for a liquid crystal display device is suitable for producing a liquid crystal display device, and a liquid crystal display device using a color filter produced by the pattern forming method of the present invention can display a high-quality image.
For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)). The liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Issued in 1994 by Industrial Research Co., Ltd.)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”.

The color filter for a liquid crystal display device is particularly effective for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Applicable. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".
In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter for a liquid crystal display element of the present invention can be applied to a liquid crystal display device composed of these known members.
For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi Co., Ltd.) Fuji Chimera Research Institute, published in 2003) ”.

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, 18-24 pages (Yasuhiro Shima), 25-30 pages (Yukiaki Yagi), etc. Have been described.

  When the color filter produced by the pattern forming method of the present invention is used in a liquid crystal display device and combined with a conventionally known three-wavelength tube of a cold cathode tube, a high contrast can be realized. By using a light source (RGB-LED) as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

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. However, the following examples other than Examples 13 to 16, 23, and 26 to 30 all correspond to reference examples.
Unless otherwise specified, “part” and “%” are based on mass.

[Example 1]
<Preparation of photosensitive resin composition (for black matrix)>
-Preparation of carbon black dispersion (K-1)-
A carbon black dispersion (K-1) was prepared according to the following formulation.
・ Carbon black (Color Black FW2 manufactured by Degussa) 26.7 parts ・ Dispersant (Disparon DA7500 manufactured by Enomoto Kasei Co., Ltd., acid value 26, amine value 40) 3.3 parts ) Copolymer (weight average molecular weight 30,000, 50% solution of propylene glycol monomethyl ether acetate) 10 parts ・ Propylene glycol monomethyl ether acetate 60 parts

The above components were stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 8 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain a carbon black dispersion (K-1). It was.
Using the obtained carbon black dispersion (K-1), a photosensitive resin composition (for black matrix) CK-1 was prepared according to the formulation shown in Table 1. Numerical values in Table 1 indicate mass ratios.

Details of each component in Table 1 are as follows.
Resin solution C-2: benzyl methacrylate / methacrylic acid (= 85/15 molar ratio) copolymer, (Mw 10,000, 50% solution of propylene glycol monomethyl ether acetate)
UV curable resin C-3: trade name Cyclomer P ACA-250 manufactured by Daicel Chemical Industries, Ltd. [Acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain, propylene glycol monomethyl ether acetate Solution (solid content: 50%)]
-Ethylenically unsaturated compound C-5: Trade name TO-1382 Toagosei Co., Ltd. (mainly a monomer having a pentafunctional acryloyl group in which a part of the terminal OH group of dipentaerythritol pentaacrylate is substituted with a COOH group component.)
Photopolymerization initiator C-7: trade name “OXE-02” Ciba Specialty Chemicals Co., Ltd./thiol compound 1; mercaptobenzthiazole: trade name “Accel M” Kawaguchi Chemical Co., Ltd./surfactant C-8: Trade name “Mega-Fak R30”, manufactured by DIC Corporation, solvent PGMEA: propylene glycol monomethyl ether acetate, solvent EEP: 3-ethoxyethyl propionate

<Formation of black matrix substrate>
-Photosensitive resin composition layer forming step-
Using the slit coater (model number HC6000, manufactured by Hirata Kiko Co., Ltd.) on the glass substrate (Corning Millennium 0.7 mm thickness), the distance between the slit and the glass substrate is obtained. Was set to 150 μm, the amount of discharge was adjusted so that the film thickness after post-baking was 1.2 μm, and coating was performed at a coating speed of 120 mm / sec.

-Pre-bake process, exposure process-
Next, after performing heating (pre-bake treatment) at 90 ° C. for 120 seconds using a hot plate, in an exposure apparatus using an Nd: YAG laser (Pulseo, third harmonic 355 nm, manufactured by Spectra-Physics), The optical system was adjusted so that the irradiation energy was about 1 mJ / cm ² with respect to the surface of the photosensitive resin composition layer, and exposure was performed through a photomask. Pattern formation was performed by performing 20 times of multiple exposure with respect to the photosensitive resin composition layer surface.

-Development process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0 part of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (1 part of CDK-1), The shower pressure was set to 0.20 MPa with 99 parts diluted pure water (25 ° C.), developed for 50 seconds, washed with pure water, and a substrate provided with a developed black matrix was obtained.

-Bake (post-bake) process-
Next, a post-baking process is performed in a clean oven at 240 ° C. for 40 minutes, and an opening serving as a colored pixel forming region is 90 μm × 200 μm in size, a black matrix thickness of 1.2 μm, and a black matrix line width of about 22 μm. A substrate having a black matrix was formed.
When the optical density (OD value) of the completed black matrix was measured using X-Rite 361T (V) (manufactured by Sakata Inx Engineering Co., Ltd.), it was 4.2.

[Examples 2, 4, 6]
-Synthesis of polymer compounds having a heterocyclic ring in the side chain-
(Synthesis Example 1: Synthesis of Polymer 1)
M-11 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer ( The mixture was stirred with Shinto Kagaku Co., Ltd. (Three-One Motor) and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after heating and stirring for 3 hours, a 30% solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer 1 by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.

(Synthesis Example 2: Synthesis of Polymer 2)
M-6 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The mixture was stirred with a scientific (three-motor) and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.80 g of V-65 was further added, and after heating and stirring for 3 hours, a 30% solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained polymer 2 by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. From the titration with sodium hydroxide, the acid value per solid content was 99 mgKOH / g.

  Among the oxime compounds used together with the thiol compound in the present invention, detailed synthesis methods for the non-commercial oxime compounds 3, 4, and 5 are shown below.

(Synthesis Example 3: Synthesis of Oxime Compound 3)
First, Compound A is synthesized according to the following scheme.
Ethylcarbazole (100.0 g, 0.512 mol) is dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) is added. Subsequently, o-tolyl chloride (81.5 g, 0.527 mol) is added dropwise over 40 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) is added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) is added dropwise over 40 minutes, and the mixture is warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water is cooled to 0 ° C., and the reaction solution is added dropwise. The precipitated solid was filtered with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (yield 164.4 g, yield 77%) having the following structure.

Next, Compound B is synthesized using Compound A according to the following scheme.
Compound A (20.0 g, 47.9 mmol) is dissolved in 64 ml of tetrahydrofuran (hereinafter referred to as THF), and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4. 79 mmol) is added. Subsequently, sodium hydroxide (2.0 g, 50.2 mmol) is added to the reaction solution and refluxed for 2 hours. Next, after cooling to 0 ° C., sodium methylate 28% methanol solution (manufactured by Nippon Shokubai Co., Ltd .: SM-28) (11.1 g, 57.4 mmol) was added dropwise over 20 minutes, and the temperature was raised to room temperature. And stir for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite (6.73 g, 57.4 mmol) is added dropwise over 20 minutes, the temperature is raised to room temperature, and the mixture is stirred for 3 hours. The reaction solution is diluted with 120 ml of acetone and added dropwise to a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. The precipitated solid was filtered with suction and washed with distilled water. Subsequently, recrystallization was performed with acetonitrile to obtain Compound B having the following structure (yield: 17.0 g, yield: 64%).

Subsequently, using compound B, oxime compound 3 is synthesized according to the following scheme.
Compound B (18.0 g, 32.4 mmol) was dissolved in 90 ml N-methylpyrrolidone and triethylamine (3.94 g, 38.9 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (3.05 g, 38.9 mmol) is added dropwise over 20 minutes, and then the temperature is raised to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then dried to give oxime compound 3 having the following structure (yield 19.5 g, Yield 99%).

The structure of the obtained oxime compound 3 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl ₃ ): 8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.81 (d, 1H , J = 8.0 Hz), 7.51-7.24 (m.10H), 7.36 (q, 2H, 7.4 Hz), 3.24-3.13 (m, 4H), 2.36. (S, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4 Hz).

(Synthesis Example 4: Synthesis of Oxime Compound 4)
First, compound A is synthesized in the same manner as the synthesis method of oxime compound 3.
Compound A (86.5 g, 209 mmol) was dissolved in 277 ml of THF, 2,6-dimethylbenzenethiol (30 g, 217 mmol) and sodium iodide (3.0 g, 20.0 mmol) were added, and the mixture was stirred at 40 ° C. Subsequently, sodium hydroxide (8.66 g, 216 mmol) was added to the reaction solution, and the mixture was refluxed at 40 ° C. for 2 hours. Next, after cooling to 0 ° C., sodium methylate 28% methanol solution (manufactured by Nippon Shokubai Co., Ltd .: SM-28) (48 g, 249 mmol) was added dropwise over 20 minutes, and the temperature was raised to room temperature for 2 hours. Stir. Next, after cooling to 0 ° C., isopentyl nitrite (29.3 g, 250 mmol) was added dropwise over 20 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was diluted with 105 ml of acetone and washed with a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. After extracting the organic phase with ethyl acetate, methanol was added and the precipitated solid was filtered with suction. Subsequently, recrystallization was performed with acetonitrile to obtain Compound C having the following structure (yield: 76.6 g, yield: 67%).

Subsequently, oxime compound 4 is synthesized by the following scheme using compound C.
Compound C (46.4 g, 85 mmol) was dissolved in 230 ml of ethyl acetate and triethylamine (10.3 g, 101 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (8.0 g, 102 mmol) was added dropwise over 20 minutes, and then the mixture was warmed to room temperature and stirred for 1 hour. The reaction solution was washed with 1000 ml of distilled water cooled to 0 ° C. and extracted with ethyl acetate. After concentration under reduced pressure, the solution was added dropwise to 100 ml of distilled water, and the precipitated solid was subjected to suction filtration, washed with 150 ml of isopropyl alcohol cooled to 0 ° C., dried, and then dried to give oxime compound 4 having the following structure (yield 49.7 g, yield 99). %).

The structure of the obtained oxime compound 4 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl ₃ ): 8.84 (s, 1H), 8.57 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.08 (d, 1H , J = 8.0 Hz), 7.446-7.24 (m, 4H), 7.48 (q, 2H, 7.4 Hz), 7.09 (d, 3H), 3.10-2.90. (M, 4H), 2.50 (s, 6H), 2.35 (s, 3H), 2.17 (s, 3H), 1.48 (t, 3H, 7.4 Hz)

(Synthesis Example 5: Synthesis of oxime compound 5)
To a 200 ml three-necked flask, 18.63 g (0.1 mol) of phenyl sulfide, 75 ml of carbon disulfide, and 14.24 g (0.1 mol) of 4-chlorobutyryl chloride were added and cooled to 0 ° C. while substituting with nitrogen gas. Thereafter, 13.47 g (0.1 mol) of aluminum (III) chloride was added little by little. After completion of the addition, the mixture was stirred at room temperature for 2 hours, and the reaction solution was poured into 100 ml of 0.5N aqueous hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed in turn with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. Magnesium sulfate was removed by filtration, the solvent was concentrated by an evaporator, and then purified by silica gel column chromatography to obtain 22.45 g (yield 77%) of compound D having the following structure.

  To a 300 ml three-necked flask was added 10.95 g (0.0757 mol) of 4-chlorothiophenol, 30 ml of THF, 20 ml of distilled water, 3.03 g (0.0757 mol) of sodium hydroxide, and 1.26 g (0.0076 mol) of potassium iodide. And stirred at room temperature. A solution prepared by dissolving 22 g (0.0757 mol) of the compound D obtained above in 20 ml of THF was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction solution was heated at 80 ° C. and stirred for 4 hours. Then, after allowing to cool to room temperature, the reaction solution was extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 18.12 g (yield 60%) of Compound E having the following structure.

To a 100 ml three-necked flask, 15 ml of methanol and 1.53 g (0.028 mol) of sodium methoxide were added, and the system was purged with nitrogen gas. After cooling the reaction solution to 0 ° C., a solution of 10.69 g (0.0268 mol) of Compound E obtained above in 20 ml of THF was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and the reaction solution was kept at 10 ° C. using a thermostatic layer, and a solution of 3.31 g (0.028 mol) of isopentyl nitrite dissolved in 10 ml of THF was dropped over 30 minutes. . After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours, and then the reaction solution was poured into a solution of distilled water 100 ml / acetic acid 3.0 ml cooled to 0 ° C.
Thereafter, the mixture was extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 7.11 g (yield 62%) of Compound F having the following structure.

To a 100 ml three-necked flask, 6.51 g (0.0152 mol) of the compound F obtained above and 20 ml of THF were added, and the system was purged with nitrogen gas and cooled to 0 ° C. with stirring. Thereto, a solution of 2.18 g (0.028 mol) of pyridine in 5 ml of THF and a solution of 1.97 g (0.025 mol) of acetyl chloride in 5 ml of THF were added dropwise simultaneously. After dropwise addition over 15 minutes, the mixture was further stirred at room temperature for 3 hours.
Thereafter, the reaction solution was poured into 200 ml of distilled water, extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dehydrated by adding magnesium sulfate. After filtering magnesium sulfate and concentrating the solvent with an evaporator, purification was performed by silica gel column chromatography to obtain 6.79 g (yield 95%) of oxime compound 5. The chemical structure was confirmed by the following analysis results.

The obtained oxime compound 5 was identified by ¹ H-NMR. The ¹ H-NMR spectrum of the obtained oxime compound 5 is shown.
(Acetone-d6: internal standard TMS) δ [ppm]: 8.05 (d, 2H), 7.59 (m, 2H), 7.52 (m, 3H), 7.39 (m, 4H), 7.25 (d, 2H), 3.31 (t, 2H), 3.13 (t, 2H), 2.19 (s, 3H)

Synthesis of alkali-soluble resin 2 containing a polymerizable group is shown as Synthesis Example 6.
(Synthesis Example 6: Synthesis of alkali-soluble resin 2)
A flask was charged with 20 parts of a styrene / acrylic acid resin having an acid value of 200 and a molecular weight of 5,000, 0.2 part of p-methoxyphenol, 0.2 part of dodecyltrimethylammonium chloride and 40 parts of propylene glycol monomethyl ether acetate. 7.6 parts of 4-epoxycyclohexyl) methyl acrylate was added dropwise and reacted at a temperature of 100 ° C. for 30 hours. The reaction solution was reprecipitated in water and dried to obtain alkali-soluble resin 2. When neutralization titration with KOH was performed, the acid value of the resin was 80 mgKOH / g.

Synthesis of alkali-soluble resin 3 containing a polymerizable group is shown as Synthesis Example 7.
(Synthesis Example 7: Synthesis of alkali-soluble resin 3)
In a reaction vessel, 8.57 parts of 1-methoxy-2-propanol (MFG, manufactured by Daicel Chemical Industries, Ltd.) was added in advance, and the temperature was raised to 90 ° C., 6.27 parts of cyclohexyl methacrylate, 5.15 parts of methacrylic acid, A mixed solution consisting of 1 part of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 8.57 parts of 1-methoxy-2-propanol was placed in a 90 ° C. reaction vessel under a nitrogen gas atmosphere for 2 hours. It was dripped over. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.
Next, 0.025 part of hydroquinone monomethyl ether and 0.084 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 5.41 parts of glycidyl methacrylate was added dropwise over 2 hours. After dripping, after reacting for 4 hours at 90 ° C. while blowing air, an alkali-soluble resin 3 having an ethylenically unsaturated group (solid content acid value; 73 mg KOH / g, Mw; 30,000) 1-methoxy-2-propanol solution (45%) was obtained.
In addition, the weight average molecular weight Mw of this resin was measured using the gel permeation chromatograph (GPC).

Synthesis of alkali-soluble resin 4 containing an epoxy group is shown as Synthesis Example 8.
(Synthesis Example 8: Synthesis of alkali-soluble resin 4)
A flask equipped with a condenser and a stirrer was charged with 7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether, followed by 18 parts of methacrylic acid and 20 parts of glycidyl methacrylate. , 5 parts of styrene, 32 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate and 25 parts of tetrahydrofurfuryl methacrylate were charged with nitrogen, and the solution was stirred gently. The temperature was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization to obtain an alkali-soluble resin 4 solution (solid content concentration = 33.4%). Mw of this resin (B) was 9,000.
In addition, the weight average molecular weight Mw of this resin was measured using the gel permeation chromatograph (GPC).

Synthesis of alkali-soluble resin 5 containing an allyl group is shown as Synthesis Example 9.
(Synthesis Example 9: Synthesis of alkali-soluble resin 5)
54 g of 1-methoxy-2-propanol was placed in a 200 mL three-necked flask equipped with a stirring rod provided with stirring blades, a reflux condenser, and a thermometer, and heated to 70 ° C. under a nitrogen stream. Plunger pump was prepared by dissolving 10.07 g of allyl methacrylate, 1.93 g of methacrylate and 0.185 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 54 g of 1-methoxy-2-propanol. Was dropped into the three-necked flask over 2.5 hours. After completion of dropping, the mixture was further stirred at 70 ° C. for 2 hours. After the heating was completed, the solution was poured into 1 L of water and re-sinked. The precipitate was filtered and then vacuum dried to obtain 9 g (yield 75%) of the polymer compound.
0.01 g of a polymer obtained as a measurement sample of the weight average molecular weight was weighed into a 10 mL volumetric flask, and about 8 mL of THF was added and dissolved at room temperature, and then the total amount was adjusted to 10 mL. This solution was measured using GPC. The weight average molecular weight of the alkali-soluble resin 5 (allyl methacrylate / methacrylic acid copolymer (molar ratio = 80/20)) was 35,000.

(Preparation of coated pigment 1)
Pigment (CI Pigment Red 254 CROMOPHTAL RED BP manufactured by Ciba Specialty Chemicals) 50 g, sodium chloride 500 g, 20 g of the above polymer 1 solution, and diethylene glycol 100 g were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). And kneading for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

(Preparation of coated pigment 2)
In the preparation of the coated pigment 1, C.I. I. Instead of Pigment Red 254, C.I. I. Pigment Green 36 (Monastral Green 6Y-CL manufactured by Nihon Lubrizol Co., Ltd.) was used, Polymer 2 was used in place of Polymer 1, and the coating pigment 2 was prepared in the same manner as the coating pigment 1. did.

-Photosensitive resin composition layer forming step-
(Preparation of pigment dispersion 1)
Pigment dispersion 1 was prepared as follows. That is, with the composition described below, a homogenizer was used and stirred for 3 hours at a rotation speed of 3,000 rpm to prepare a mixed solution, and further bead dispersion using 0.1 mmφ zirconia beads Dispersion treatment was carried out for 8 hours using a machine Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.).

-Coated pigment 1 24 parts-C.I. I. Pigment Red 177 6 parts Dispersbyk 161 manufactured by Big Chemie [30% solution] 16 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer, propylene having a weight average molecular weight Mw of 5000 Glycol methyl ether acetate solution (solid content 50%) 8 parts Propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) 146 parts

(Preparation of photosensitive resin composition CR-1)
Components of the following composition were further added to the obtained pigment dispersion 1, and mixed by stirring to prepare a red (R) photosensitive resin composition CR-1.
Alkali-soluble resin 1: copolymer of benzyl methacrylate and methacrylic acid (molar ratio = 70/30) Weight average molecular weight = 5,000 12 parts Ethylenically unsaturated compound: dipentaerythritol hexaacrylate (Nippon Kayaku ( Co., Ltd., KAYARAD DPHA) 26 parts Photopolymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Hodogaya Chemical Co., Ltd., B-CIM ] 3 parts, photopolymerization initiator: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) (Irgacure OXE01, manufactured by Ciba Specialty Chemicals) 9 parts, photopolymerization Initiator: Diethylaminobenzophenone (EABF, manufactured by Hodogaya Chemical Co., Ltd.) 1 part ・ thiol compound 2: N-phenylmer 1 part of ptbenzimidazole / epoxy compound: (DIC Corporation, Epicron 695) 4 parts / mixed solution of propylene glycol methyl ether acetate and 3-ethoxyethyl propionate (= 80/20 [mass ratio]) 200 parts / polymerization Inhibitor: p-methoxyphenol 0.001 part. Surfactant 1 (30 mass% solution of methyl ethyl ketone in the following structure 1) 1 part

(Photosensitive resin composition layer formation)
The obtained red (R) photosensitive resin composition CR-1 was applied to the black matrix forming surface side of the substrate provided with the black matrix. Specifically, as in the case of forming the photosensitive resin composition layer of Example 1, the slit and the black matrix substrate were formed so that the layer thickness of the photosensitive resin composition layer after post-baking was about 2.0 μm. The coating was performed at a coating speed of 120 mm / second by adjusting the interval and the discharge amount.

-Colored layer pre-baking step, colored layer exposure step-
Next, after performing heating (pre-baking treatment) at 100 ° C. for 120 seconds using a hot plate, with an exposure apparatus using an Nd: YAG laser (Pulseo, third harmonic 355 nm, manufactured by Spectra-Physics), The optical system was adjusted so that the irradiation energy was about 1 mJ / cm ² with respect to the surface of the photosensitive resin composition layer, and exposure was performed through a photomask. Pattern formation was performed by performing 20 times of multiple exposure with respect to the photosensitive resin composition layer surface.

-Colored layer development process, colored layer baking (post-baking) process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0 part of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (1 part of CDK-1), The shower pressure was set to 0.2 MPa with 99 parts of pure water diluted at 25 ° C., developed for 45 seconds, and washed with pure water.
Next, post-baking treatment was performed in a 220 ° C. clean oven for 30 minutes to form a substrate having heat-treated red pixels.

  A green (G) pixel was formed on a substrate having a red pixel by using the photosensitive resin composition CG-1 described below. Furthermore, the blue (B) pixel was also prepared using the photosensitive resin composition CB-1 described below on the substrate having the red pixel and the green pixel.

(Preparation of pigment dispersion 2)
A pigment dispersion 2 was prepared in the same manner except that the pigment content of the pigment dispersion 1 (coated pigment 1, PR254) was changed to the coated pigment 2.

(Preparation of photosensitive resin composition CG-1)
Components of the following composition were further added to the obtained pigment dispersion 2 and mixed by stirring to prepare a green (G) photosensitive resin composition CG-1.
Alkali-soluble resin 1: copolymer of benzyl methacrylate and methacrylic acid (molar ratio = 70/30) Weight average molecular weight = 5,000 12 parts Ethylenically unsaturated compound: dipentaerythritol hexaacrylate (Nippon Kayaku ( Co., Ltd., KAYARAD DPHA) 26 parts Photopolymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Hodogaya Chemical Co., Ltd., B-CIM) ) 3 parts-Photopolymerization initiator: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Specialty Chemicals) Irgacure OXE02) 5 parts / photopolymerization initiator: diethylaminobenzophenone (EABF, Hodogaya Chemical Co., Ltd.) 1 part / thiol Compound 2: N-phenylmercaptobenzimidazole 1 part / epoxy compound: (Epiclon 695 manufactured by DIC) 4 parts / Propylene glycol methyl ether acetate and 3-ethoxyethyl propionate (= 80/20 [mass ratio]) 200 parts of solution, polymerization inhibitor: 0.001 part of p-methoxyphenol, 1 part of surfactant 1

(Preparation of pigment dispersion 3)
The pigment of the coated pigment 2 is C.I. I. Pigment Blue 15: 6 was used to prepare the coated pigment 3, and the pigment dispersion 2 was adjusted by using the coated pigment 3 instead of the coated pigment 2, and the others were adjusted to the coated pigment 2, and the pigment dispersion. A pigment dispersion 3 was prepared in the same manner as in the adjustment of 2.

(Preparation of photosensitive resin composition CB-1)
Components of the following composition were further added to the obtained pigment dispersion 3 and mixed by stirring to prepare a blue (B) photosensitive resin composition CB-1.
Alkali-soluble resin 1: copolymer of benzyl methacrylate and methacrylic acid (molar ratio = 70/30) Weight average molecular weight = 5,000 18 parts Ethylenically unsaturated compound: dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd., KAYARAD DPHA) 32 parts Photopolymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Hodogaya Chemical Co., Ltd., B-CIM) ) 3 parts-Photopolymerization initiator: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Specialty Chemicals) Irgacure OXE02) 5 parts, photopolymerization initiator: diethylaminobenzophenone (EABF manufactured by Hodogaya Chemical Co., Ltd.) 1 part, thiol Compound 2: N-phenyl mercaptobenzimidazole 1 part / epoxy compound: (DIC Corporation, Epicron 695) 4 parts / propylene glycol methyl ether acetate and 3-ethoxyethyl propionate (= 80/20 [mass ratio]) 200 parts of a mixed solution of the polymerization inhibitor: 0.001 part of p-methoxyphenol and 1 part of the surfactant 1

Example 12
(Preparation of photosensitive resin composition)
The following raw materials were mixed to prepare a photosensitive resin composition for a photospacer.
-PGMEA 56 parts-Diethylene glycol ethyl methyl ether 114 parts-Resin A 59.4 parts-DPHA (Thin diluted with PGMEA to a solid content of 76% by mass, manufactured by Nippon Kayaku Co., Ltd.) 21.1 parts-B-CIM (Hodogaya Chemical Co., Ltd.) 2.8 parts EABF (Hodogaya Chemical Co., Ltd.) 0.7 parts Axel M (Kawaguchi Chemical Co., Ltd.) 0.75 parts Surfactant 1 0.3 parts

(Photosensitive resin composition layer formation)
The obtained photosensitive resin composition for photospacers was apply | coated to the color filter formation surface side of the color filter substrate after ITO vapor deposition. Specifically, in the same manner as in Example 1, the interval between the slit and the substrate and the discharge amount were adjusted so that the film thickness of the photosensitive resin composition layer after post-baking was about 4.0 μm, and the coating was performed. The coating was performed at a speed of 120 mm / second.

-Pre-bake process, exposure process-
Next, after performing heating (pre-baking treatment) at 100 ° C. for 120 seconds using a hot plate, with an exposure apparatus using an Nd: YAG laser (Pulseo, third harmonic 355 nm, manufactured by Spectra-Physics), The optical system was adjusted so that the irradiation energy was about 1 mJ / cm ² with respect to the surface of the photosensitive resin composition layer, and exposure was performed through a photomask. Pattern formation was performed by performing 20 times of multiple exposure with respect to the photosensitive resin composition layer surface.

-Development process, baking (post-baking) process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1.0 part of a potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials) (1 part of CDK-1), The shower pressure was set to 0.2 MPa with 99 parts of pure water diluted at 25 ° C., developed for 45 seconds, and washed with pure water.
Next, post-baking treatment was performed for 30 minutes in a 220 ° C. clean oven, and a heat-treated 16 μmφ photo spacer was formed on the black matrix.

[Examples 3, 5, 7-11, 13-25]
Photosensitive resin composition in the same manner as in Examples 2, 4, 6, and 12, with the types and addition amounts of the pigment dispersion, alkali-soluble resin, photopolymerization initiator, and thiol compound being changed as shown in Table 2. Were prepared to produce a substrate having pixels of each color or a color filter substrate having a photo spacer.

Details of the components in Table 2 are as follows.
Oxime compound 1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure OXE02 manufactured by Ciba Specialty Chemicals) )
Oxime compound 2: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) (Irgacure OXE01, manufactured by Ciba Specialty Chemicals)
Biimidazole compound: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (B-CIM manufactured by Hodogaya Chemical Co., Ltd.)
-Thiol compound 1: Trade name "Accel M" manufactured by Kawaguchi Chemical Industry Co., Ltd.-Thiol compound 2: N-phenyl mercaptobenzimidazole

Example 26
Components of the following composition were further added to the pigment dispersion 3 and mixed by stirring to prepare blue (B) photosensitive resin compositions.
Alkali-soluble resin 5: Copolymer of allyl methacrylate and methacrylic acid (molar ratio = 80/20) Weight average molecular weight = 35,000 18 parts Ethylenically unsaturated compound: Pentaerythritol tetraacrylate (Shin Nakamura Chemical Co., Ltd. ( Co., Ltd., NK Ester A-TMMT) 32 parts Photopolymerization initiator: Oxime compound 3 19 parts Thiol compound 2: N-phenyl mercaptobenzimidazole 5 parts Epoxy compound: EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.) 4 parts ・ Propylene glycol methyl ether acetate and 3-ethoxyethyl propionate (= 80/20 [mass ratio]) mixed solution 200 parts ・ Polymerization inhibitor: p-methoxyphenol 0.001 part ・ Surfactant: Mega Fuck F-554 (manufactured by DIC Corporation) 1 part As above Using Ltd. photosensitive resin composition, to prepare a substrate having a blue pixel in the same manner as in Example 6.

[Examples 27 to 30]
A blue (B) photosensitive resin composition was prepared in the same manner as in Example 26 except that the types and addition amounts of the photopolymerization initiator (oxime compound), thiol compound and surfactant were changed as shown in Table 3. A substrate having blue pixels was prepared.

<Production of liquid crystal display device>
An alignment film made of polyimide was further provided on the color filter with a photo spacer obtained as described above.
-Formation of liquid crystal alignment split projections-
A coating liquid for photosensitive resin layer for protrusions having the following formulation A was applied onto the ITO transparent electrode on the color filter by the same slit coater as described above and dried to form a photosensitive resin layer for protrusions.
<Coating liquid for photosensitive resin layer for protrusions: Formulation A>
-Positive resist solution 53.3 parts (FH-2413F, manufactured by FUJIFILM Electronics Materials Co., Ltd.)
・ Methyl ethyl ketone 46.7 parts ・ Surfactant 1 (30% solution of methyl ethyl ketone in structure 1 described above) 0.04 parts

Subsequently, it exposed at 150 mJ / cm < ² > using the mirror projection type exposure machine (model number MPA-8000, Canon Inc. make).
Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying on the photosensitive resin layer for protrusions at 33 ° C. for 30 seconds in a shower type developing device, and an unnecessary portion (exposure) of the photosensitive resin layer for protrusions was exposed. Part) was developed and removed. Then, projections patterned into a desired shape were formed on the ITO transparent electrode of the color filter. Next, the color filter substrate on which the protrusions were formed was baked at 240 ° C. for 50 minutes, so that the height of the color filter was 1.5 μm and the vertical cross-sectional shape (the surface parallel to the normal direction of the glass substrate surface) was obtained. It was possible to form alignment-dividing protrusions having a shape).
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to a black matrix outer frame provided so as to surround the colored pixel group of the color filter, and MVA mode liquid crystal is dropped to form a counter substrate. After the substrates were bonded together and irradiated with UV, the sealant was cured by heat treatment. A liquid crystal cell was thus obtained. A polarizing plate HLC2-2518 (manufactured by Sanritz Co., Ltd.) was pasted on both sides of this liquid crystal cell, and then placed on the back surface side of the liquid crystal cell provided with the polarizing plate by constituting a backlight of a cold cathode tube, A liquid crystal display device was obtained.

[Comparative Examples 1-8]
In place of the thiol compound 2 in the compositions of Examples 2 to 7, Example 12, and Example 1, each was replaced with the same mass of N-phenylglycine (manufactured by Kanto Chemical Co., Inc.), and a comparative photosensitive resin. Compositions were prepared, and Comparative Examples 1 to 6, Comparative Example 7, and Comparative Example 8 were prepared in the same manner as the respective examples to prepare substrates having pixels of each color.

Moreover, about Examples 1-30, it replaces with a Nd: YAG laser, and it is by exposing by 20 mJ / cm < ² > using the proximity exposure machine (Hitachi High-Technologies company make, LE5565A) which uses a high pressure mercury lamp as a light source. Pixel formation was performed. The results are referred to as Comparative Examples 1a to 30a, respectively.
The surface roughness of the photosensitive resin composition layer was determined by the following method using the substrate provided with the light-shielding, RGB colored layer, and transparent layer of Examples and Comparative Examples obtained as described above. evaluated. The results are shown in Table 4 and Table 5.

[Evaluation of surface roughness]
Each surface roughness was measured using AFM (Dimension 3100, manufactured by Digital Instruments). The measurement area was 10 μm square.

[Evaluation of line width stability]
When the development time is further increased from the point of the number of seconds of the development time in which the average line width after development is the most stable (optimum development time) with respect to the change of the development time, the time taken to change by 2 μm The number (number of seconds from the optimum development time) was determined.

  From Tables 4 and 5, from the photosensitive resin composition for ultraviolet light laser and the photosensitive resin composition layer produced by the pattern forming method of the present invention, the surface of the light shielding, RGB colored pixel, transparent layer (photospacer) Is smooth regardless of the type of photopolymerization initiator. Moreover, by producing with the photosensitive resin composition for ultraviolet lasers and the pattern forming method of the present invention, the line width stability of the pattern is increased, a manufacturing margin is generated, and an improvement in productivity can be expected. In contrast, the comparative example formulation lacking the factors of the photosensitive resin composition of the present invention and the comparative example not exposed with the ultraviolet light laser have a large surface roughness and inferior pattern line width stability. . Further, when the liquid crystal display device was assembled using each of the color filters prepared in the examples and comparative examples, the example had less light leakage in a dark place and the image quality was improved.

Claims (11)

(A) a resin, (B) an ethylenically unsaturated compound, (C) a photopolymerization initiator containing at least one oxime ester compound represented by the following general formula (2) or (3) , and (D) photosensitivity The photosensitive resin composition for ultraviolet laser exposure containing the thiol compound of the range of 0.2 mass%-4 mass% with respect to solid content of a photosensitive resin composition.

In general formulas (2) and (3), R ₁ and R ₂ each independently represents a monovalent substituent, X represents a monovalent substituent or a hydrogen atom, and A represents a divalent organic group. , Ar represents an aryl group.   The photosensitive resin composition for ultraviolet laser exposure according to claim 1, wherein the photosensitive resin composition further contains (E) a colorant. The photosensitive resin composition for ultraviolet laser exposure according to claim 1, wherein the (D) thiol compound is a compound represented by the following general formula (1).

In general formula (1), Q represents NR, a sulfur atom, or an oxygen atom. R represents a hydrogen atom, an alkyl group, or an aryl group. A ¹ represents an atomic group that forms a heterocycle with N═C—X.   The photosensitive resin composition for ultraviolet laser exposure according to any one of claims 1 to 3, further comprising at least one biimidazole compound as the (C) photopolymerization initiator. The photosensitive resin composition for ultraviolet laser exposure according to claim 2, wherein the content of the colorant (E) is in the range of 25% by mass to 75% by mass with respect to the total solid content of the photosensitive resin composition. . The photosensitive resin composition for ultraviolet laser exposure according to any one of claims 1 to 5 , wherein the ultraviolet laser is a solid laser or a gas laser. The photosensitive resin composition for ultraviolet laser exposure according to any one of claims 1 to 6 , wherein an exposure wavelength of the ultraviolet laser is in a range of 300 nm to 380 nm. The pattern formation method which exposes the photosensitive resin composition for ultraviolet light laser exposure of any one of Claim 1 to 7 to pattern shape with an ultraviolet light laser, and hardens an exposure area | region. A color filter having a pattern formed by the pattern forming method according to claim 8 . The manufacturing method of the color filter which forms a color filter with the pattern formation method of Claim 8 . A liquid crystal display device comprising the color filter according to claim 9 .