KR20200030567A - Photosensitive coloring composition, cured film, pattern formation method, color filter, solid-state imaging element and image display device - Google Patents

Abstract

Provided is a photosensitive coloring composition capable of forming a cured film excellent in discoloration resistance to a developer. Further, a cured film, a method for forming a pattern, a color filter, a solid-state imaging element, and an image display device are provided. The photosensitive coloring composition has a photopolymerization initiator a whose absorption coefficient of light at a wavelength of 365 nm in methanol exceeds 1.0 × 10 ² mL / gcm, and an absorption coefficient of light at a wavelength of 365 nm in methanol of 1.0 × 10 ² mL / gcm or less, It contains the photopolymerization initiator b which has an extinction coefficient of light of wavelength 254 nm of 1.0 x 10 ³ mL / gcm or more, an alkali-soluble resin, and a color material having a polymerizable group. The content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more.

Description

Photosensitive coloring composition, cured film, pattern formation method, color filter, solid-state imaging element and image display device

The present invention relates to a photosensitive coloring composition. More specifically, it relates to a photosensitive coloring composition used for formation of colored pixels and the like of a color filter. Moreover, it is related with the cured film using a photosensitive coloring composition, the formation method of a pattern, a color filter, a solid-state imaging element, and an image display apparatus.

Recently, with the spread of digital cameras, mobile phones with cameras, and the like, demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has grown significantly. Color filters are used as key devices for displays and optical elements.

The color filter is produced by applying a colored photosensitive composition for forming pixels of each color on a support, pre-baking at about 100 ° C, then forming a pattern for exposure and development, and then post-baking. Post-baking is a heat treatment to promote curing of the film after development, and is performed at a relatively high temperature. For example, in Patent Document 1, post-baking is performed on the film after development at a temperature of 200 ° C or higher.

In recent years, organic electroluminescence (organic EL) formation of an emission color source in an image display device and organic materialization of a photoelectric conversion film in an image sensor have been studied. Many of these members have low heat resistance. Therefore, it is considered to manufacture a color filter at a low temperature. For example, Patent Document 2 includes (i) a step of forming a layer on a substrate using a photosensitive coloring composition, (ii) a step of exposing the photosensitive coloring composition layer to light having a wavelength of 350 nm or more and 380 nm or less, (iii) ) A process of alkali developing the photosensitive coloring composition layer and (iv) a step of exposing the photosensitive coloring composition layer with light having a wavelength of 254 to 350 nm, in this order, as the photosensitive coloring composition, (a) of light having a wavelength of 365 nm in methanol A polymerization initiator having an absorption coefficient of 1.0 × 10 ³ mL / gcm or more, (b) in methanol, an absorption coefficient of light having a wavelength of 365 nm is 1.0 × 10 ² mL / gcm or less, and an absorption coefficient of light having a wavelength of 254 nm is 1.0 × 10 ³ mL / gcm or more polymerization initiator, (c) a compound having an unsaturated double bond, (d) an alkali-soluble resin, and (e) a colorant, the total solid content of the photosensitive coloring composition, (a) the content of the polymerization initiator is 1.5 ~ 10% by mass, (b) containing a polymerization initiator A method for producing a color filter using a photosensitive coloring composition having an amount of 1.5 to 7.5% by mass is described.

Patent Document 1: Japanese Patent Application Publication No. 2015-143330 Patent Document 2: Japanese Patent Application Publication No. 2015-041058

As mentioned above, recently, it is considered to manufacture a color filter at a lower temperature.

On the other hand, when the present inventor conducted a study on a photosensitive coloring composition containing a coloring material and an alkali-soluble resin, when the photosensitive coloring composition was cured at a low temperature to form a cured film, the obtained cured film was discolored with respect to the developer. It was found that the castle tends to be low.

Accordingly, an object of the present invention is to provide a photosensitive coloring composition capable of forming a cured film excellent in discoloration resistance to a developer. In addition, an object of the present invention is to provide a cured film, a method for forming a pattern, a color filter, a solid-state imaging element, and an image display device.

As a result of earnest examination, the present inventors found that a photosensitive coloring composition comprising a specific photopolymerization initiator to be described later and a color material having a polymerizable group can form a cured film excellent in discoloration resistance to a developer even when cured at a low temperature. Thus, the present invention has been completed. That is, the present invention is as follows.

<1> a photopolymerization initiator a whose absorption coefficient of light at a wavelength of 365 nm in methanol exceeds 1.0 x 10 ² mL / gcm, and

A photopolymerization initiator b having an absorption coefficient of light of 365 nm wavelength in methanol of 1.0 × 10 ² mL / gcm or less, an absorption coefficient of light of wavelength 254 nm of 1.0 × 10 ³ mL / gcm or more,

Alkali-soluble resin,

A photosensitive coloring composition containing a colorant having a polymerizable group,

The photosensitive coloring composition in which the content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more.

<2> The photosensitive coloring composition according to <1>, in which the light absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator a is 1.0 × 10 ³ mL / gcm or more.

<3> The photosensitive coloring composition as described in <1> or <2>, in which the photoinitiator a is an oxime compound.

<4> The photosensitive coloring composition as described in any one of <1>-<3>, in which the photoinitiator b is a hydroxyacetophenone compound.

The photosensitive coloring composition in any one of <1>-<4> which contains 50-500 mass parts of photopolymerization initiator a with respect to 100 mass parts of <5> photopolymerization initiator b.

The photosensitive coloring composition in any one of <1>-<5> whose total content of the photoinitiator a and the photoinitiator b in the whole solid content of a <6> photosensitive coloring composition is 3 to 17 mass%.

<7> The coloring material is a photosensitive coloring composition in any one of <1>-<6> which is a dye multimer.

<8> A cured film obtained by curing the photosensitive coloring composition according to any one of <1> to <7>.

<9> A step of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition according to any one of <1> to <7>,

A step of exposing the photosensitive coloring composition layer in a pattern by irradiating light having a wavelength of more than 350 nm and less than or equal to 380 nm;

A step of alkali developing the photosensitive coloring composition layer after exposure;

The pattern formation method which has the process of irradiating the photosensitive coloring composition layer after image development, and irradiating the light of wavelength 254-350 nm.

<10> A color filter having the cured film according to <8>.

<11> A solid-state imaging device having the cured film according to <8>.

<12> An image display device having the cured film according to <8>.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive coloring composition which can form the cured film excellent in the discoloration resistance with respect to a developing solution can be provided. Moreover, a cured film, a method of forming a pattern, a color filter, and a solid-state imaging element can be provided.

Hereinafter, the content of the present invention will be described in detail.

In the description of the group (atomic group) in this specification, the notation that does not describe substitution or unsubstitution includes a group (atom group) having a substituent together with a group having no substituent (atom group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Moreover, as a light used for exposure, active light rays or radiations, such as bright spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams, are generally mentioned.

In the present specification, the numerical range indicated by using "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from all components of the composition.

In the present specification, "(meth) acrylate" represents both or both of acrylate and methacrylate, and "(meth) acrylic" represents both of acrylic and methacryl, or either, "(Meth) allyl" represents both or both of allyl and metalyl, and "(meth) acryloyl" represents both or both of acryloyl and methacryloyl.

In the present specification, the term "process" is included in this term when the desired action of the process is achieved even if it is not only an independent process but can not be clearly distinguished from other processes.

In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Photosensitive coloring composition>

The photosensitive coloring composition of the present invention,

A photopolymerization initiator a whose absorption coefficient of light at a wavelength of 365 nm in methanol exceeds 1.0 × 10 ² mL / gcm,

A photopolymerization initiator b having an absorption coefficient of light of 365 nm wavelength in methanol of 1.0 × 10 ² mL / gcm or less, an absorption coefficient of light of wavelength 254 nm of 1.0 × 10 ³ mL / gcm or more,

Alkali-soluble resin,

A photosensitive coloring composition containing a colorant having a polymerizable group,

It is characterized in that the content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more.

The photosensitive coloring composition of the present invention contains photopolymerization initiator a and photopolymerization initiator b as photopolymerization initiators in the above-described predetermined ratios, and can be cured properly to the core of the cured film by exposure. And in this invention, since the coloring material which has a polymerizable group is used, when hardening a photosensitive coloring composition, the polymerizable group of a coloring material reacts with components other than the coloring material of a photosensitive coloring composition, and a coloring material becomes easy to blow in a cured film. , It is possible to form a cured film excellent in discoloration resistance to the developer. For this reason, discoloration after image development can be effectively suppressed. For example, when a pattern (pixel) of a cured film of each color is sequentially formed using a multi-color photosensitive coloring composition to produce a color filter having pixels of multiple colors, upon formation of pixels after the second color, The pixels formed in the previous step are also exposed to the developer, but by using the photosensitive coloring composition of the present invention, a cured film excellent in discoloration resistance to the developer can be formed. Discoloration from previously formed pixels can be suppressed.

Moreover, according to the photosensitive coloring composition of this invention, in the first exposure (exposure before image development), the photosensitive coloring composition can be hardened suitably. For this reason, a pattern with good rectangularity can be formed. And the whole photosensitive coloring composition can be hardened almost by the next exposure (exposure after image development). For this reason, a pattern excellent in discoloration resistance to a developer can be formed while having excellent pattern forming properties.

In addition, the photosensitive coloring composition of the present invention has a particularly remarkable effect when a dye having a polymerizable group is used as a color material having a polymerizable group. When a dye was used as a color material, affinity for the developer tended to be high, and decolorization to the developer tended to occur easily. For this reason, in the conventional photosensitive coloring composition, it was necessary to heat-treat at high temperature, and to harden the film | membrane sufficiently. However, according to the photosensitive coloring composition of the present invention, by using a dye having a polymerizable group, even when cured at a low temperature, a cured film excellent in discoloration resistance to a developer can be formed, so the effect of the present invention is particularly remarkable. In addition, it is also possible to form a cured film that is clearer and has a higher color value by using a dye.

Hereinafter, the photosensitive coloring composition of this invention is demonstrated in detail.

<< photopolymerization initiator >>

The photosensitive coloring composition of this invention contains a photoinitiator. Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound such as acylphosphine oxide, and hexaaryl biimi Oxime compounds such as dazol compounds and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoacetophenone compounds, hydroxyacetophenone compounds, and phenylglyoxylate compounds. have. As a specific example of a photopolymerization initiator, the description of paragraph No. 0265 to 0268 of JP 2013-029760 A can be referred to, for example, and this content is incorporated herein.

As the photopolymerization initiator, the present invention may use a bifunctional or trifunctional or higher photopolymerization initiator. As specific examples of such a photopolymerization initiator, Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. WO2015 / 004565, Japanese Patent Application Publication No. 2016-532675, paragraph numbers 0417 to 0412, International Dimers of oxime compounds described in paragraph numbers 0039 to 0055 of WO2017 / 033680, and compounds (E) and compounds (G) described in Japanese Patent Publication No. 2013-522445, International Publication WO2016 / 034963 And Cmpd1 to 7 described in the heading.

Examples of the phenyl glyoxylate compound include phenyl glyoxylic acid methyl ester and the like. DAROCUR-MBF (made by BASF Corporation) etc. are mentioned as a commercial item.

As an amino acetophenone compound, the amino acetophenone compound described in Unexamined-Japanese-Patent No. 10-291969 is mentioned, for example. Moreover, as an amino acetophenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all are made by BASF Corporation) can also be used.

Examples of the acylphosphine compound include an acylphosphine compound described in Japanese Patent Publication No. 4225898. As a specific example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide etc. are mentioned. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.

As a hydroxyacetophenone compound, the compound represented by following formula (V) is mentioned.

Expression (V)

[Formula 1]

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represents a hydrogen atom or a substituent, and Rv ² and Rv ³ may combine with each other to form a ring, and m is an integer from 0 to 4 Indicates.

Examples of the substituent represented by Rv ¹ include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). The alkyl group and the alkoxy group are preferably straight or branched, and more preferably straight chain. The alkyl group and the alkoxy group represented by Rv ¹ may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxyl group, a group having a hydroxyacetophenone structure, and the like. Hydroxy may be mentioned as the hydroxyl group having acetophenone structure, formula (V) Rv ¹ is bonded a benzene ring, or a group of the structure of a hydrogen atom has been removed from one of the Rv ^1.

Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferable. Further, Rv ² and Rv ³ may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably a straight chain or a branch, and more preferably a straight chain.

The following compounds are mentioned as a specific example of the compound represented by Formula (V).

[Formula 2]

As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.

As an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used, for example. Moreover, as an oxime compound, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Patent Publication No. 2000-066385, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2004-534797, Japanese publication The compound etc. described in patent publication 2006-342166 can also be used. As a specific example of an oxime compound, 1,2-octane ion, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. In commercial products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, manufactured by BASF) are suitably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Archles NCI -930, Adeka Optomer N-1919 (Photopolymerization initiator 2 of JP 2012-014052 A) (above, manufactured by ADEKA Corporation) can be used.

Moreover, as an oxime compound, the compound of Unexamined-Japanese-Patent No. 2009-519904 in which the oxime was connected to the N position of a carbazole ring, the compound of Unexamined-patent publication No. 726657 in which a hetero substituent was introduce | transduced at the benzophenone site | part, a nitrite at the pigment site | part The compound described in Japanese Unexamined Patent Publication No. 2010-015025 and United States Patent Publication No. 2009-292039, the ketoxime compound described in International Publication No. WO2009 / 131189, the triazine skeleton and the oxime skeleton are contained in the same molecule. You may use the compound of Unexamined-Japanese-Patent No. 2009-221114 etc. which has the maximum absorption at 405 nm and has good sensitivity with respect to a g-ray source, etc. may be used. Preferably, for example, paragraph Nos. 0274 to 0306 of JP 2013-029760 A can be referred to, and this content is incorporated herein.

Moreover, as an oxime compound, the oxime compound which has a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 is mentioned. This content is incorporated herein.

Moreover, as an oxime compound, the oxime compound which has a benzofuran skeleton can also be used. Specific examples include compounds OE-01 to OE-75 described in International Publication No. WO2015 / 036910.

Moreover, as an oxime compound, the oxime compound which has a skeleton in which at least 1 benzene ring of a carbazole ring became a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in international publication WO2013 / 083505 is mentioned.

Moreover, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. As specific examples of the oxime compound having a fluorine atom, the compound described in JP 2010-262028 A, the compound 24, 36-40 in JP 2014-500852 A, the compound described in JP 2013-164471 A (C-3) and the like. This content is incorporated herein.

Moreover, as an oxime compound, the oxime compound which has a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. As specific examples of the oxime compound having a nitro group, the compounds described in paragraphs 0031 to 0047 of JP 2013-114249 and JP-A 2014-137466 are described in paragraphs 0008 to 0012, 0070 to 0079, and Japanese patent publication 4223071 The compound described in paragraph number 0007-0025, Adeka Acles NCI-831 (made by ADEKA Corporation), etc. are mentioned.

Although the specific example of an oxime compound is shown below, this invention is not limited to these.

[Formula 3]

[Formula 4]

In the present invention, as a photopolymerization initiator, a photopolymerization initiator a (hereinafter also referred to as a photopolymerization initiator a) whose absorption coefficient of light at a wavelength of 365 nm in methanol exceeds 1.0 × 10 ² mL / gcm,

The photopolymerization initiator b (hereinafter also referred to as photopolymerization initiator b) of light having a wavelength of 365 nm in methanol having an absorption coefficient of 1.0 × 10 ² mL / gcm or less and an absorption coefficient of light having a wavelength of 254 nm of 1.0 × 10 ³ mL / gcm or more is used in combination. . As the photopolymerization initiator a and the photopolymerization initiator b, a compound having the above extinction coefficient can be selected from the above-mentioned compounds and used.

In addition, in this invention, the extinction coefficient at the said wavelength of a photoinitiator is a value measured as follows. That is, the photopolymerization initiator was dissolved in methanol to prepare a measurement solution, and was calculated by measuring the absorbance of the measurement solution described above. Specifically, the above-described measurement solution was placed in a glass cell having a width of 1 cm, and absorbance was measured using a UV-Vis-NIR spectrum meter (Cary5000) manufactured by Agilent Technologies, and applied to the following formula, to a wavelength of 365 nm and a wavelength of 254 nm. The extinction coefficient (mL / gcm) was calculated.

[Equation 1]

In the above formula, ε is the absorption coefficient (mL / gcm), A is the absorbance, c is the concentration of the photopolymerization initiator (g / mL), and l is the optical path length (cm).

The light absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator a is a value exceeding 1.0 × 10 ² mL / gcm, preferably 1.0 × 10 ³ mL / gcm or more, and 1.0 × 10 ³ to 1.0 × 10 ⁴ mL It is more preferable that it is / gcm, more preferably 2.0 × 10 ³ ~ 9.0 × 10 ³ mL / gcm, and particularly preferably 3.0 × 10 ³ ~ 8.0 × 10 ³ mL / gcm.

In addition, the light absorption coefficient of light having a wavelength of 254 nm in methanol of the photopolymerization initiator a is preferably 1.0 × 10 ⁴ to 1.0 × 10 ⁵ mL / gcm, and more preferably 1.5 × 10 ⁴ to 9.5 × 10 ⁴ mL / gcm. It is more preferably 3.0 × 10 ⁴ ~ 8.0 × 10 ⁴ mL / gcm.

As the photopolymerization initiator a, an oxime compound, an aminoacetophenone compound, and an acylphosphine compound are preferable, an oxime compound and an acylphosphine compound are more preferable, and an oxime compound is more preferable. As a specific example of a photoinitiator a, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (For commercial products, for example, IRGACURE-OXE01, manufactured by BASF ), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (as a commercial product, for example, IRGACURE-OXE02 , Manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (as a commercial product, for example, IRGACURE-819, manufactured by BASF), (C-13) shown in the specific example of the above oxime compound ) And the like.

The light absorption coefficient of light of 365 nm in methanol in the photopolymerization initiator b is 1.0 × 10 ² mL / gcm or less, preferably 10 to 1.0 × 10 ² mL / gcm, and 20 to 1.0 × 10 ² mL / gcm It is more preferable. Further, the difference between the light absorption coefficient of light at a wavelength of 365 nm in methanol of the photopolymerization initiator a and the light absorption coefficient of light at a wavelength of 365 nm in methanol of the photopolymerization initiator b is preferably 9.0 × 10 ² mL / gcm or more, and 9.0 × 10 ² It is more preferable that it is ∼1.0 × 10 ⁵ mL / gcm, and more preferably 9.0 × 10 ² ∼1.0 × 10 ⁴ mL / gcm. In addition, the light absorption coefficient of light having a wavelength of 254 nm in methanol of the photopolymerization initiator b is 1.0 × 10 ³ mL / gcm or more, preferably 1.0 × 10 ³ to 1.0 × 10 ⁶ mL / gcm, and 5.0 × 10 ³ to 1.0 It is more preferable that x 10 ⁵ mL / gcm, and more preferably 1.0 × 10 ⁴ ~ 5.0 × 10 ⁵ mL / gcm.

As the photopolymerization initiator b, a hydroxyacetophenone compound, a phenylglyoxylate compound, an aminoacetophenone compound, an acylphosphine compound is preferable, a hydroxyacetophenone compound and a phenylglyoxylate compound are more preferable, and a hydroxyacetophenone Compounds are more preferred. Moreover, as a hydroxyacetophenone compound, the compound represented by Formula (V) mentioned above is preferable. As a specific example of a photoinitiator b, 1-hydroxy-cyclohexyl-phenyl-ketone (For a commercial item, for example, IRGACURE-184, BASF Corporation make), 1- [4- (2-hydroxy ethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one (as a commercial item, for example, IRGACURE-2959, manufactured by BASF) and the like.

As a combination of the photopolymerization initiator a and the photopolymerization initiator b, the photopolymerization initiator a is an oxime compound, and the photopolymerization initiator a is a oxime compound because it can increase the absorption coefficient of light having a wavelength of 350 nm or more and 380 nm or less and a wavelength of 254 nm or more and 350 nm or less. The combination is preferably a hydroxyacetophenone compound, a photopolymerization initiator a is an oxime compound, and a combination in which the photopolymerization initiator b is a compound represented by the formula (V) described above is more preferable.

Content of photoinitiator a is 1.5 mass% or more in all solid content of the photosensitive coloring composition of this invention, and 1.5-15 mass% is preferable. From the viewpoint of adhesion of the cured film (pattern) after development to the support, the lower limit of the content of the photopolymerization initiator a is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. From the viewpoint of refinement of the development pattern, the upper limit of the content of the photopolymerization initiator a is preferably 14.5% by mass or less, more preferably 12.5% by mass or less, and even more preferably 9% by mass or less. The photopolymerization initiator a may contain only 1 type, or may contain 2 or more types. When 2 or more types of photoinitiator a are included, it is preferable that these totals become said range.

Content of photoinitiator b is 1.5 mass% or more in all solid content of the photosensitive coloring composition of this invention, and 1.5-10 mass% is preferable. From the viewpoint of the discoloration resistance of the resulting cured film, the lower limit of the content of the photopolymerization initiator b is preferably 1.6% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. From the viewpoint of refinement of the development pattern, the upper limit of the content of the photopolymerization initiator b is preferably 9.5% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5% by mass or less. The photopolymerization initiator b may contain only 1 type, or may contain 2 or more types. When 2 or more types of photoinitiator b are included, it is preferable that these totals become said range.

It is preferable that the photosensitive coloring composition of this invention contains 50-500 mass parts of photoinitiator a with respect to 100 mass parts of photopolymerization initiator b. The upper limit is preferably 400 parts by mass or less, and more preferably 350 parts by mass or less for the reason that it is easy to form a cured film excellent in discoloration resistance. Moreover, the lower limit is preferably 100 parts by mass or more, and more preferably 150 parts by mass or more, because the residual film ratio after development is high and it is easy to form a cured film excellent in adhesion to a support.

It is preferable that content of the total of the photoinitiator a and the photoinitiator b in all solid content of the photosensitive coloring composition of this invention is 3 to 17 mass% or more. From the viewpoint of stability with time of the composition, the lower limit is preferably 3.2% by mass or more, more preferably 3.5% by mass or more, and even more preferably 4.5% by mass or more. From the viewpoint of refinement of the development pattern, the upper limit is preferably 16% by mass or less, more preferably 15% by mass or less, and even more preferably 14% by mass or less.

The photosensitive coloring composition of the present invention may contain photopolymerization initiators other than photopolymerization initiator a and photopolymerization initiator b (hereinafter, also referred to as other photopolymerization initiators) as the photopolymerization initiator, but it is preferable that the other photopolymerization initiator is not substantially contained. When it does not contain another photoinitiator substantially, it is preferable that content of another photoinitiator is 1 mass part or less with respect to 100 mass parts of total photoinitiator a and photopolymerization initiator b, and it is more preferable that it is 0.5 mass part or less, It is more preferably 0.1 parts by mass or less, and even more preferably, containing no other photopolymerization initiator.

<< Color material with polymerizable group >>

The photosensitive coloring composition of this invention contains the coloring material which has a polymerizable group. The color material having a polymerizable group may be a pigment or a dye, but is preferably a dye. That is, it is preferable that the color material which has a polymerizable group is a dye which has a polymerizable group. The cured film obtained by using a photosensitive coloring composition containing a dye as a colorant tended to be easily decolored by a developer, but by using a polymerizable group as a dye, even when cured at a low temperature, it has excellent decoloring resistance to a developer. A cured film can be formed. For this reason, the effect of the present invention is more remarkable.

In addition, in this specification, a dye refers to the dye compound dissolved in water or an organic solvent. For example, a pigment compound that dissolves in an amount of 0.1% by mass or more with respect to cyclohexanone or propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C is preferable.

The color material having a polymerizable group includes triarylmethane pigment structure, xanthene pigment structure, anthraquinone pigment structure, cyanine pigment structure, squarylium pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, subphthalo Cyanine pigment structure, azo pigment structure, pyrazolotriazole pigment structure, dipyrromethene pigment structure, isoindoline pigment structure, thiazole pigment structure, benzimidazoleone pigment structure, perinone pigment structure, pyrrolopyrrole pigment structure , Diketopyrrolopyrrole pigment structure, diimmonium pigment structure, naphthalocyanine pigment structure, relene pigment structure, dibenzofuranone pigment structure, merocyanine pigment structure, croconium pigment structure and oxonol pigment structure It is preferable that it is a compound which has a dye structure to become, a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure, a cyan Pigment structure, squarylium pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment structure, thiazole pigment structure, pyrazolotriazole pigment structure and dipyrromethene pigment It is more preferable that it is a compound having a dye structure selected from a structure, it is more preferable that it is a compound having a dye structure selected from a triarylmethane dye structure, a xanthene dye structure and a dipyrromethene dye structure, and a triarylmethane dye It is particularly preferable to be a compound having a structure or a xanthene dye structure.

(A compound having a triarylmethane pigment structure)

As a compound which has a triarylmethane dye structure, the compound represented by following formula (TP) is mentioned.

Expression (TP)

[Formula 5]

In formula (TP), Rtp ¹ to Rtp ⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp ⁵ is a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ shows the (Rtp ⁹ and Rtp ¹⁰ represents a hydrogen atom, an alkyl group or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent. a, b and c represent the integer of 0-4. When a, b and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ^{8 may} be connected to each other to form a ring. X represents an anion. When X is not present, at least one of Rtp ¹ to Rtp ⁸ contains an anion. At least one of Rtp ¹ to Rtp ⁸ contains a polymerizable group.

Rtp ¹ to Rtp ⁴ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp ⁵ is a hydrogen atom or NRtp ⁹ Rtp ¹⁰ are preferred, NRtp ⁹ Rtp ¹⁰ is particularly preferred. Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. Examples of the substituents represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ include groups from the substituent T group described later and polymerizable groups.

In formula (TP), X represents a counter anion. When X is not present, at least one of Rtp ¹ to Rtp ⁸ contains an anion. The counter anion is not particularly limited. It may be an organic anion or an inorganic anion. The counter anion is preferably an organic anion. Examples of counter anions include fluorine anions, chlorine anions, bromine anions, iodine anions, cyanide ions, perchloric acid anions, and non-nucleophilic anions. It is preferable that it is a non-nucleophilic anion from the viewpoint of heat resistance. Examples of counter anions include known non-nucleophilic anions described in Japanese Patent Laid-Open No. 2007-310315, paragraph No. 0075, the contents of which are incorporated herein. Here, non-nucleophilic means a property that the pigment does not attack the nucleus by heating.

The counter anion is preferably an imide anion (for example, a bis (sulfonyl) imide anion), a tris (sulfonyl) methyl anion, an anion having a boron atom, and a bis (sulfonyl) imide anion and a tris (sulfur) Fonyl) methyl anion is more preferable, and bis (sulfonyl) imide anion is more preferable. Examples of the anion having a boron atom include tetrafluoroborate anion, tetraphenylborate anion, and tetraperfluorophenylborate anion. The molecular weight of the counter anion is preferably 100 to 1,000, and more preferably 200 to 500.

In Formula (TP), a, b, or c each independently represents an integer of 0 to 4. Especially a and c, respectively, 0 or 1 is preferable, and 0 is more preferable. b is preferably an integer of 0 to 2, more preferably 0 or 2.

Equation (TP) in, ~ ¹ Rtp Rtp those containing anions at least one of ^7, as the anion, a -SO _{3 ^{-, -COO -, -PO 4 -}} , bis (alkylsulfonyl) imide anion, tris ( Sulfonyl) methide anions and tetraarylborate anions are preferred, bis (sulfonyl) imide anions, tris (sulfonyl) methide anions and tetraarylborate anions are more preferred, and bis (sulfonyl) imide anions And tris (sulfonyl) methide anions are more preferred. Specifically, a structure in which at least one of Rtp ¹ to Rtp ⁷ is substituted with formula (P) is exemplified.

Expression (P)

[Formula 6]

In formula (P), L represents a single bond or a divalent linking group, and X ¹ represents an anion.

In formula (P), L represents a single bond or a divalent linking group. As the divalent linking group, it is preferable to represent a group consisting of -NR ^10- , -O-, -SO _2- , an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, or a combination thereof. In particular, a group consisting of a combination of -NR ¹⁰ -and -SO ₂ and an alkylene group containing a fluorine atom, a group consisting of a combination of -O- and an arylene group containing a fluorine atom, or -NR ¹⁰ -and- A group consisting of a combination of SO ₂ and an alkylene group containing a fluorine atom is preferred.

In -NR ^10- , R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom is preferable.

As for the carbon number of the alkylene group containing a fluorine atom, 1-10 are preferable, 1-6 are more preferable, and 1-3 are more preferable. These alkylene groups are more preferably a perfluoroalkylene group. Specific examples of the fluorine-substituted alkylene group include difluoromethylene group, tetrafluoroethylene group, and hexafluoropropylene group.

As for carbon number of the arylene group containing a fluorine atom, 6-20 are preferable, 6-14 are more preferable, and 6-10 are more preferable. As a specific example of the arylene group containing a fluorine atom, a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, a hexafluoro-2-naphthylene group, etc. are mentioned.

Type (P) of, X is ^1, represents an _{^{anion, -SO 3 -, -COO -,}} -PO 4 -, bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion, and tetra-aryl anion One kind selected from bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion is more preferred, and bis (sulfonyl) imide anion or tris ( Sulfonyl) methide anions are more preferred.

When at least one of Rtp ¹ to Rtp ⁸ contains an anion, a structure in which at least one of Rtp ¹ to Rtp ⁸ is substituted with formula (P-1) is also preferable.

Expression (P-1)

[Formula 7]

In Formula (P-1), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. Examples of the divalent linking group represented by L ¹ include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, a group consisting of -O-, -S-, or a combination thereof. L ² represents -SO ₂ -or -CO-. G represents a carbon atom or a nitrogen atom. n1 represents 2 when G is a carbon atom, and 1 when G is a nitrogen atom. R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n1 is 2, two R ^{6 s} may be the same or different. As for carbon number of the alkyl group containing the fluorine atom represented by R ⁶ , 1-10 are preferable, 1-6 are more preferable, and 1-3 are more preferable. As for the carbon number of the aryl group containing the fluorine atom represented by R ⁶ , 6-20 are preferable, 6-14 are more preferable, and 6-10 are more preferable.

(Compound having a xanthene dye structure)

As a compound which has a xanthene dye structure, the compound represented by following formula (J) is mentioned.

(Equation J)

[Formula 8]

In Formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m is 0 to Represents an integer of 5. X represents a counter anion. When X is not present, at least one of R ⁸¹ to R ⁸⁵ contains an anion. At least one of R ⁸¹ to R ⁸⁵ contains a polymerizable group.

Examples of the substituents that R ⁸¹ to R ⁸⁵ in Formula (J) can take include groups listed as substituents T described later, and polymerizable groups. In the formula (J), R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to each other by a 5-membered, 6-membered or 7-membered saturated ring, or 5-membered , 6 or 7 membered unsaturated ring may be formed. Examples of the ring to be formed include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, and cyclohex A sencyclic ring, a benzene ring, a pyridine ring, a pyrazine ring, and a pyridazine ring are mentioned, Preferably, a benzene ring and a pyridine ring are mentioned.

When the ring to be formed is a group that can be further substituted, the substituents described in R ⁸¹ to R ⁸⁵ may be substituted, or when substituted with two or more substituents, these substituents may be the same or different.

In Formula (J), X represents a counter anion. As a counter anion, the counter anion demonstrated by Formula (TP) mentioned above is mentioned. When X is not present, at least one of R ⁸¹ to R ⁸⁵ contains an anion. Moreover, in Formula (J), when at least 1 of R ⁸¹ -R ⁸⁵ contains an anion, the anion demonstrated by Formula (TP) mentioned above is mentioned as an anion.

(Compound having a dipyrromethene dye structure)

As a compound having a dipyrromethene dye structure, a dipyrromethene compound and a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a metal or metal compound are preferable. For example, a dipyrromethene pigment represented by formula (PM) is preferred.

Expression (PM)

[Formula 9]

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, Or a heterocyclic group. The substituent T group mentioned later is mentioned as these substituents. At least one of R ¹ to R ⁷ contains a polymerizable group.

The metal or metal compound forming the dipyrromethene metal complex compound will be described. The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and includes bivalent metal atoms, divalent metal oxides, divalent metal hydroxides, or divalent metal chlorides. For example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl, SiCl ₂ , Metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ . Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex Is preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferred, Fe, Zn, Cu, Co, B, or VO (V = O) is the most desirable. Among these, Zn is particularly preferable.

For details of the dipyrromethene dye structure, the descriptions of paragraphs 0045 to 0095 of Japanese Patent Application Laid-Open No. 2014-132348 and the descriptions of paragraphs 0033 to 0136 of Japanese Patent Application Laid-Open No. 2011-095732 can be referred to, and the contents of this document are incorporated herein. Is used.

(Substitution group T)

The following group is mentioned as a substituent T group. Alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkaneyl group (preferably an alkynyl group having 2 to 30 carbon atoms), aryl group (preferably Is an aryl group having 6 to 30 carbon atoms, an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably having 6 to 30 carbon atoms) Aryloxy group), heteroaryloxy group, acyl group (preferably an acyl group having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably Aryloxycarbonyl group having 7 to 30 carbon atoms, acyloxy group (preferably acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably acylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably Is an alkoxycarbonylamino group having 2 to 30 carbon atoms, aryloxycarbonylamino group (bar Preferably aryloxycarbonylamino group having 7 to 30 carbon atoms, sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkyl Cyo group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (Preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 6 to 30 carbon atoms), heteroaryl sulfonyl group (preferably 1 to 30 carbon atoms), alkylsulfinyl group (preferably 1 to 30 carbon atoms), Aryl sulfinyl group (preferably 6 to 30 carbon atoms), heteroaryl sulfinyl group (preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxyl group, carboxyl group, sulfo group, phosphoric acid group , Carboxylic acid amide group, sulfonic acid amide group, imide acid group, mercapto group, halogen atom, sia Group, an alkyl sulfinyl group, aryl sulfinyl group, a hydroxy large group, an imino group, a heteroaryl group (preferably having 1 to 30 carbon atoms). When these groups are further substituted groups, they may further have a substituent. As a substituent, the group demonstrated by the substituent T mentioned above is mentioned.

As a polymerizable group which a color material has, ethylenically unsaturated groups, such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, are mentioned.

It is preferable that the color material having a polymerizable group is a large amount of dyes because it is easy to form a cured film excellent in discoloration resistance to a developer. The dye multimer is a dye compound having two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The dye structure in one molecule may be the same dye structure, or may be a different dye structure. In addition, in this invention, the other dye structure means that not only the dye structure in which a dye skeleton differs but also the dye structure in which a dye skeleton is the same and the kind of the substituent which is attached to the dye skeleton differs is included.

As the dye multimer, a dye multimer comprising at least one of a repeating unit represented by formula (A), a repeating unit represented by formula (B), and a repeating unit represented by formula (C), or a formula described later ( The dye multimer represented by D) is preferred. That is, the dye multimer is a dye multimer having a repeating unit represented by formula (A) (also referred to as a dye multimer (A)), and a dye multimer having a repeating unit represented by formula (B) (pigment multimer (B) ), A dye multimer having a repeating unit represented by formula (C) (also called a dye multimer (C)), and a dye multimer represented by a formula (D) (also called a dye multimer (D)) Preference is given to the dye multimer (A) or the dye multimer (D).

(Pigment multimer (A))

It is preferable that a dye multimer (A) contains the repeating unit represented by Formula (A). The proportion of repeating units represented by formula (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, of all the repeating units constituting the dye multimer (A). , 50% by mass or more is particularly preferred. The upper limit may be 100% by mass or less, or 95% by mass or less.

[Formula 10]

In Formula (A), X ¹ represents a main chain of a repeating unit, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a pigment structure.

In Formula (A), X ¹ represents the main chain of a repeating unit. X ¹ is a linking group or the like formed by a polymerization reaction, and a main chain derived from a compound having a (meth) acrylic group, a styrene group, a vinyl group, or an ether group is preferable. Moreover, the aspect in which the main chain has a cyclic alkylene group is also preferable. X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer. The linking groups represented by the following (XX-1) to (XX-25) are preferred, and (XX-1), (XX-2), (XX-10) to (XX-17), (XX-18), ( It is more preferably selected from XX-19), (XX-24) and (XX-25), and (XX-1), (XX-2), (XX-10) to (XX-17), (XX -24) and (XX-25) are more preferred.

In the following formula, * is a binding site with L ^{1 in} formula (A). Me represents a methyl group. Moreover, R in (XX-18) and (XX-19) represents a hydrogen atom, a C1-C5 alkyl group, or a phenyl group.

[Formula 11]

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, and -COO- , -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and a linking group formed by connecting two or more of them. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

The carbon number of the alkylene group is preferably 1 to 30. The upper limit is more preferably 25 or less, and more preferably 20 or less. The lower limit is more preferably 2 or more, and more preferably 3 or more. The alkylene group may be either straight chain, branched or cyclic. The alkylene group may have a substituent or may be unsubstituted. As a substituent, the group demonstrated by the substituent T group is mentioned.

6-20 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable. The arylene group may have a substituent or may be unsubstituted. As a substituent, the group demonstrated by the substituent T group is mentioned.

The heterocyclic linking group is preferably a 5- or 6-membered ring. As for the hetero atom which a heterocyclic linking group has, an oxygen atom, a nitrogen atom, and a sulfur atom are preferable. As for the number of hetero atoms which a heterocyclic linking group has, 1-3 are preferable. The heterocyclic linking group may have a substituent or may be unsubstituted. As a substituent, the group demonstrated by the substituent T group is mentioned.

D ¹ represents a dye structure. The type of the dye structure represented by D ¹ is not particularly limited. Triarylmethane pigment structure, xanthene pigment structure, anthraquinone pigment structure, cyanine pigment structure, squarylium pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment Structure, pyrazolotriazole pigment structure, dipyrromethene pigment structure, isoindoline pigment structure, thiazole pigment structure, benzimidazole pigment structure, perinone pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment Structure, diimmonium pigment structure, naphthalocyanine pigment structure, relene pigment structure, dibenzofuranone pigment structure, merocyanine pigment structure, croconium pigment structure, oxonol pigment structure and the like. The dye structure represented by D ¹ may contain a polymerizable group.

It is preferable that the dye multimer (A) has a repeating unit having a polymerizable group in addition to the repeating unit represented by the formula (A). Moreover, in the case where the dye structure represented by D ¹ in the formula (A) described above does not have a polymerizable group, the dye multimer (A) has a repeating unit having a polymerizable group.

The dye multimer (A) may contain other repeating units in addition to the repeating units represented by the formula (A). Other repeating units may contain functional groups such as polymerizable groups and acid groups. It is not necessary to include a functional group. Moreover, in the case where the dye structure represented by D ¹ in the formula (A) described above does not have a polymerizable group, the dye multimer (A) has a repeating unit having a polymerizable group.

It is preferable that the ratio of the repeating unit having a polymerizable group is 0 to 50% by mass of all repeating units constituting the dye multimer (A). The lower limit is more preferably 1% by mass or more, and even more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and even more preferably 30% by mass or less.

Examples of the acid group include a carboxyl group, sulfonic acid group, and phosphoric acid group. Only one type of acid group may be included, or two or more types may be included. It is preferable that the proportion of the repeating unit having an acid group is 0 to 50% by mass of all repeating units constituting the dye multimer (A). The lower limit is more preferably 1% by mass or more, and even more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and even more preferably 30% by mass or less.

As other functional groups, groups consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, development promoters such as lactones, acid anhydrides, amides, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylenes Hydrophilicity regulators, such as an oxide group, a hydroxyl group, a maleimide group, and an amino group, etc. are mentioned, It can introduce suitably. In the group consisting of 2 to 20 unsubstituted alkyleneoxy chain repeats, the number of repeats of the alkyleneoxy chains is preferably 2 to 15, and more preferably 2 to 10. One alkyleneoxy chain is represented by-(CH ₂ ) _n O-, n is an integer, but n is preferably 1 to 10, 1 to 5 is more preferable, and 2 or 3 is more preferable.

Although specific examples of other repeating units are shown, the present invention is not limited thereto. In the following structural formulae, Me represents a methyl group and Et represents an ethyl group.

[Formula 12]

[Formula 13]

(Pigment multimer (B))

The dye multimer (B) includes a repeating unit represented by formula (B). The proportion of the repeating units represented by formula (B) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, of all the repeating units constituting the dye multimer (B). , 50% by mass or more is particularly preferred. The upper limit may be 100% by mass or less, or 95% by mass or less.

[Formula 14]

Formula (B) of the, X ² represents a main chain of the repeating unit, L ² represents a single bond or a divalent linking group, D ² represents a dye structure having a Y ² and an ionic bond or coordination bond possible, Y ² is Represents a group capable of ionic or coordination bonding with D ² ;

X ² is synonymous with X ^{1 in} Formula (A), and the preferred range is also the same.

L ² represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, and -COO- , -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and a linking group formed by connecting two or more of them. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. The details of the divalent linking group are the same as L ^{1 in} Formula (A). L ² is preferably a single bond or a divalent linking group in which an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO- and two or more of them are combined.

Y ² may be any group capable of ionic bonding or coordination bonding with D ² . For example, an anionic group, a cationic group, etc. are mentioned. As the anionic _{^{group, -SO 3 -, -COO -,}} -PO 4 -, -PO 4 H -, bis (sulfonyl), and the like already de anion, tris (alkylsulfonyl) methide anion, and tetra-aryl anion have. Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium and phosphonium), and ammonium cations are particularly preferred. As the cation, there may be mentioned -N (R) ₃ ^+. R each independently represents a hydrogen atom or an alkyl group, and at least one of R represents an alkyl group. 1-10 are preferable, and, as for carbon number of an alkyl group, 1-5 are more preferable. The alkyl group may be either straight chain, branched or cyclic, but straight chain is preferred.

D ² represents a dye structure having a group capable of ionic bonding or coordinate bonding with Y ² . The type of the dye structure is not particularly limited, and a dye structure of the type described in D ¹ is exemplified. Examples of the group capable of ionic bonding or coordination bonding with Y ^{2 of} D ² include anionic groups and cationic groups described in Y ² . Moreover, when the balance of the charge of D ² is unevenly distributed in either a cation or an anion, it is also possible to bond with Y ² in the cation portion or anion portion of D ² . The dye structure represented by D ² may have a polymerizable group.

The dye multimer (B) may contain other repeating units and the like described in the dye multimer (A) in addition to the repeating units represented by the formula (B). Moreover, you may further contain the repeating unit represented by Formula (A) mentioned above, and the repeating unit represented by Formula (C) mentioned later. In addition, when the dye structure represented by D ² of the formula (B) described above does not have a polymerizable group, the dye multimer (B) has a repeating unit having a polymerizable group.

(Pigment multimer (C))

It is preferable that a dye multimer (C) contains the repeating unit represented by Formula (C). The proportion of repeating units represented by formula (C) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, of all the repeating units constituting the dye multimer (C). , 50% by mass or more is particularly preferred. The upper limit may be 100% by mass or less, or 95% by mass or less.

[Formula 15]

In formula (C), L ³ represents a single bond or a divalent linking group, D ³ represents a pigment structure, and m represents 0 or 1.

In Formula (C), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, and -COO- , -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and a linking group formed by connecting two or more of them. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

As for the carbon number of an alkyl group and an alkylene group, 1-30 are preferable. The upper limit is more preferably 25 or less, and more preferably 20 or less. The lower limit is more preferably 2 or more, and more preferably 3 or more. The alkyl group and the alkylene group may be either straight chain, branched or cyclic.

6-20 are preferable and, as for carbon number of an aryl group and an arylene group, 6-12 are more preferable.

The heterocyclic linking group and the heterocyclic group are preferably a 5 or 6-membered ring. The hetero atom of the heterocyclic linking group and the heterocyclic group is preferably an oxygen atom, a nitrogen atom, and a sulfur atom. As for the number of hetero atoms which a heterocyclic linking group and a heterocyclic group have, 1-3 are preferable.

The alkylene group, arylene group, heterocyclic linking group, alkyl group, aryl group, and heterocyclic group may be unsubstituted or may have a substituent. A polymerizable group and an acid group are mentioned as a substituent. Further, a group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, a developing accelerator such as lactone, acid anhydride, amide, cyano group, long chain and cyclic alkyl group, aralkyl group, aryl group, polyalkylene oxide group , Hydrophilicity regulators, such as a hydroxyl group, a maleimide group, and an amino group, etc., as a substituent.

L ³ is preferably an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, -S- and a linking group combining two or more thereof.

D ³ represents a pigment structure. The type of the dye structure is not particularly limited, and a dye structure of the type described in D1 is exemplified. The dye structure represented by D ³ may have a polymerizable group.

m represents 0 or 1, 1 is preferable.

The dye multimer (C) may contain other repeating units described in the dye multimer (A) in addition to the repeating units represented by the general formula (C).

(Pigment multimer (D))

It is preferable that a dye multimer (D) is represented by Formula (D).

[Formula 16]

In Formula (D), L ⁴ represents a (n + k) valent linking group, L ⁴¹ and L ⁴² each independently represent a single bond or a divalent linking group, D ⁴ represents a pigment structure, and P ⁴ is Represents a substituent; n represents 2-15, k represents 0-13, and n + k is 2-15. The n D ⁴ may be different from each other or may be the same. When k is 2 or more, a plurality of P ⁴ may be different from each other or may be the same.

2-14 are preferable, n, 2-8 are more preferable, 2-7 are especially preferable, and 2-6 are more preferable. As for k, 1-13 are preferable, 1-10 are more preferable, 1-8 are more preferable, 1-7 are especially preferable, and 1-6 are still more preferable.

L ⁴¹ and L ⁴² each independently represent a single bond or a divalent linking group. As the divalent linking group, 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms The group consisting of up to the sulfur atom is included, may be unsubstituted, or may further have a substituent. As a specific example, a bivalent linking group is a group in which two or more of the following structural units or the following structural units are combined.

[Formula 17]

The (n + k) valent linking group represented by L ⁴ is 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 hydrogens. Atoms and groups consisting of 0 to 20 sulfur atoms are included. Examples of the (n + k) valent linking group include groups consisting of two or more of the following structural units or the following structural units in combination (which may form a ring structure).

[Formula 18]

Specific examples of the (n + k) valent linking group include the linking group described in Japanese Patent Application Publication No. 2008-222950, paragraphs 0071 to 7002, and the linking group described in Japanese Patent Application Publication No. 2013-029760, paragraph number 0176.

In General Formula (D), D ⁴ represents a dye structure. The type of the dye structure is not particularly limited, and a dye structure of the type described in D ¹ is exemplified. The dye structure represented by D ⁴ may contain a polymerizable group.

In the formula (D), the substituent P ⁴ indicating there may be mentioned acid group, a polymerizable group or the like. Moreover, the substituent represented by P ⁴ may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, k P ⁴ may be the same or different. When the dye structure represented by D ⁴ does not contain a polymerizable group, at least one of k P ⁴ represents a polymerizable group.

The dye multimer represented by formula (D) is preferably a structure represented by formula (D-1).

[Formula 19]

In the formula (D-1), L ⁴ represents a (n + k) valent linking group. n represents 2-15, k represents 0-13. D ⁴ represents a dye structure, and P ⁴ represents a substituent. B ⁴¹ and B ⁴² each independently represent a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO _2- , -NROC-, or -CONR-. Shows. R represents a hydrogen atom, an alkyl group, or an aryl group. C ⁴¹ and C ⁴² each independently represent a single bond or a divalent linking group. S represents a sulfur atom. The n D ⁴ may be different from each other or may be the same. When k is 2 or more, a plurality of P ⁴ may be different from each other or may be the same. n + k is 2-15.

L ^4, D ⁴ and P ⁴ of the formula (D-1) is a L ^4, D ⁴ and P ⁴ and consent of formula (D).

B ⁴¹ and B ⁴² in the formula (D-1) are preferably a single bond, -O-, -CO-, -O ₂ C-, -CO _2- , -NROC-, or -CONR-, and a single bond. , -O-, -CO-, -O ₂ C- or -CO ₂ -is more preferred. R represents a hydrogen atom, an alkyl group, or an aryl group.

As the divalent linking group represented by C ⁴¹ and C ⁴² in the formula (D-1), an alkylene group, an arylene group, and a group combining them are preferable. 1-30 are preferable and, as for carbon number of an alkylene group, 1-10 are more preferable. The alkylene group may be either straight chain, branched or cyclic. 6-30 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable.

The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and more preferably 6000 or more. As an upper limit, 30000 or less is more preferable, and 20000 or less is more preferable. By satisfying the above range, it is easy to produce a cured film excellent in discoloration resistance.

As for content of the coloring material which has a polymerizable group, 5-40 mass% is preferable in all solid content of the photosensitive coloring composition. The lower limit is more preferably 6% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 35% by mass or less, and even more preferably 30% by mass or less.

Moreover, it is preferable that content of the coloring material which has a polymerizable group is 25-500 mass parts with respect to 100 mass parts in total of photoinitiator a and photoinitiator b. The lower limit is more preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 100 parts by mass or more. The upper limit is more preferably 450 parts by mass or less, more preferably 400 parts by mass or less, and particularly preferably 350 parts by mass or less. If it is this range, a cured film excellent in discoloration resistance with respect to a developing solution is more easily obtained.

<< other color materials >>

The photosensitive coloring composition of the present invention may further contain a color material (hereinafter also referred to as another color material) that does not have a polymerizable group. The other color material may be either a pigment or a dye. Examples of the pigment include inorganic pigments and organic pigments, and are preferably organic pigments. As an average particle diameter of a pigment, 20-300 nm is preferable, 25-250 nm is more preferable, and 30-200 nm is more preferable. The "average particle diameter" as used herein means the average particle diameter of the secondary particles collected by the primary particles of the pigment. In addition, the particle size distribution of the secondary particles of the pigment (hereinafter, simply referred to as "particle size distribution") means that the secondary particles entering (average particle size ± 100) nm are 70% by mass or more, preferably 80% by mass or more. It is preferred. In addition, the particle size distribution of secondary particles can be measured using a scattering intensity distribution. In addition, the average particle diameter of the primary particles can be obtained by observing with a scanning electron microscope (SEM) or transmission electron microscope (TEM), measuring the particle size at 100 parts where particles are not aggregated, and calculating the average value. have.

As an organic pigment, what is shown below is mentioned, for example.

Color Index (CI) 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, 174, 175, 176 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (above, yellow pigment),

CI 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 Etc (more, orange pigment),

CI 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, 269, 270, 272, 279, etc. ( Abnormality, red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment).

Further, as the green pigment, a zinc halide phthalocyanine pigment having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms may be used. As a specific example, the compound described in international publication WO2015 / 118720 is mentioned.

Moreover, the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP 2012-247591 A and paragraphs 0047 of JP 2011-157478 A.

There is no restriction | limiting in particular as a dye, A well-known dye can be used. As the chemical structure, pyrazole azo-based, anilino-azo-based, triarylmethane-based, anthraquinone-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole-azo-based, pyridone-azo-based, cyanine-based, phenothiazines And dyes such as pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene. Moreover, the thiazole compound described in JP 2012-158649 Azo compound described in JP 2011-184493 Azo compound described in JP 2011-145540 A can also be preferably used. Moreover, as a yellow dye, the quinophthalone compound as described in paragraph No. 0011-0034 of Unexamined-Japanese-Patent No. 2013-054339, the quinophthalone compound as described in paragraph No. 0013-0058 of Unexamined-Japanese-Patent No. 2014-026228 can also be used.

When the photosensitive coloring composition of this invention contains another color material, 5-50 mass% is preferable in content of the other color materials in all solid content of the photosensitive coloring composition. The lower limit is more preferably 6% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less.

Moreover, it is preferable that content of a pigment is 50 mass% or more as for other color materials, it is more preferable that it is 70 mass% or more, and it is more preferable that it is 80 mass% or more.

Moreover, 20-70 mass% of all solid content in the photosensitive coloring composition is preferable as the total amount of the color material which has a polymerizable group and another color material. The lower limit is more preferably 25% by mass or more, and even more preferably 30% by mass or more. The upper limit is more preferably 70% by mass or less, and even more preferably 55% by mass or less.

Moreover, the content of the dye in the color material (total color material having a polymerizable group and other color material) contained in the photosensitive coloring composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, It is more preferable that it is 30 mass% or more.

<< resin >>

The photosensitive coloring composition of this invention contains resin. As resin, alkali-soluble resin etc. are mentioned. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the use of a binder. Further, a resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such a use of the resin is an example, and a resin may be used for purposes other than these uses.

In the photosensitive coloring composition of this invention, it is preferable that content of resin is 1-80 mass% in all solid content of the photosensitive coloring composition. The lower limit is more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit is more preferably 70% by mass or less, and even more preferably 60% by mass or less.

(Alkali soluble resin)

The photosensitive coloring composition of this invention contains alkali-soluble resin. As the alkali-soluble resin, a resin having a group that promotes alkali dissolution can be appropriately selected. Examples of the group that promotes alkali dissolution (hereinafter also referred to as an acid group) include carboxyl groups, phosphoric acid groups, sulfo groups, phenolic hydroxyl groups, and the like, and carboxyl groups are preferred. The alkali-soluble resin may have only one type of acid group, or two or more types.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 to 100,000. Moreover, as for the number average molecular weight (Mn) of alkali-soluble resin, 1000-20,000 are preferable.

It is preferable that the acid value of alkali-soluble resin is 25-200 mgKOH / g. The lower limit is more preferably 30 mgKOH / g or more, and more preferably 40 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less.

As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred. Moreover, from a viewpoint of developability control, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin are preferable.

As the alkali-soluble resin, a polymer having a carboxyl group in the side chain is preferable. For example, copolymers having repeating units derived from monomers such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinylbenzoic acid, partially esterified maleic acid, furnace And alkali-soluble phenolic resins such as convex resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having an acid anhydride added to the polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, 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, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, and polymethylmethacrylate macromonomer. As for the other monomer which can be copolymerized with these (meth) acrylic acid, only 1 type may be sufficient and 2 or more types may be sufficient as it.

The alkali-soluble resin may have a repeating unit derived from a maleimide compound. As a maleimide compound, N-alkyl maleimide, N-aryl maleimide, etc. are mentioned. As a repeating unit derived from a maleimide compound, the repeating unit represented by Formula (C-mi) is mentioned.

[Formula 20]

In the formula (C-mi), Rmi represents an alkyl group or an aryl group. The alkyl group preferably has 1 to 20 carbon atoms. The alkyl group may be linear, branched or cyclic. 6-20 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are more preferable. Rmi is preferably an aryl group.

Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate A / (meth) acrylic acid / polypolymer composed of another moromer can be preferably used. In addition, a copolymer of 2-hydroxyethyl (meth) acrylate and other monomers, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzylmethod described in JP-A-7-140654. Acrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropylacrylate / polymethylmethacrylate macromonomer / benzylmethacrylate / methacrylic acid copolymer, 2-hydroxyethylmethacrylate / Polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. can also be preferably used.

As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group may be used. (Meth) allyl group, (meth) acryloyl group, etc. are mentioned as a polymerizable group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in a side chain or the like is useful. As commercially available products of alkali-soluble resins having a polymerizable group, Diana NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (polyurethane acrylate oligomer containing a carboxyl group, manufactured by Diamond Shamrock Co., Ltd.), biscoat R-264, KS resist 106 (all manufactured by Osaka Yuki Chemical Industry Co., Ltd.), Cyclomer P series (e.g., ACA230AA), Flaxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebecryl3800 (Daicel U Shibi Corporation), Acricure RD-F8 (made by Nippon Shokubai Co., Ltd.), DP-1305 (made by Fujifilm Fine Chemicals Co., Ltd.), and the like.

As the alkali-soluble resin, an alkali-soluble resin containing a repeating unit having a hydroxyl group is preferable. According to this aspect, affinity with a developer is improved, and it is easy to form a pattern excellent in rectangularity. In the alkali-soluble resin containing a repeating unit having a hydroxyl group, 30 to 100 mgKOH / g is preferable as the hydroxyl group of the alkali-soluble resin. The lower limit is more preferably 35 mgKOH / g or more, and more preferably 40 mgKOH / g or more. The upper limit is more preferably 80 mgKOH / g or less. When the hydroxyl group of the alkali-soluble resin is in the above range, it is easy to form a pattern excellent in rectangularity. As an alkali-soluble resin containing the repeating unit which has a hydroxyl group, resin of the following structure is mentioned, for example.

[Formula 21]

The alkali-soluble resin is a compound represented by the following formula (ED1) and at least one compound selected from compounds represented by formula (1) of JP 2010-168539 (hereinafter, these compounds are referred to as "ether dimer") It is also preferable to include a polymer formed by polymerizing a monomer component containing ().

[Formula 22]

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

As a specific example of the ether dimer, for example, paragraph No. 0317 of JP 2013-029760 A can be referred to, and this content is incorporated in this specification. As for the ether dimer, only 1 type may be sufficient and 2 or more types may be sufficient as it.

As a polymer formed by polymerizing a monomer component containing an ether dimer, for example, a polymer having the following structure can be mentioned.

[Formula 23]

The alkali-soluble resin may contain repeating units derived from the compound represented by the following formula (X).

[Formula 24]

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. Shows. n represents the integer of 1-15.

The alkali-soluble resin can take into account the description of Japanese Patent Laid-Open No. 2012-208494, paragraphs 0558 to 0571 (corresponding U.S. Patent Application Publication No. 2012/0235099, paragraphs 0685 to 0700), which are incorporated herein by reference. Is used for. Moreover, the copolymer (B) described in paragraph No. 0029 to 0063 of JP 2012-032767 A and the alkali-soluble resin used in Examples, and the binder resin described in JP 2012-208474 A of paragraph No. 0088-0098 And the binder resin used in Examples, the binder resin used in Examples and Binder Resins of Japanese Patent Application Publication No. 2012-137531, and the binder resins used in Examples, Paragraph Nos. 0132 to 0143 of Japanese Patent Application Publication No. 2013-024934 Binder resins used in Examples and Binder resins used in Examples, Paragraph Nos. 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and Paragraph Nos. 0030-0072 of Japanese Patent Laid-Open Nos. 2012-032770 You can also use the binder resin described in. These contents are incorporated herein.

As for content of alkali-soluble resin, 1-50 mass% is preferable in all solid content of the photosensitive coloring composition. The lower limit is more preferably 2% by mass or more, and even more preferably 3% by mass or more. The upper limit is more preferably 40% by mass or less, and even more preferably 35% by mass or less. The photosensitive coloring composition of this invention may contain only 1 type of alkali-soluble resin, and may contain 2 or more types. When 2 or more types are included, it is preferable that the total becomes the said range.

(Dispersant)

The photosensitive coloring composition of this invention can contain resin as a dispersing agent. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).

Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups. As the acid dispersant (acidic resin), when the total amount of the amount of the acid group and the amount of the basic group is 100 mol%, a resin in which the amount of the acid group occupies 70 mol% or more is preferable, and a resin consisting essentially of only an acid group is more preferable. . The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acid dispersant (acidic resin) is preferably 10 to 105 mgKOH / g.

Moreover, a basic dispersing agent (basic resin) represents a resin in which the amount of the basic group is larger than the amount of the acid group. As the basic dispersant (basic resin), when the total amount of the amount of the acid group and the amount of the basic group is 100 mol%, a resin whose amount of the basic group exceeds 50 mol% is preferable. The basic group possessed by the basic dispersant is preferably an amino group.

As a dispersing agent, for example, a polymer dispersing agent [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (Meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like. From the structure, the polymer dispersant can be further classified into a straight-chain polymer, a terminal-modified polymer, a graft polymer, and a block polymer. The polymer dispersant adsorbs on the surface of the pigment and acts to prevent reaggregation. For this reason, terminal modified polymers, graft polymers, and block polymers having anchor sites on the pigment surface are preferred structures. In addition, the dispersant described in JP 2011-070156 Paragraph Nos. 0028 to 0124 and the dispersant described in JP 2007-277514 A are also preferably used. These contents are incorporated herein.

In this invention, a graft copolymer can also be used as a dispersing agent. The details of the graft copolymer can be referred to the description of paragraphs 0131 to 0160 of JP 2012-137564 A, and this content is incorporated herein. Moreover, in this invention, as a dispersing agent, the resin containing a nitrogen atom in a main chain can also be used. Resins (hereinafter also referred to as oligoimine resins) containing a nitrogen atom in the main chain include poly (lower alkyleneimine) repeat units, polyallylamine repeat units, polydiallylamine repeat units, and methoxyxylenediamine It is preferable to include an epichlorohydrin polycondensate repeating unit and a repeating unit having at least one nitrogen atom selected from polyvinylamine repeating units. For the oligoimine-based resin, the description of paragraph No. 0102 to 0174 of JP 2012-255128 A can be referred to, and this content is incorporated herein.

A dispersant may also use a commercial item. For example, the product described in paragraph No. 0129 of JP 2012-137564 A can also be used as a dispersant. For example, the DISPERBYK series (for example, DISPERBYK-161 etc.) by BYKChemie are mentioned. Moreover, the resin demonstrated as said dispersing agent can also be used for uses other than a dispersing agent. For example, it can also be used as a binder.

The content of the dispersant is preferably 1 to 200 parts by mass based on 100 parts by mass of the pigment. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.

(Other resins)

The photosensitive coloring composition of this invention can contain resin (otherwise resin) other than the dispersing agent and alkali-soluble resin mentioned above as resin. As other resins, for example, (meth) acrylic resin, (meth) acrylamide resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin , Polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, and the like. Other resins may be used alone or in combination of two or more from these resins.

<< polymerizable compound >>

It is preferable that the photosensitive coloring composition of this invention contains a polymeric compound in addition to the coloring material which has a polymerizable group. As a polymerizable compound, the compound etc. which have an ethylenically unsaturated group are mentioned, for example. Examples of the ethylenically unsaturated group include a vinyl group, (meth) allyl group, and (meth) acryloyl group. It is preferable that a polymerizable compound is a compound (radical polymerizable compound) polymerizable by a radical. In addition, in this specification, a polymerizable compound is a compound different from the color material which has a polymerizable group. It is preferable that a polymerizable compound is a compound which does not have a dye structure.

As the polymerizable compound, any of chemical forms such as a monomer, a prepolymer and an oligomer may be used, but a monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more.

The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and a compound containing 3 to 6 ethylenically unsaturated groups More preferred. Moreover, it is preferable that a radical polymerizable compound is a 3-15 functional (meth) acrylate compound, and it is more preferable that it is a 3-6 functional (meth) acrylate compound. Specific examples of the radically polymerizable compound include compounds described in paragraphs 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, and paragraphs 0254 to 0257 of JP 2008-292970 A. And these contents are incorporated herein.

The polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA as a commercial product; Nippon Kayaku ( Note), NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and the structure in which these (meth) acryloyl groups are bonded through ethylene glycol and / or propylene glycol residues Compounds of (e.g., SR454, SR499 commercially available from Sartomer) are preferred. Oligomer types of these can also be used. Moreover, NK ester A-TMMT (made by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, DPCA-20 (made by Nippon Kayaku Co., Ltd.) can also be used as a radically polymerizable compound. Moreover, as a radically polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, iso It is also preferable to use trifunctional (meth) acrylate compounds such as ethyleneoxy-modified cyanuric acid tri (meth) acrylate and pentaerythritol tri (meth) acrylate. As a commercial product of a trifunctional (meth) acrylate compound, Aaronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305 , M-303, M-452, M-450 (manufactured by Toa Kosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (made by Nippon Kayaku Co., Ltd.) ) And the like.

The polymerizable compound may have an acid group. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable. As a commercial item of a radically polymerizable compound having an acid group, Aaronix M-510, M-520, Aaronix TO-2349 (manufactured by Toagosei Co., Ltd.), etc. may be mentioned.

The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, solubility in a developer is good, and if it is 40 mgKOH / g or less, it is advantageous in manufacturing and handling.

It is also preferable that the polymerizable compound is a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is commercially available as, for example, KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

It is also preferable that a polymerizable compound is a compound which has an alkyleneoxy group. The polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and a 3-6 function having 4-20 ethyleneoxy groups ( It is more preferable that it is a meth) acrylate compound. As a commercial item of a polymerizable compound having an alkyleneoxy group, for example, SR-494, which is a tetrafunctional (meth) acrylate having 4 ethyleneoxy groups manufactured by Sartomer, and trifunctional (meth) having 3 isobutyleneoxy groups. And acrylate KAYARAD TPA-330.

Examples of the polymerizable compound are those described in Japanese Patent Application Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Application Publication No. Hei 2-032293, and Japanese Patent Application Publication No. Hei 2-016765. Ethylene acrylate, ethylene oxide described in Japanese Patent Application Publication No. 58-049860, Japanese Patent Application Publication No. 56-017654, Japanese Patent Application Publication No. 62-039417, Japanese Patent Application Publication No. 62-039418 Uretaine compounds having a system skeleton are also suitable. Moreover, it is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecules described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. Hei1-105238. . As a commercial product, UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 And AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

Moreover, as a polymerizable compound, it is also preferable to use 8UH-1006, 8UH-1012 (above, manufactured by Daisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. .

Moreover, as a polymerizable compound, the compound described in Unexamined-Japanese-Patent No. 2017-048367, Japanese Patent Publication No. 6057891, and Japanese Patent Publication No. 6031807 can also be used.

As for content of a polymerizable compound, 0.1-50 mass% is preferable in all solid content of the photosensitive coloring composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less.

Moreover, it is preferable that content of a polymeric compound is 25-500 mass parts with respect to 100 mass parts of color materials which have a polymerizable group. The lower limit is more preferably 30 parts by mass or more, and even more preferably 50 parts by mass or more. The upper limit is more preferably 450 parts by mass or less, and even more preferably 300 parts by mass or less. If the content of the polymerizable compound is within the above range, refinement of the development pattern can be expected more.

Moreover, 20-80 mass% is preferable in the total solid content of the photosensitive coloring composition as the total amount of the coloring material which has a polymerizable compound and a polymerizable group. The lower limit is more preferably 25% by mass or more, and even more preferably 40% by mass or more. The upper limit is more preferably 75% by mass or less, and even more preferably 60% by mass or less. When the total amount described above is within the above range, a cured film that is more excellent in adhesion to the support is easily obtained.

Moreover, it is preferable that the total amount of the coloring material which has a polymerizable compound and a polymerizable group is 25-500 mass parts with respect to 100 mass parts of total of photoinitiator a and photoinitiator b. The lower limit is more preferably 30 parts by mass or more, and even more preferably 50 parts by mass or more. The upper limit is more preferably 450 parts by mass or less, and even more preferably 300 parts by mass or less. If it is this range, a cured film excellent in the discoloration resistance with respect to a developing solution, adhesiveness with a support body, etc. is more easily obtained.

<< compound having an epoxy group >>

It is preferable that the photosensitive coloring composition of this invention contains the compound which has an epoxy group further. According to this aspect, the mechanical strength and the like of the obtained cured film can be improved. As a compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. It is preferable to have 2 to 100 epoxy groups in one molecule. The upper limit may be, for example, 10 or less, or 5 or less.

The epoxy equivalent of the compound having an epoxy group (= molecular weight of the compound having an epoxy group / number of epoxy groups) is preferably 500 g / eq or less, more preferably 100-400 g / eq, and more preferably 100-300 g / eq. Do.

The compound having an epoxy group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecular compound (for example, a molecular weight of 1000 or more, in the case of a polymer, a weight-average molecular weight of 1000 or more). do. The molecular weight of the compound having an epoxy group (in the case of a polymer, the weight average molecular weight) is preferably 200 to 100,000, and more preferably 500 to 50000. The upper limit of the molecular weight (in the case of a polymer, the weight average molecular weight) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less.

As the compound having an epoxy group, the compounds described in paragraphs 0034 to 0036 of JP 2013-011869, paragraphs 0147 to 0156 of JP 2014-043556, and paragraphs 0085 to 0092 of JP 2014-089408 You can also use These contents are incorporated herein.

When the photosensitive coloring composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass in the total solid content of the photosensitive coloring composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more, for example. As an upper limit, 30 mass% or less is more preferable, for example, 20 mass% or less is more preferable. The compound having an epoxy group may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a total amount becomes the said range. Moreover, the content of the compound having an epoxy group is preferably 1 to 400 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the polymerizable compound.

<< solvent >>

It is preferable that the photosensitive coloring composition of this invention contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as the solubility of each component and the coatability of the photosensitive coloring composition are satisfied.

Examples of the organic solvent include the following organic solvents. As the esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl acetate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate) , Ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionic acid, ethyl 3-alkyloxypropionic acid, etc. (for example, methyl 3-methoxypropionic acid, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-alkyloxypropionic acid alkyl esters (for example Cotton, 2-alkyloxypropionic acid methyl, 2-alkyloxypropionic acid ethyl, 2-alkyloxypropionic acid propyl, etc. (e.g., 2-methoxypropionic acid methyl, 2-methoxypropionic acid ethyl, 2-methoxypropionic acid profile, 2 -Methyl ethoxypropionic acid, ethyl 2-ethoxypropionic acid)), methyl 2-alkyloxy-2-methylpropionic acid and ethyl 2-alkyloxy-2-methylpropionic acid (for example, 2-methoxy-2-methylpropionic acid) Methyl, 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutaneate, ethyl 2-oxobutaneate, and the like. . As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, And propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned, for example. As aromatic hydrocarbons, for example, toluene, xylene, and the like are exemplified. However, it may be preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents for reasons such as environmental reasons (for example, 50 mass based on the total amount of organic solvent) ppm (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less).

The organic solvents may be used alone or in combination of two or more. When using two or more types of organic solvents in combination, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether , 2 selected from butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate It is a mixed liquid composed of more than one species.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably does not substantially contain a peroxide. Moreover, it is preferable to use the organic solvent with a small metal content, for example, it is preferable that the metal content of an organic solvent is 10 mass parts per billion (ppb) or less. If necessary, the metal content of the organic solvent may be a mass ppt (parts per trillion) level, and such high-purity solvents are provided by, for example, Toyo Kosei Co., Ltd. (Kagaku High School Nippon, November 13, 2015) Work).

The content of the solvent is preferably an amount such that the total solid content of the photosensitive coloring composition is 5 to 80% by mass. The lower limit is preferably 10% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

<< curing accelerator >>

The photosensitive coloring composition of the present invention may be added with a curing accelerator for the purpose of promoting the reaction of the polymerizable compound or lowering the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkane thiol, and more preferably a compound represented by formula (T1).

Expression (T1)

[Formula 25]

(In formula (T1), n represents the integer of 2-4, and L represents a 2-4 tetravalent coupling group.)

In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and L is particularly preferably an alkylene group having 2 to 12 carbon atoms. As a specific example of a polyfunctional thiol compound, the compound represented by the following structural formulas (T2)-(T4) is mentioned, and the compound represented by formula (T2) is especially preferable. It is possible to use such a polyfunctional thiol compound in combination of one kind or plural.

[Formula 26]

In addition, the curing accelerator is a methylol-based compound (for example, a compound exemplified as a crosslinking agent in Japanese Patent Application Publication No. 2015-034963, paragraph No. 0246), amines, phosphonium salts, amidine salts, and amide compounds (above, eg For example, a curing agent described in paragraph No. 0186 of JP 2013-041165), a base generator (for example, an ionic compound disclosed in JP 2014-055114), and a cyanate compound (for example, Japanese Patent Application Publication No. 2012-150180, the compound described in paragraph No. 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in Japanese Patent Application Publication No. 2011-253054), an onium salt compound (for example For example, a compound exemplified as an acid generator in paragraph No. 0216 of JP 2015-034963 A, a compound described in JP 2009-180949 A) can also be used. .

When the photosensitive coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9 mass%, and more preferably 0.8 to 6.4 mass%, in the total solid content of the photosensitive coloring composition.

<< surfactant >>

The photosensitive coloring composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

By incorporating a fluorine-based surfactant in the photosensitive coloring composition of the present invention, liquid properties (especially fluidity) when prepared as a coating liquid are improved, and uniformity and liquid-liquidity after coating can be further improved. That is, in the case of forming a film using a coating liquid to which a photosensitive coloring composition containing a fluorine-based surfactant is applied, the interfacial tension between the coated surface and the coating liquid is lowered, and the wettability to the coated surface is improved to improve the coated surface. The coating properties are improved. For this reason, it is possible to more appropriately form a film having a uniform thickness with a small thickness variation.

The fluorine-containing content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in the above range is effective in terms of uniformity of the thickness of the coating film and liquid-repellency, and also has good solubility in the photosensitive coloring composition.

As the fluorine-based surfactant, for example, Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above, manufactured by DIC Corporation) , Fluorad FC430, FC431, FC171 (above, Sumitomo 3M Co., Ltd.), SUPRRON S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (above, Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like. As the fluorine-based surfactant, the compounds described in Japanese Patent Application Laid-Open No. 2015-117327, paragraphs 0015 to 1158, and the compounds described in Japanese Patent Laid-Open Publication No. 2011-132503, can be used.

The fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heated, an acrylic compound in which a portion of the functional group containing a fluorine atom is cut to volatilize the fluorine atom can also be suitably used. As such a fluorine-based surfactant, DIC Corporation's Megapak DS series (Kagaku High School Nippon, February 22, 2016) (Nikkei Sangyo status, February 23, 2016), for example Megapak DS- 21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Such a fluorine-based surfactant can take into account the description of Japanese Patent Application Laid-open No. 2016-216602, the contents of which are incorporated herein.

As the fluorine-based surfactant, a block polymer can also be used. For example, the compound described in JP 2011-089090 A can be cited. The fluorine-based surfactant (meth) having a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). ) A fluorinated polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as fluorine-based surfactants used in the present invention. In the following formula,% representing the proportion of repeating units is mol%.

[Formula 27]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000.

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. As a specific example, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A are exemplified. As a commercial item, Megapak RS-101, RS-102, RS-718-K, RS-72-K etc. by DIC Corporation are mentioned, for example.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , Sobitan Fatty Acid Ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspur 20000 (Nihon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Junyaku High School Co., Ltd.), Pionein D-6112, D-6112-W, D-6315 (Yoshi Takemoto ( Note), Olfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.) and the like.

As a cationic surfactant, organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Corporation), and the like.

Examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co., Ltd.), and the like.

Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (above, manufactured by Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK-307, BYK-323, BYK-330 (above, manufactured by Big Chemical), and the like.

As for content of surfactant, 0.001-2.0 mass% is preferable in all solid content of the photosensitive coloring composition, and 0.005-1.0 mass% is more preferable. As surfactant, only 1 type may be used and 2 or more types may be combined. When 2 or more types are included, it is preferable that a total amount is the said range.

<< silane coupling agent >>

The photosensitive coloring composition of this invention can contain a silane coupling agent. As a silane coupling agent, a silane compound having at least two functional groups having different reactivity in one molecule is preferable. The silane coupling agent includes at least one tile selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, Silane compounds having an alkoxy group are preferred. As a specific example of a silane coupling agent, for example, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. make, KBM-602), N-β-aminoethyl-γ- Aminopropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), N-β-aminoethyl-γ-aminopropyl triethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-602), γ -Aminopropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-903), γ-aminopropyl triethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloxypropyl tri Methoxysilane (Shin-Etsu Chemical Co., Ltd. product, KBM-503), 3-glycidoxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. product, KBM-403) etc. are mentioned. For details of the silane coupling agent, description of paragraph No. 0155 to 1158 of JP 2013-254047 A can be referred to, and this content is incorporated herein.

When the photosensitive coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, in the total solid content of the photosensitive coloring composition, 0.1 mass%-5 mass% is especially preferable. The photosensitive coloring composition of this invention may contain only 1 type of silane coupling agent, or may contain 2 or more types. When 2 or more types are included, it is preferable that these total amounts become the said range.

<< polymerization inhibitor >>

It is also preferable that the photosensitive coloring composition of this invention contains a polymerization inhibitor. Examples of the polymerization inhibitor 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 salt (ammonium salt, first cerium salt, etc.) and the like. have.

When the photosensitive coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass in the total solid content of the photosensitive coloring composition. The photosensitive coloring composition of the present invention may contain only one type of polymerization inhibitor or two or more types. When 2 or more types are included, it is preferable that the total amount becomes said range.

<< Ultraviolet absorbent >>

The photosensitive coloring composition of this invention can contain a ultraviolet absorber. As the ultraviolet absorber, conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, etc. Can be used. For the details of these, the descriptions of paragraphs 0052 to 0072 of Japanese Patent Application Publication No. 2012-208374 and paragraphs 0317 to 0334 of Japanese Patent Application Publication No. 2013-068814 can be referred to, and these contents are incorporated herein. As a commercial item of a ultraviolet absorber, UV-503 (made by Daito Chemical Co., Ltd.) etc. is mentioned, for example. Moreover, as a benzotriazole compound, you may use the MYUA series (made by Miyoshi Yushi Co., Ltd., Kagaku Kogyo Nibo, February 1, 2016).

When the photosensitive coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and more preferably 0.1 to 3% by mass in all solid content of the photosensitive coloring composition. % Is particularly preferred. Moreover, only 1 type may be used and two or more types of ultraviolet absorbers may be used. When using 2 or more types, it is preferable that a total amount falls into the said range.

<< Other additives >>

In the photosensitive coloring composition of the present invention, various additives such as fillers, adhesion promoters, antioxidants, and anti-agglomerates can be blended, if necessary. Examples of these additives include additives described in Japanese Patent Laid-Open No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein. Moreover, as an antioxidant, a phenol compound, a phosphorus compound (for example, the compound described in Unexamined-Japanese-Patent No. 2011-090147, Paragraph No. 0042), a thioether compound, etc. can be used. As a commercial item, the Adekastave series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO made by ADEKA Corporation, for example -330, etc.). As for antioxidant, only 1 type may be used and 2 or more types may be used. The colored composition of the present invention may contain the sensitizer or light stabilizer described in paragraph No. 0078 of JP 2004-295116A, and a thermal polymerization inhibitor described in paragraph No. 0081 of the same publication.

Although the metal element may be contained in the photosensitive coloring composition depending on the raw material to be used, from the viewpoint of suppressing the occurrence of defects, the content of the Group 2 element (calcium, magnesium, etc.) in the coloring composition is preferably 50 ppm by mass or less, and 0.01 ~ 10 mass ppm is more preferable. Moreover, it is preferable that the total amount of the inorganic metal salt in a photosensitive coloring composition is 100 mass ppm or less, and 0.5-50 mass ppm is more preferable.

The water content of the photosensitive coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fisher method.

The photosensitive coloring composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface (flatness, etc.), adjusting the film thickness, and the like. Although the value of the viscosity can be appropriately selected as necessary, for example, 0.3 mPa · s to 50 mPa · s at 25 ° C. is preferable, and 0.5 mPa · s to 20 mPa · s is more preferable. As a method for measuring the viscosity, for example, a Toki Sangyo-made viscometer RE85L (rotor: 1 ° 34 '× R24, measurement range 0.6 to 1200 mPa · s) can be used to measure the temperature at 25 ° C.

The storage container of the photosensitive coloring composition of the present invention is not particularly limited, and a known storage container can be used. Further, for the purpose of suppressing the mixing of impurities into raw materials or compositions as a storage container, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of six types of six-layer resins or a bottle made of six types of resins in a seven-layer structure. Do. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

The photosensitive coloring composition of this invention can be used suitably as a photosensitive coloring composition for formation of a coloring pixel in a color filter. Examples of the colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow color pixels, and the like. Moreover, since the color material contained in a blue pixel often has absorption with respect to i-rays, in the conventional photosensitive coloring composition, curing by exposure tends to be insufficient. For this reason, post-baking at a high temperature has been required in the past to form blue pixels. However, according to the present invention, by curing at a low temperature, a blue pixel (cured film) excellent in discoloration resistance to a developer can be formed, and the effect of the present invention is more remarkably exhibited.

When the photosensitive coloring composition of the present invention is used as a color filter for use in a liquid crystal display device, the voltage retention ratio of the liquid crystal display element provided with the color filter is preferably 70% or more, and more preferably 90% or more. Well-known means for obtaining a high voltage retention ratio can be appropriately introduced, and typical means include use of a material with high purity (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition. The voltage retention ratio can be measured, for example, by the method described in paragraph 0243 of JP 2011-008004 A, paragraphs 0123 to 0129 of JP 2012-224847 A, and the like.

<Preparation method of photosensitive coloring composition>

The photosensitive coloring composition of this invention can be prepared by mixing the above-mentioned components. When mixing and preparing a photosensitive coloring composition, the entire component may be dissolved and / or dispersed in a solvent at the same time to prepare a photosensitive coloring composition, and if necessary, each component may be suitably used as two or more solutions or dispersions. You may mix these with (when apply | coating), and prepare the photosensitive coloring composition.

Moreover, when preparing a photosensitive coloring composition containing a pigment, in preparing a photosensitive coloring composition, it is also preferable to include the process of dispersing a pigment. In the process of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, compression, impact, shearing, and cavitation. Specific examples of these processes include beads mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like. In addition, in the grinding of the pigment in the sand mill (bead mill), it is preferable to use beads with a small diameter, or to increase the filling rate of the beads, and to treat them under conditions of increasing the grinding efficiency. Moreover, it is preferable to remove defect particles by filtration, centrifugation, etc. after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "dispersed technology Daejeon, issued by Joho Kiko Co., Ltd., July 15, 2005" or "the actual synthesis of dispersion technology and industrial applications centered on suspension (solid / liquid dispersion system)" The publication and publication of the Business Development Center Publication, October 10, 1978 ", Japanese Patent Application Publication No. 2015-157893, paragraph No. 0022, can be suitably used. Moreover, in the process of dispersing a pigment, you may perform a particle refinement process in a salt milling process. Materials, equipment, processing conditions, and the like used in the salt milling process can be referred to, for example, Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629.

When preparing a photosensitive coloring composition, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. As a filter, if it is a filter conventionally used for filtration use, etc., it is not specifically limited and can be used. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). And filters using materials such as (including high-density and / or ultra-high molecular weight polyolefin resins). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The hole diameter of the filter is 0.01 to 7. About 0 μm is suitable, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm.

Moreover, as a filter, it is also preferable to use a filter using a fibrous filter medium. As a fibrous filter medium, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example. As a filter using a fibrous filter medium, specifically, filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Rocky Techno Corporation are exemplified.

When using a filter, you may combine other filters. In that case, filtration using each filter may be performed only once, or may be performed two or more times.

For example, filters of different hole diameters may be combined within the above-described range. The hole diameter here can refer to the nominal value of a filter maker. As a commercially available filter, for example, you can select from various filters provided by Nippon Paul Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nihon Integris Co., Ltd. (formerly Nippon Microlis Co., Ltd.) or Kits Micro Filter Co., Ltd.

In addition, filtration using the first filter may be performed only with a dispersion, mixed with other components, and then filtered with a second filter. As the second filter, one formed of the same material or the like as the first filter can be used.

<Cured film>

The cured film of this invention is a cured film obtained from the photosensitive coloring composition of this invention mentioned above. The cured film of this invention can be used suitably as a colored pixel of a color filter. Examples of the colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow color pixels. The film thickness of the cured film can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

<How to form a pattern>

The pattern forming method of the present invention comprises the steps of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition of the present invention described above,

A step of exposing the photosensitive coloring composition layer in a pattern by irradiating light having a wavelength of more than 350 nm and less than or equal to 380 nm;

A step of alkali developing the photosensitive coloring composition layer after exposure;

The photosensitive coloring composition layer after alkali development has a step of irradiating and exposing light having a wavelength of 254 to 350 nm. Further, if necessary, a step of forming a photosensitive coloring composition layer on a support and baking before exposure (pre-baking step) and a step of baking an alkali developed pattern (post-baking step) may be provided. Hereinafter, each process is demonstrated.

In the process of forming a photosensitive coloring composition layer, a photosensitive coloring composition layer is formed on a support body using a photosensitive coloring composition.

There is no restriction | limiting in particular as a support body, It can select suitably according to the use. For example, a glass substrate, a solid-state imaging element substrate on which a solid-state imaging element (light-receiving element) is employed, a silicon substrate, and the like can be given. Further, on these substrates, an undercoat layer may be provided, if necessary, to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface.

As a method of applying the photosensitive coloring composition on the support, various methods such as slit coating, inkjet method, rotation coating, flexible coating, roll coating, and screen printing can be used.

The photosensitive coloring composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, prebaking is not required. When prebaking, the prebaking temperature is preferably 120 ° C or lower, more preferably 110 ° C or lower, and even more preferably 105 ° C or lower. The lower limit may be, for example, 50 ° C or higher, or 80 ° C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. The pre-baking can be performed with a hot plate, an oven, or the like.

Next, the photosensitive coloring composition layer is irradiated with light having a wavelength of 350 nm or more and 380 nm or less, and exposed in a pattern. For example, the photosensitive coloring composition layer can be exposed in a pattern by exposing it through a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed part of the photosensitive coloring composition layer can be hardened. As the radiation (light) that can be used at the time of exposure, light having a wavelength of more than 350 nm and 380 nm or less is preferable, and light having a wavelength of 355 to 370 nm is preferable, and i-ray is more preferable. As the irradiation amount (exposure amount), for example, 30 to 1500 mJ / cm ² is preferable, and 50 to 1000 mJ / cm ² is more preferable. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19 vol% or less (eg, 15 vol%, 5 vol%, substantially oxygen-free) ), Or may be exposed under a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) with an oxygen concentration exceeding 21% by volume. In addition, the exposure illumination may be selected from is possible, and usually in the range of ^{1000W / m 2 ~ 100000W / m} 2 ( for ^{example, 5000W / m 2, 15000W /} m 2, 35000W / m 2) to set properly. Oxygen concentration and exposure illuminance may be combined as appropriate, and the conditions, for example, roughness on the oxygen concentration of 10 volume% 10000W / m ^2, 20000W roughness in oxygen concentration 35 vol% / m ² and the like.

It is preferable that the reaction rate of the polymerizable compound in the photosensitive coloring composition layer after exposure is more than 30% and less than 60%. By setting it as such a reaction rate, it can be set as the state which hardened | cured a polymeric compound suitably. Here, the reaction rate of the polymerizable compound refers to the proportion of the ethylenically unsaturated groups reacted in all the ethylenically unsaturated groups of the polymerizable compound.

Next, the photosensitive coloring composition layer after exposure is alkali-developed. That is, the photosensitive coloring composition layer of the unexposed portion is removed using an alkali developer to form a pattern. The temperature of the alkali developer is preferably 20 to 30 ° C, for example. The development time is preferably 20 to 300 seconds.

As the alkali developer, an alkaline aqueous solution in which an alkali agent is diluted with pure water is preferably used. Examples of the alkali agent include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. Side, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8 And organic alkaline compounds such as diazabicyclo [5.4.0] -7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium metasilicate. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Moreover, surfactant may be further included in the alkali developer. The surfactant mentioned above is mentioned as an example of surfactant, Non-ionic surfactant is preferable. The alkali developer may be prepared as a concentrate once from a viewpoint of convenience of transport or storage, and may be diluted to a concentration necessary for use. The dilution ratio is not particularly limited, but can be set, for example, in a range of 1.5 to 100 times. Moreover, it is preferable to wash (rinse) with pure water after image development. Moreover, when using the developing solution which consists of such an alkaline aqueous solution, it is preferable to wash (rinse) with pure water after image development.

Next, the photosensitive coloring composition layer after alkali development is exposed by irradiating light having a wavelength of 254 to 350 nm. Hereinafter, exposure after alkali development is also called post exposure. As the radiation (light) that can be used in post-exposure, ultraviolet rays having a wavelength of 254 to 300 nm are preferable, and ultraviolet rays having a wavelength of 254 nm are more preferable. Post-exposure can be performed, for example, using an ultraviolet photoresist curing apparatus. The ultraviolet photoresist curing apparatus may be irradiated with light (eg, i-line) other than the light having a wavelength of 254 to 350 nm, for example.

The difference between the wavelength of light used for exposure before alkali development and the wavelength of light used for exposure after alkali development (post exposure) is preferably 200 nm or less, and more preferably 100 to 150 nm. Irradiation dose (exposure dose) is, 30 ~ 4000mJ / cm ² are preferred, and more preferably 50 ~ 3500mJ / cm ^2. The oxygen concentration at the time of exposure can be appropriately selected. The conditions explained by the exposure process before alkali development mentioned above are mentioned.

The reaction rate of the polymerizable compound in the photosensitive coloring composition layer after post exposure is preferably 60% or more. The upper limit may be 100% or less, or 90% or less. By setting it as such a reaction rate, the cured state of the photosensitive coloring composition layer after exposure can be made more favorable.

In the present invention, by exposing the photosensitive coloring composition layer in two steps before and after alkali development, the photosensitive coloring composition can be appropriately cured with the first exposure (exposure before alkali development), and the next exposure (exposure after development) As a result, the entire photosensitive coloring composition can be cured almost completely. As a result, even under low temperature conditions, the photosensitive coloring composition can be sufficiently cured, and a pattern (cured film) excellent in discoloration resistance to a developer can be formed.

In the pattern formation of the present invention, post-baking may also be performed after post-exposure. In the case of post-baking, 50 to 120 ° C (more preferably 80 to 100 ° C), in the case of using an organic electroluminescent element as a light-emitting color source of the image display device, or when the photoelectric conversion film of the image sensor is made of an organic material It is preferable to perform heat treatment (post-baking) at ℃, more preferably 80 to 90 ° C). The post-baking can be performed continuously or in a batch mode by using heating means such as a hot plate, a convection oven (hot air circulation dryer), and a high-frequency heater. In addition, in the case of forming a pattern by a low-temperature process, post-baking is not necessary.

The thickness of the pattern (hereinafter also referred to as a pixel) after post-exposure (after post-baking when post-baking is performed after post-exposure) is preferably 0.1 to 2.0 μm. The lower limit is preferably 0.2 μm or more, and more preferably 0.3 μm or more. The upper limit is preferably 1.7 μm or less, and more preferably 1.5 μm or less.

The width of the pixel is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, and more preferably 10.0 μm or less.

The Young's modulus of the pixel is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

It is preferable that the pixel has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably, for example, 0.1 nm or more. The surface roughness can be measured, for example, using AFM (atomic force microscope) Dimension3100 manufactured by Veeco.

Moreover, although the contact angle of water on a pixel can be set to a suitably preferable value, it is typically in the range of 50 to 110 °. The contact angle can be measured using, for example, a contact angle meter CV-DT · A type (manufactured by Kyowa Kamen Chemical Co., Ltd.).

It is preferable that the pixel has a high volume resistance value. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω · cm or more, and more preferably 10 ¹¹ Ω · cm or more. Although the upper limit is not specified, it is preferably, for example, 10 ¹⁴ Ω · cm or less. The volume resistance value of the pixel can be measured, for example, using an ultra-high ohmmeter 5410 (manufactured by Advantest).

<Color filter>

Next, the color filter of the present invention will be described. The color filter of this invention has the cured film of this invention mentioned above. In the color filter of the present invention, the film thickness of the cured film can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more. The color filter of the present invention can be used for solid-state imaging elements such as CCDs (charge-coupled elements) and CMOS (complementary metal oxide film semiconductors) and image display devices.

<Solid imaging device>

The solid-state imaging element of the present invention has the cured film of the present invention described above. The structure of the solid-state imaging device of the present invention is not particularly limited as long as it is provided with the cured film of the present invention and functions as a solid-state imaging device, but the following structures are exemplified.

On the substrate, a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light-receiving area of a solid-state imaging device (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.), A light-shielding film having only a light-receiving portion of a photodiode opened on the photodiode and a transfer electrode, and a device protective film made of silicon nitride or the like formed to cover the entire light-shielding film and the photodiode light-receiving portion on the light-shielding film. It has a structure. Moreover, the structure which has a condensing means (for example, a micro lens, etc. below) on a device protective film and under a color filter (the side close to a board | substrate), the structure which has a condensing means on a color filter etc. may be sufficient. Further, the color filter may have a structure in which a cured film forming each colored pixel is embedded in a space divided by, for example, a grid by partition walls. It is preferable that the partition wall in this case has a low refractive index for each colored pixel. Examples of the imaging device having such a structure include devices described in JP 2012-227478 A and JP 2014-179577 A. The imaging device provided with the solid-state imaging element of the present invention can be used not only for a digital camera or an electronic device (cell phone, etc.) having an imaging function, but also for an on-vehicle camera or a surveillance camera.

<Image display device>

The cured film of this invention can be used for image display apparatuses, such as a liquid crystal display device and an organic electroluminescence display device. For the definition of the image display device and the details of each image display device, for example, "electronic display device (Akio Sasaki, Kosaka High School, published in 1990)", "Display device (Sumiaki Ibuki, Sankyo) Tosho Co., Ltd. published by the first year of Heisei). Moreover, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (Tatsuo Uchida, High School Chosaka Co., Ltd., issued in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, it can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology".

Example

The present invention will be specifically described below with reference to Examples. Materials, amounts, proportions, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "part" and "%" are based on mass.

<Preparation of pigment dispersion composition>

(Pigment dispersion P1)

CI Pigment Blue 15: 6 20.0 parts by mass (average primary particle diameter 55 nm), pigment dispersant (DISPERBYK-161, BYK Chemie) 2.40 parts by mass, dispersant 1 2.40 parts by mass, propylene glycol monomethyl ether The mixed solution of 175.2 parts by mass of acetate (PGMEA) was mixed and dispersed for 3 hours using a bead mill (zirconia beads having a diameter of 0.3 mm). Subsequently, dispersion treatment was performed at a pressure of 2000 kg / cm ^{3 at} a flow rate of 500 g / min using a high pressure disperser NANO-3000-10 equipped with a decompression mechanism (manufactured by Nippon Biei Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion liquid P1. About the obtained pigment dispersion liquid P1, the average primary particle diameter of the pigment was measured by dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso)), and was 24 nm.

· Dispersant 1: Resin with the following structure (value added to the main chain is molar ratio, Mw = 11000)

[Formula 28]

(Pigment dispersion P2)

A pigment dispersion liquid P2 was obtained in the same manner as the pigment dispersion liquid P1, except that the dispersion resin A described in paragraph No. 0577 of JP 2013-195854 A was used in place of the dispersant 1.

<Preparation of photosensitive coloring composition>

(Example 1)

The raw materials shown below were mixed and stirred, followed by filtration through a filter made of nylon having a pore diameter of 0.45 µm (manufactured by Nippon Paul Co., Ltd.) to prepare a photosensitive coloring composition.

Pigment dispersion P1 ... 60.0 parts by mass

Photopolymerization initiator (initiator 1) ... 1.68 parts by mass

Photopolymerization initiator (initiator 4) ... 0.63 parts by mass

Alkali-soluble resin (Resin A) ... 0.60 parts by mass

Polymerizable compound (M1) ... 6.00 parts by mass

Dye (V1) ... 20.0 parts by mass

Epoxy compound (EHPE 3150, Daicel Co., Ltd.) ... 0.66 parts by mass

Polymerization inhibitor (p-methoxyphenol) ... 0.0007 parts by mass

Surfactant (1 mass% cyclohexanone solution of the compound of the following structure (Mw = 14000, the numerical value of% representing the proportion of repeating units is mol%): 2.50 parts by mass

[Formula 29]

Cyclohexanone ... 7.74 parts by mass

(Examples 2 to 18, Comparative Examples 1 to 4)

Photosensitive coloring composition in the same manner as in Example 1 except that the type of the pigment dispersion, the type and content of the photopolymerization initiator, the type of the alkali-soluble resin, the type of the dye, and the type of the polymerizable compound were changed as described in the table below. Was prepared. In addition, the numerical value of the content described in the column of the photoinitiator of the following table is content in all solid content of the photosensitive coloring composition.

[Table 1]

(Examples 19-22)

A photosensitive coloring composition was prepared in the same manner as in Example 1, except that the content of the dye (V1) was changed as described in the table below. In the following table, the mass ratio of the color material having a polymerizable group and the photopolymerization initiator (the total amount of initiators 1 and 4) is also recorded.

[Table 2]

The raw materials listed in the above table are as follows.

(Photopolymerization initiator)

Initiator 1: IRGACURE-OXE01 (manufactured by BASF, the absorption coefficient of light at a wavelength of 365 nm in methanol is 6969 mL / gcm)

Initiator 2: IRGACURE-OXE02 (manufactured by BASF, the absorption coefficient of light at a wavelength of 365 nm in methanol is 7749 mL / gcm)

Initiator 3: Compound of the following structure (the absorption coefficient of light at a wavelength of 365 nm in methanol is 18900 mL / gcm)

[Formula 30]

Initiator 4: IRGACURE 2959 (manufactured by BASF, the absorption coefficient of light at a wavelength of 365 nm in methanol is 48.93 mL / gcm, and the absorption coefficient of light at a wavelength of 254 nm is 3.0 × 10 ⁴ mL / gcm.)

Initiator 5: IRGACURE 184 (manufactured by BASF, the absorption coefficient of light at a wavelength of 365 nm in methanol is 88.64 mL / gcm, and the absorption coefficient of light at a wavelength of 254 nm is 3.3 × 10 ⁴ mL / gcm.)

(Alkali soluble resin)

Resin A: Resin having the following structure (Mw = 11000, acid value = 31.5 mgKOH / g, the value added to the main chain is a molar ratio.)

[Formula 31]

Resin B: Resin of the following structure (Mw = 30000, acid value = 112.8 mgKOH / g, the numerical value added to the main chain is a molar ratio.)

[Formula 32]

Resin C: Alkali-soluble resin J5 described in JP 2013-225112 Para. No. 0573

Resin D: Resin B-1 described in JP 2010-049161 Paragraph No. 0150

(dyes)

Dye V1: 20% by mass of cyclohexanone solution of a dye multimer having the following structure (a dye having a polymerizable group)

[Formula 33]

Dye V2: a 20% by mass cyclohexanone solution of a dye multimer having the following structure (a dye having a polymerizable group, and a value added to the main chain is Mw = 13000)

[Formula 34]

Dye V3: a cyclohexanone solution of 20% by mass of a dye multimer having the following structure (a dye having no polymerizable group, and the numerical value added to the main chain is Mw = 12000)

[Formula 35]

Dye V4: a cyclohexanone solution of 20% by mass of a dye compound (a dye having a polymerizable group) having the following structure

[Formula 36]

(Polymerizable compound)

M1: Mixture of compounds of the following structure (the compound on the left: the compound on the right = 7: 3 (molar ratio))

[Formula 37]

M2: Compound of the structure

[Formula 38]

<Evaluation>

(Color resistance)

On the glass substrate, each photosensitive coloring composition was applied using a spin coater so that the film thickness after pre-baking was 1.6 µm, and heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C.

Next, using an ultraviolet photoresist curing apparatus (UMA-802-HC-552; manufactured by Ushio Denki Co., Ltd.), exposure was performed at an exposure amount of 3000 mJ / cm ² to produce a cured film.

About the obtained cured film, the transmittance | permeability of the light of 300-800 nm wavelength was measured using the spectrophotometer (reference: glass substrate) of the ultraviolet visible near infrared spectrophotometer UV3600 (made by Shimadzu Corporation). Moreover, the differential interference image was observed by reflection observation (50 times magnification) using the optical microscope BX60 manufactured by OLYMPUS.

Subsequently, the cured film was immersed in an alkali developer at 25 ° C (FHD-5, manufactured by Fujifilm Electronics Materials Co., Ltd.) for 5 minutes, dried and then subjected to spectral measurement again, and the transmittance fluctuation before and after immersion in the alkali developer was calculated. Then, the discoloration resistance was evaluated according to the following criteria.

Transmittance variation = | T0-T1 |

T0 is the transmittance of the cured film before immersion in the alkali developer, and T1 is the transmittance of the cured film after immersion in the alkali developer.

AA: The transmittance fluctuation in the whole range of wavelength 300-800nm is less than 2%.

A: The transmittance fluctuation in the entire range of wavelengths 300 to 800 nm is less than 5%, and in some ranges, the transmittance fluctuation is 2% or more and less than 5%.

B: The transmittance fluctuation in the entire range of wavelengths 300 to 800 nm is less than 7.5%, and in some ranges, the fluctuation in transmittance is 5% or more and less than 7.5%.

C: The transmittance fluctuation in the entire range of wavelengths 300 to 800 nm is less than 10%, and in some ranges, the fluctuation in transmittance is 7.5% or more and less than 10%.

D: The transmittance fluctuation is 10% or more in at least a part of the wavelength of 300 to 800 nm.

(Evaluation of residual film ratio and adhesion)

On a 8 inch (20.32 cm) glass substrate sprayed with hexamethyldisilazane, each photosensitive coloring composition was applied using a spin coater so that the film thickness after prebaking was 1.6 μm, and using a hot plate at 100 ° C. Heat treatment (pre-baking) was performed for 120 seconds.

Subsequently, an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Corporation) was used to pass an island pattern mask of 3.0 μm square at a wavelength of 365 nm and irradiated at 300 mJ / cm ² (to obtain a line width of 3.0 μm It is the required exposure dose).

Subsequently, the glass substrate on which the coating film after exposure was formed was placed on a horizontal rotating table of a spin-shower developer (DW-30 type; manufactured by Chemtronics Co., Ltd.), and the developer (CD-2000 (Fujifilm Electronics Materials ( Paddle development was performed at 23 ° C for 180 seconds using a 40% dilution of Note)) to form a colored pattern (pixel) on the glass substrate. The glass substrate on which the coloring pattern (pixel) is formed is fixed to a horizontal rotating table by a vacuum chuck method, and while rotating the glass substrate at a rotation speed of 50 rpm by a rotating device, pure water is ejected from the ejection nozzle above the center of rotation. It supplied and rinsed, and thereafter spin-dried to form a colored pattern (pixel).

The residual film rate was measured by using a scanning electron microscope (S-4800, manufactured by Hitachi High Technologies) to measure the thickness of the film before and after development. The higher the residual film ratio, the more preferable it is, and more preferably 80% or more.

Residual rate (%) = (thickness before development / thickness after development) × 100

AA: Residual rate is 87.5% or more

A: Residual rate is more than 82.5%, less than 87.5%

B: Residual rate is 80% or more and less than 82.5%

C: Residual rate is less than 80%

The adhesiveness was observed using the optical microscope for the colored pattern formed on the glass substrate, and evaluated by the following criteria.

AA: There is no peeling of a coloring pattern.

A: The peeling of a coloring pattern exists in 1 to 5 pixels out of 100 pixels

B: The peeling of a coloring pattern exists in 6 to 15 pixels out of 100 pixels.

C: Peeling of a coloring pattern exists in 16 pixels or more out of 100 pixels

[Table 3]

As shown in the above table, the examples were excellent in discoloration resistance. In contrast, Comparative Example 1, photopolymerization initiator a and photopolymerization initiator b, which contained only one of photopolymerization initiator a and photopolymerization initiator b, which did not use a colorant having a polymerizable group, contained 1.5 mass of the content. Comparative Example 4, which was less than%, was inferior in discoloration resistance to Examples.

Claims (12)

A photopolymerization initiator a whose absorption coefficient of light at a wavelength of 365 nm in methanol exceeds 1.0 × 10 ² mL / gcm,
A photopolymerization initiator b having a light absorption coefficient at a wavelength of 365 nm in methanol of 1.0 × 10 ² mL / gcm or less, a light absorption at a wavelength of 254 nm of 1.0 × 10 ³ mL / gcm or more,
Alkali-soluble resin,
A photosensitive coloring composition containing a colorant having a polymerizable group,
The content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more. The method according to claim 1,
The photosensitive coloring composition of the said photopolymerization initiator a whose absorption coefficient of the light of wavelength 365nm in methanol is 1.0x10 ³ mL / gcm or more. The method according to claim 1 or claim 2,
A photosensitive coloring composition, wherein the photopolymerization initiator a is an oxime compound. The method according to any one of claims 1 to 3,
A photosensitive coloring composition, wherein the photopolymerization initiator b is a hydroxyacetophenone compound. The method according to any one of claims 1 to 4,
A photosensitive coloring composition containing 50 to 500 parts by mass of the photopolymerization initiator a with respect to 100 parts by mass of the photopolymerization initiator b. The method according to any one of claims 1 to 5,
The photosensitive coloring composition whose total content of the said photoinitiator a and the said photoinitiator b in all solid content of the said photosensitive coloring composition is 3 to 17 mass%. The method according to any one of claims 1 to 6,
The coloring material is a large amount of dye, a photosensitive coloring composition. A cured film obtained by curing the photosensitive coloring composition according to claim 1. A step of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition according to any one of claims 1 to 7,
A step of exposing the photosensitive coloring composition layer in a pattern by irradiating light having a wavelength of more than 350 nm and less than or equal to 380 nm;
Alkali-developing the photosensitive coloring composition layer after the exposure,
The pattern formation method which has the process of irradiating the photosensitive coloring composition layer after the said development, and irradiating the light of wavelength 254-350 nm. A color filter having the cured film according to claim 8. A solid-state imaging device having the cured film according to claim 8. An image display device having the cured film according to claim 8.