JP2009221114A - Compound having polymerization-initiating function, polymerization initiator, polymerizable composition, color filter and method for producing the same, and solid state imaging element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having a polymerization-initiating function and high sensitivity to the light of wavelength of 365 nm and 405 nm, a polymerization initiator, a polymerizable composition excellent in stability over time and forming a cured film inhibiting discoloration by heating over time by using the same, furthermore, a color filter by using the same and a method for producing the color filter, and a solid state image-taking element by using the same. <P>SOLUTION: This compound is expressed by general formula (1) [wherein, A is O or S; R<SP>1</SP>is an alkenyl, an aryl, a heterocyclic ring, -CN, -COOR<SP>4</SP>or -CON(R<SP>4</SP>R<SP>5</SP>); R<SP>2</SP>is -CN, -COOR<SP>4</SP>or -CON(R<SP>4</SP>R<SP>5</SP>); the R<SP>1</SP>, R<SP>2</SP>may form a ring by bonding with each other; and R<SP>3</SP>is an alkyl or an aryl]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a compound having a polymerization initiating function, a polymerization initiator, a polymerizable composition, a color filter and a method for producing the same, and a solid-state imaging device.

Examples of the polymerizable composition include a photopolymerizable composition in which a monomer is polymerized by light irradiation, and a thermopolymerizable composition in which a monomer is polymerized by heat. Although the component content differs depending on the purpose, the polymerizable composition contains a monomer, that is, a polymerizable compound, a polymerization initiator, a binder, a colorant and the like. For example, there is a photopolymerizable composition obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond. Since such a photopolymerizable composition is polymerized and cured when irradiated with light, it is used in photocurable inks, photosensitive printing plates, color filters, various photoresists, and the like.
Moreover, as a photopolymerizable composition, there exists another aspect which generate | occur | produces an acid by irradiation of light, for example, and uses the generated acid as a catalyst. Specifically, it is used as a material for image formation, anti-counterfeiting, detection of energy dose by utilizing the coloring reaction of the dye precursor with the generated acid as a catalyst, or the decomposition reaction with the generated acid as a catalyst. Is used for positive resists for semiconductor manufacturing, TFT manufacturing, color filter manufacturing, micromachine component manufacturing, etc.

  In recent years, photopolymerizable compositions that are particularly sensitive to light sources of short wavelengths (365 nm and 405 nm) have been desired for various applications, and compounds exhibiting excellent sensitivity to such short wavelength light sources, for example, There is an increasing demand for photopolymerization initiators. However, since a photopolymerization initiator having excellent sensitivity generally lacks stability, a photopolymerization initiator that satisfies the improvement in sensitivity and the stability over time is desired.

Therefore, oxime ester derivatives are proposed in the following Patent Documents 1 to 4 as photopolymerization initiators used in the photopolymerizable composition. However, these known oxime ester compounds have not yet been satisfactory in terms of sensitivity because of their low absorbance at wavelengths of 365 nm and 405 nm.
Moreover, the present situation is that a photopolymerizable composition having excellent sensitivity to light with a short wavelength such as 365 nm and 405 nm is desired as well as excellent temporal stability.
Furthermore, for example, Patent Document 5 discloses a colored radiation-sensitive composition for a color filter containing an oxime compound, but the stability over time and the sensitivity to light with a short wavelength are still insufficient. there were. Moreover, in the colored radiation-sensitive composition for color filters, the reproducibility of the hue after pattern formation has become a new problem, and improvement of the problem that the colorability changes with time has been strongly desired.
Patent Document 6 discloses an oxime initiator having a methylenethiophene mother nucleus, which acts as a sulfonic acid generator and has insufficient function as a radical polymerization initiator. It was.

On the other hand, a color filter for an image sensor has a strong demand for a high color density and a thin film of the color filter in order to improve image quality due to high light condensing property and high color separation of a solid-state imaging device such as a CCD. When a large amount of coloring material is added to obtain a high coloring density, the sensitivity is insufficient to faithfully reproduce the shape of a fine pixel pattern of 2.5 μm or less, and overall pattern loss tends to occur frequently. There is. In order to eliminate this loss, it is necessary to irradiate light with higher energy, so that the exposure time becomes longer and the manufacturing yield is significantly reduced. From the above, the colored radiation-sensitive composition for color filters is highly sensitive because it needs to obtain good pattern formation properties while containing a colorant (colorant) at a high concentration. Currently, it is desired to polymerize and cure.
US Pat. No. 4,255,513 US Pat. No. 4,590,145 JP 2000-80068 A JP 2001-233842 A JP 2006-196425 A EP1392675B1

An object of the present invention is to provide a compound having a polymerization initiation function with high sensitivity to light having wavelengths of 365 nm and 405 nm, and a polymerization initiator containing the compound. It is another object of the present invention to provide a polymerizable composition capable of forming a cured film that has high sensitivity to light with wavelengths of 365 nm and 405 nm, is excellent in stability with time, and can suppress coloring due to heat.
Furthermore, an object of the present invention is to provide a color filter having a colored pattern having a good pattern shape and excellent adhesion to a support, and a high production of the color filter, using the polymerizable composition. Another object of the present invention is to provide a solid-state imaging device including the color filter.

Specific means for achieving the above object are as follows.
<1> A compound represented by the following general formula (1) and having a polymerization initiation function.

In the general formula (1), A represents an oxygen atom or a sulfur atom, and R ¹ represents an alkenyl group, an aryl group, a heterocyclic group, —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). To express. R ² represents —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² may combine with each other to form a ring. R ³ represents an alkyl group or an aryl group.

  <2> A polymerization initiator containing a compound represented by the following general formula (1) and having a polymerization initiation function.

In the general formula (1), A represents an oxygen atom or a sulfur atom, and R ¹ represents an alkenyl group, an aryl group, a heterocyclic group, —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). To express. R ² represents —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² may combine with each other to form a ring. R ³ represents an alkyl group or an aryl group.

  <3> A polymerizable composition comprising at least a polymerization initiator represented by (A) the general formula (1) and containing a compound having a polymerization initiating function, and (B) a radical polymerizable monomer. It is a thing.

  <4> The polymerizable composition as described in <3> above, further comprising (C) a colorant.

  <5> The polymerizable composition according to <3> or <4>, further including (D) a binder.

  <6> The polymerizable composition according to <4> or <5>, wherein the colorant (C) is a pigment or a dye.

  <7> The polymerizable composition according to <6>, wherein the solid content of the pigment or the dye is 50% by mass to 80% by mass with respect to the total solid content of the polymerizable composition. It is.

  <8> The polymerizable composition according to any one of <3> to <7>, wherein the (B) radical polymerizable monomer has an acid group.

  <9> The polymerizable composition according to any one of <5> to <8>, wherein the (D) binder has a double bond.

  <10> A color filter having a colored pattern formed using the polymerizable composition according to any one of <4> to <9>.

  <11> A polymerizable composition layer forming step of forming a polymerizable composition layer on the support using the polymerizable composition according to any one of <4> to <9>, and A color filter comprising: an exposure step of exposing the polymerizable composition layer through a mask; and a development step of developing the polymerizable composition layer after exposure to form a colored pattern. Is the method.

  <12> A solid-state imaging device comprising the color filter according to <10>.

According to the present invention, there is provided a compound having a polymerization initiating function having high sensitivity to light having wavelengths of 365 nm and 405 nm, and a polymerization initiator containing the compound. It is another object of the present invention to provide a polymerizable composition capable of forming a cured film that has high sensitivity to light with wavelengths of 365 nm and 405 nm, is excellent in stability with time, and can suppress coloring due to heat.
Furthermore, an object of the present invention is to provide a color filter having a colored pattern having a good pattern shape and excellent adhesion to a support, and a high production of the color filter, using the polymerizable composition. And a solid-state imaging device including the color filter can be provided.

<Specific oxime compound>
The compound of the present invention is represented by the following general formula (1) and has a polymerization initiation function. Hereinafter, a compound represented by the following general formula (1) and having a polymerization initiating function is appropriately referred to as “specific oxime compound” or “specific compound”.

In the general formula (1), A represents an oxygen atom or a sulfur atom, and R ¹ represents an alkenyl group, an aryl group, a heterocyclic group, —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). To express. R ² represents —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² may combine with each other to form a ring. R ³ represents an alkyl group or an aryl group.

  In the general formula (1), A represents an oxygen atom or a sulfur atom, and preferably a sulfur atom.

In the general formula (1), R ¹ represents an alkenyl group, an aryl group, a heterocyclic group, —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). The alkenyl group, aryl group, and heterocyclic group represented by R ¹ may each have a substituent. In —COOR ⁴ and —CON (R ⁴ R ⁵ ) represented by R ¹ , R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or a heterocyclic group.

The alkenyl group represented by R ¹ is preferably an alkenyl group having 2 to 20 carbon atoms.
Examples of the alkenyl group that may have a substituent include a vinyl group, an allyl group, and a styryl group.
The alkenyl group represented by R ¹ is more preferably an alkenyl group having 2 to 10 carbon atoms.

The aryl group represented by R ¹ is preferably an aryl group having 6 to 30 carbon atoms.
Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, and a 5-naphthacenyl group. 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group , Mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarter naphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, Bianthracenyl group, teranthracenyl group, quarteranthracenyl , Anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group A group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, an obalenyl group, and the like.
The aryl group represented by R ¹ is more preferably an aryl group having 6 to 20 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms.

The heterocyclic group represented by R ¹ is not limited as long as it is a cyclic group containing a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, and includes a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. An aromatic or aliphatic heterocyclic ring is preferable.
Examples of the heterocyclic group which may have a substituent include, for example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl. Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group , Indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β -Carborinyl group, phena Trizinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, phenalsadinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl Group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.
The heterocyclic group represented by R ¹ is more preferably a C 6-20 heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom, and even more preferably a C 6-10 heterocyclic group.

R ¹ and R ² may be bonded to each other to form a ring, and may have a divalent linking group between R ¹ and R ² . The divalent linking group may further have a substituent. Examples of the divalent linking group include thiocarbonyl.

The alkyl groups represented by R ⁴ and R ⁵ are preferably each independently an alkyl group having 1 to 30 carbon atoms.
Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an ocdadecyl group, an isopropyl group, an isobutyl group, and sec- Butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methyl Sulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-triphenyl Examples include a fluoromethylphenacyl group and a 3-nitrophenacyl group.

The aryl group and heterocyclic group represented by R ⁴ and R ⁵ have the same meanings as the aryl group and heterocyclic group described in R ¹ .
R ⁴ when R ¹ is represented by COOR ⁴ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom containing 6 nitrogen atoms, oxygen atoms or sulfur atoms. A heterocyclic group having 20 to 20 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heterocyclic group having 6 to 10 carbon atoms containing a nitrogen atom is more preferable.
Among these, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a phenylethyl group, a phenoxymethyl group, or a pyridinyl group is preferable.

When R ¹ is represented by —CON (R ⁴ R ⁵ ), R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or nitrogen. A C6-C20 heterocyclic group containing an atom, an oxygen atom or a sulfur atom is more preferred, and a C1-C10 alkyl group, a C6-C10 aryl group, or a nitrogen atom-containing C6 10 to 10 heterocyclic groups are more preferred.
Among these, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a phenylethyl group, a phenoxymethyl group, or a pyridinyl group is preferable.

Among the alkenyl group, aryl group, heterocyclic group, —CN, COOR ⁴ , and —CON (R ⁴ R ⁵ ), R ¹ is preferably a phenyl group, a toluyl group, or a naphthyl group.

R ⁴ when R ² is represented by COOR ⁴ and R ⁴ and R ⁵ when R ² is represented by —CON (R ⁴ R ⁵ ) are the same as those described in R ¹ . Synonymous with group.
R ⁴ when R ² is represented by COOR ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom having 6 nitrogen atoms, oxygen atoms, or sulfur atoms. -20 heterocyclic groups are more preferable, C1-C10 alkyl groups, C6-C10 aryl groups, or C6-C10 heterocyclic groups containing a nitrogen atom are more preferable.
Among _{them, -COOCH 3, -COOCH 2 CH 3} , or -COOC ₆ H ₅ are preferred, -COOCH ₃ are more preferred.

When R ¹ is represented by —CON (R ⁴ R ⁵ ), R ⁴ and R ⁵ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or nitrogen. A C6-C20 heterocyclic group containing an atom, an oxygen atom or a sulfur atom is more preferred, and a C1-C10 alkyl group, a C6-C10 aryl group, or a nitrogen atom-containing C6-C6 10 heterocyclic groups are more preferred.
Among _{them, -CON (CH 3) 2,} -CON (CH 2 CH 3) 2, or -CON _{(C 6} H _{5) 2} is preferable, -CON _{(CH 3) 2} is more preferable.

Additional -CN, COOR ^4, and among -CON of ^{(R 4 R 5), R} 2 is, -CN are preferred.

R ³ represents an alkyl group or an aryl group. The alkyl group or aryl group represented by R ³ may have a substituent. The alkyl group represented by R ³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. The aryl group represented by R ³ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms.
Among these, from the viewpoint of increasing sensitivity, R ³ is preferably an alkyl group having 1 to 3 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferable.

The carbon number of the alkenyl group, aryl group, and alkyl group represented by R ^{1 to} R ⁵ is a total value including the carbon number of the substituent.
A preferable combination of A and R ^{1 to} R ³ in the general formula (1) is a combination of each preferable range.

  Specific examples (A-1) to (A-29) of the compound (specific oxime compound) represented by the general formula (1) are shown below, but the present invention is not limited to these compounds.

[Synthesis example of specific oxime compound]
A method for synthesizing the compound (specific oxime compound) represented by the general formula (1) will be described. The following “Compound A-1” and the like correspond to the compounds represented by the specific examples (A-1) to (A-29).

(Synthesis Example 1: Compound A-1)
Sodium methoxide (160 mmol) was dissolved in 80 mL of methanol, and the methanol solution was cooled to 0 ° C. in an ice bath. Cyanomethylbenzene (46 mmol) was added to the methanol solution, and 2-nitrothiophene (46 mmol) was added after 5 minutes to obtain a reaction product 1. The resulting reaction product 1 was stirred at 0 ° C. for 2 hours, poured into 100 mL of water, and neutralized with acetic acid. The neutralized reaction product 1 was extracted three times with ethyl acetate and washed twice with 100 mL of an aqueous sodium chloride solution. Next, after drying with magnesium sulfate, the organic solvent was distilled off under reduced pressure, and silica gel column chromatography was performed using eluent (hexane / ethyl acetate = 4/1 to 1/1) and silica gel of Wakogel C-200. To obtain an oxime compound. The yield of the obtained oxime compound was 20 mmol.
Further, the obtained oxime compound was dissolved in THF, triethylamine (22 mmol) and acetyl chloride (22 mmol) were added, and the mixture was stirred at room temperature for 2 hours to obtain a reaction product 2. The obtained reaction product 2 was poured into water, extracted with ethyl acetate, and washed with distilled water. Then, it dried with magnesium sulfate and concentrated to obtain a solid. The resulting solid was recrystallized from ethyl acetate to obtain the target compound A-1 in a yield of 10 mmol.
Compound A-1 was identified using ¹ H-NMR. The results are as follows. ¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.46 (s, 3H), 6.16 (d, J = 6.8 Hz, 1H), 6.86 (d, J = 6.8 Hz, 1H) ), 7.2-7.5 (m, 5H)

(Synthesis Example 2: Compound A-2)
Compound A-2 was obtained in the same manner as in Synthesis Example 1 except that 2-methylcyanomethylbenzene was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. In the same manner as in Synthesis Example 1, compound A-2 was identified. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.38 (s, 3H), 2.47 (s, 3H), 6.17 (d, J = 6.8 Hz, 1H), 6.88 ( d, J = 6.8 Hz, 1H), 7.2-7.5 (m, 4H)

(Synthesis Example 3: Compound A-3)
Compound A-3 was obtained in the same manner as in Synthesis Example 1 except that 2,6-dimethylcyanomethylbenzene was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. It was. Further, Compound A-3 was identified in the same manner as in Synthesis Example 1. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.22 (s, 6H), 2.44 (s, 3H), 6.12 (d, J = 6.8 Hz, 1H), 6.84 ( d, J = 6.8 Hz, 1H), 7.2-7.5 (m, 3H)

(Synthesis Example 4: Compound A-4)
Compound A-4 was synthesized in the same manner as in Synthesis Example 1 except that 2,4,6-trimethylcyanomethylbenzene was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. Got. In the same manner as in Synthesis Example 1, compound A-4 was identified. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.20 (s, 3H), 2.22 (s, 6H), 2.44 (s, 3H), 6.19 (d, J = 6. 8 Hz, 1 H), 6.89 (d, J = 6.8 Hz, 1 H), 7.21 (s, 2 H)

(Synthesis Example 5: Compound A-5)
Compound A-5 was obtained in the same manner as in Synthesis Example 1 except that 2-methoxycyanomethylbenzene was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. In the same manner as in Synthesis Example 1, compound A-5 was identified. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.44 (s, 3H), 3.51 (s, 3H), 6.05 (d, J = 6.8 Hz, 1H), 6.72 ( d, J = 6.8 Hz, 1H), 7.2-7.4 (s, 4H)

(Synthesis Example 6: Compound A-6)
The compound A-6 was obtained in the same manner as in Synthesis Example 1 except that 2-methoxycarbonylcyanomethylbenzene was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. . Further, Compound A-6 was identified in the same manner as in Synthesis Example 1. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.49 (s, 3H), 3.91 (s, 3H), 6.06 (d, J = 6.8 Hz, 1H), 6.86 ( d, J = 6.8 Hz, 1H), 7.2-7.5 (m, 4H)

(Synthesis Example 7: Compound A-7)
Compound A-7 was obtained in the same manner as in Synthesis Example 1 except that 2-trifluoromethylcyanomethylbenzene was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. It was. In the same manner as in Synthesis Example 1, Compound A-7 was identified. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.51 (s, 3H), 6.16 (d, J = 6.8 Hz, 1H), 6.96 (d, J = 6.8 Hz, 1H) ), 7.3-7.6 (m, 4H)

(Synthesis Example 8: Compound A-8)
Compound A-8 was obtained in the same manner as in Synthesis Example 1 except that pentafluorocyanomethylbenzene was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. Further, Compound A-8 was identified in the same manner as in Synthesis Example 1. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.51 (s, 3H), 6.26 (d, J = 6.8 Hz, 1H), 6.99 (d, J = 6.8 Hz, 1H) )

(Synthesis Example 9: Compound A-21)
Compound A-21 was obtained in the same manner as in Synthesis Example 1 except that malononitrile was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. Further, Compound A-21 was identified in the same manner as in Synthesis Example 1. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.44 (s, 3H), 6.16 (d, J = 6.8 Hz, 1H), 6.96 (d, J = 6.8 Hz, 1H) )

(Synthesis Example 10: Compound A-22)
Compound A-22 was obtained in the same manner as in Synthesis Example 1 except that dimethyl malonate was used instead of cyanomethylbenzene in the synthesis method of Compound A-1 shown in Synthesis Example 1. Further, Compound A-22 was identified in the same manner as in Synthesis Example 1. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 2.44 (s, 3H), 3.85 (s, 6H), 6.16 (d, J = 6.8 Hz, 1H), 6.96 ( d, J = 6.8 Hz, 1H)

(Synthesis Example 11: Compound A-26)
Compound A-26 was obtained in the same manner as in Synthesis Example 1 except that benzoyl chloride was used instead of acetyl chloride in the synthesis method of Compound A-1 shown in Synthesis Example 1. Further, Compound A-26 was identified in the same manner as in Synthesis Example 1. The results are as follows.
¹ H-NMR (CDCl ₃ ) δ [ppm]: 6.16 (d, J = 6.8 Hz, 1H), 6.96 (d, J = 6.8 Hz, 1H), 7.2-7.4 (M, 10H)

Since the specific oxime compound of the present invention has the above structure, it has a polymerization initiating function. This is presumed that since the specific oxime compound of the present invention has high absorption at 365 nm and 405 nm, the absorbed light energy can be efficiently used for cleavage of the N—O bond of the specific oxime compound. . Therefore, it is considered that the amount of radical generation is large, the monomer polymerization rate is improved, and the sensitivity is improved.
In addition, since the N—O bond is the weakest bond in the structure of the specific oxime compound, even when heat energy is applied to the specific oxime compound, the thermal energy is sensitively sensed and N It is considered that radicals are likely to be generated by breaking the —O bond.
Therefore, the specific oxime compound of the present invention can be suitably used as a polymerization initiator.

<Polymerization initiator>
The polymerization initiator of the present invention is represented by the following general formula (1), and contains a compound having a polymerization initiation function.

In the general formula (1), A represents an oxygen atom or a sulfur atom, and R ¹ represents an alkenyl group, an aryl group, a heterocyclic group, —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). To express. R ² represents —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² may combine with each other to form a ring. R ³ represents an alkyl group or an aryl group.

  In the polymerization initiator of the present invention, the compound represented by the general formula (1) and having a polymerization initiation function (specific oxime compound) is preferably used in the preferred structure described above.

  The polymerization initiator of the present invention may further contain a compound having a general polymerization initiation function as long as the effects of the present invention are not impaired. At this time, the content of the specific oxime compound with respect to the total solid content of the polymerization initiator of the present invention is preferably 50% by mass or more, and more preferably 80% by mass or more.

<Polymerizable composition>
The polymerizable composition of the present invention contains (A) a polymerization initiator represented by the general formula (1) and containing a compound having a polymerization initiating function, and (B) a radical polymerizable monomer. Features. The polymerizable composition of the present invention preferably further contains (C) a colorant. As long as the effects of the present invention are not impaired, (D) a binder and (E) solvent may be further added, or other components may be added as necessary.
Since the polymerization initiator of the polymerizable composition of the present invention contains the specific oxime compound of the present invention, it has excellent sensitivity to heat and light as described above. In particular, even when the polymerizable composition containing the polymerization initiator of the present invention has excellent sensitivity to a 365 nm or 405 nm light source that is a short wavelength light source and contains a high concentration of colorant, Easy to cure with sensitivity.
Hereinafter, the component which the polymeric composition of this invention contains is demonstrated.

[(A) Polymerization initiator containing a compound represented by the general formula (1) and having a polymerization initiation function]
The polymerizable composition of the present invention comprises (A) a compound represented by the general formula (1) and having a polymerization initiation function, that is, a polymerization initiator containing a specific oxime compound. The details of the polymerization initiator containing the specific oxime compound are as described above.

  The polymerizable composition of the present invention may further contain a known polymerization initiator in addition to the polymerization initiator containing the (A) specific oxime compound. Known polymerization initiators include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, and t-butyl peroxybenzoate; Azo compounds such as 2,2'-azobisisobutyronitrile.

  The polymerization initiator containing the (A) specific oxime compound is 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, particularly preferably based on the total solid content of the polymerizable composition. It can add in the ratio of 1 mass%-20 mass%. By setting this range, good sensitivity and pattern shape can be obtained.

[(B) Radical polymerizable monomer]
The polymerizable composition of the present invention contains (B) a radical polymerizable monomer (also referred to as “polymerizable compound”). (B) The radical polymerizable monomer is not particularly limited as long as it is a polymerizable compound that generates radicals by heat or light, but is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond. It is preferable to have at least one terminal ethylenically unsaturated bond. More preferably, it is selected from compounds having two or more terminal ethylenically unsaturated bonds.
Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

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

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

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

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

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

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

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

  Among the polymerizable monomers shown above, the (B) radical polymerizable monomer used in the present invention has an acid group (also referred to as “acidic functional group”) from the viewpoint of improving developability and improving residues. Further preferred. Hereinafter, the radical polymerizable monomer having an acid group is also referred to as a “specific polymerizable compound”.

  When the specific photopolymerizable compound having an acid group is contained in the polymerizable composition, the crosslink density is increased by the thermally polymerizable functional group or the photopolymerizable functional group of the specific polymerizable compound, and the acidic functional group of the specific polymerizable compound This increases alkali solubility. Therefore, by adding a specific polymerizable compound having an acidic functional group even if the amount of a component that does not have curing reactivity and is not alkali-soluble, such as a colorant or a polymerization initiator, is increased in the polymerizable composition. Since the crosslinking density and alkali solubility are increased, excellent polymerizability and alkali developability can be obtained.

  The specific photopolymerizable compound having an acidic functional group is preferably a compound that can be dissolved or dispersed in an alkaline developer. Examples of the acidic functional group possessed by the specific photopolymerizable compound include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. From the viewpoint of solubility in an alkali developer and handling of the composition, the carboxyl group is preferable.

  As a specific photopolymerizable compound having an acidic functional group, (1) by modifying a monomer or oligomer having three or more thermal polymerizable functional groups or photopolymerizable functional groups together with a hydroxy group with a dibasic acid anhydride Those introduced with a carboxyl group, or (2) those introduced with a sulfonic acid group by modifying an aromatic compound having three or more thermopolymerizable functional groups or photopolymerizable functional groups with concentrated sulfuric acid or fuming sulfuric acid Etc. can be used. Moreover, you may use the oligomer which contains the monomer which is the specific photopolymerizable compound itself as a repeating unit as a specific photopolymerizable compound.

The specific photopolymerizable compound in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (11) or (12).
In the general formula (11) and the general formula (12), when T ¹ or G ¹ represents an alkyleneoxy chain, the terminal on the carbon atom side is bonded to R ¹ , X ¹ and W ¹ .

In the general formula (11), R ¹ , T ¹ , and X ¹ each independently represent any of the groups shown below as R ¹ , T ¹ , or X ¹ . n represents an integer of 0 to 14.

In the general formula (12), Z ¹ and G ¹ each independently represent any of the groups shown below as Z ¹ or G ¹ . W ¹ is synonymous with the group represented by R ¹ or X ¹ in the general formula (11), and 3 or more of 6 W ¹ represent R ¹ . p represents an integer of 0 to 14.

Among the compounds represented by the general formula (11) or the general formula (12), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.
Specifically, exemplary compounds (C-1) to (C-12) shown below are preferable, and among them, exemplary compounds (C-1), (C-2), (C-3), and (C-5) And (C-7) are most preferred.

About the said polymeric compound, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a final photosensitive material. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. A method of adjusting both sensitivity and strength by using a compound) is also effective.
In addition, the selection and use method of the polymerizable compound is important for the compatibility and dispersibility with other components in the polymerizable composition (eg, binder, polymerization initiator, colorant (pigment, dye, etc.)). For example, the compatibility may be improved by using a low-purity compound or a combination of two or more types, and a specific structure for the purpose of improving the adhesion of the substrate and the overcoat layer described later. May also be selected.

  The polymerizable compound is preferably used in the range of 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass with respect to the total solid content of the polymerizable composition. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, and the like.

[(C) Colorant]
The polymerizable composition of the present invention preferably contains (C) a colorant. By containing a colorant, a colored polymerizable composition having a desired color can be obtained.
Since the polymerizable composition of the present invention contains (A) a polymerization initiator containing a specific oxime compound, it has excellent sensitivity to heat and light, and is particularly a short wavelength light source of 365 nm or 405 nm. Therefore, even when the colorant is contained in a high concentration, it can be cured with high sensitivity.

The colorant (C) used in the polymerizable composition of the present invention is not particularly limited. If the polymerizable composition of the present invention is used for producing a color filter, a color pixel of the color filter is formed. Any of chromatic colorants such as R, G and B, and black colorants generally used for forming a black matrix can be used.
(C) The colorant is preferably a pigment or a dye, and various conventionally known dyes and pigments can be used singly or in combination of two or more, depending on the use of the polymerizable composition. It is selected appropriately.
Further, the (C) colorant may be used as a pigment dispersion composition prepared by mixing (C) a colorant and a known surfactant.

  Hereinafter, the colorant that can be used in the photopolymerizable composition of the present invention will be described in detail by taking a colorant suitable for a color filter application as an example.

  Various conventionally known inorganic pigments or organic pigments can be used as the pigment. In consideration of the high transmittance, it is preferable that both the inorganic pigment and the organic pigment are as fine as possible. Moreover, when handling property is also considered, 0.01 micrometer-0.1 micrometer are preferable and, as for the average particle diameter of the said pigment, 0.01 micrometer-0.05 micrometer are more preferable.

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

As the organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Examples thereof include carbon black.

  Of these, examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Black 1

  In the present invention, those having a basic nitrogen atom in the structure of the pigment itself can be preferably used. These pigments having a basic nitrogen atom exhibit good dispersibility in the polymerizable composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the polymerizable component and the pigment has an influence.

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below.

  For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. Examples of anthraquinone pigments include C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred.

The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50, more preferably 100: 7 to 100: 40, and still more preferably 100: 10 to 100: 30. If it is less than 100: 5, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. If it exceeds 100: 50, the dominant wavelength becomes shorter than the short wavelength, and the deviation from the NTSC target hue may become large.
In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.

The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, more preferably 100: 15 to 100: 140, and still more preferably 100: 30 to 100: 120.
If it is less than 100: 5 or more than 100: 150, the target color tone may not be obtained.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture of this with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred.

The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.
If it exceeds 100: 30, the transmitted wavelength may be short and the target color tone may not be obtained.

Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably 100: 0 to 100: 60, more preferably 100: 0 to 100: 50, and still more preferably 100: 0 to 100: 40.
If it exceeds 100: 60, the problem of peeling off of the black matrix may occur, which is not preferable.

  When the colorant (C) of the present invention is used for a color filter, the primary particle diameter of the pigment is preferably 10 to 100 nm, more preferably 10 to 70 nm, and even more preferably 10 to 50 nm, from the viewpoint of color unevenness and contrast. Preferably, 10 to 40 nm is most preferable.

  In addition, the dye used in the present invention can be appropriately selected from known dyes according to the purpose and the like, and can be contained not only in one kind but also in combination of two or more kinds.

Among these, organic solvent-soluble dyes (hereinafter referred to as “organic solvent-soluble dyes”) are preferable. The organic solvent-soluble dye that can be used in the present invention is not particularly limited, and any dye known in the art for color filters can be used as long as it is an organic solvent-soluble dye.
Here, the organic solvent solubility means a property that the dye is completely dissolved as a 20% solution in the organic solvent (25 ° C.).

  Examples of organic solvent-soluble dyes include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, and U.S. Patents. Examples include dyes described in US Pat. No. 4,808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, and JP-A-6-35183. .

The chemical structure includes azo compounds such as pyrazole azo, anilino azo, pyrazolo triazole azo, and pyridone azo, and triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolo. Examples of the dye include pyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo.
Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes and anthrapyridone dyes.

In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof are also useful.

Hereinafter, the acid dye and its derivative will be described.
The acidic dye is not particularly limited as long as it is a pigment having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developer used for the preparation of a composition or a development process, It is selected in consideration of all required performances such as salt formation with a basic compound, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

Hereinafter, although the specific example of an acidic dye is given, in this invention, it is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes mentioned above, acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Acid Green 25;
And the like and derivatives of these dyes are preferred.

  The derivative of the acid dye is not particularly limited as long as it can be used as an inorganic salt of an acid dye having a sulfonic acid or a carboxylic acid, a salt with a nitrogen-containing compound, and can be dissolved as a curable composition solution. It is selected in consideration of all the required performances such as solubility in organic solvents and developer, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

  The content of the colorant (C) is preferably 50% by mass to 80% by mass with respect to the total solid content of the polymerizable composition.

[(D) Binder]
The polymerizable composition of the present invention preferably contains (D) a binder.
When the polymerizable composition contains (D) a binder (binder polymer), film properties of a recording layer (for example, a colored pattern) formed using the polymerizable composition can be improved.
Moreover, it is also preferable embodiment to use a linear organic polymer as (D) binder. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film-forming agent for an image recording material but also according to its use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
When copolymerizing and using an alkali-soluble resin as a copolymer, monomers other than the (B) radical polymerizable monomer mentioned above can also be used as a compound to be copolymerized. Examples of other monomers include the following compounds (1) to (13).

  (1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as

  (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

  (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate and the like.

  (4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

  (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

  (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

  (7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

  (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  (9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

  (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.

  (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.

  (12) A methacrylic acid monomer having a hetero atom bonded to the α-position. Examples thereof include compounds described in Japanese Patent Application Nos. 2001-115595 and 2001-115598.

Among these, (meth) acrylic resin having an allyl group, a vinyl ester group and a carboxyl group in the side chain, and a double bond in the side chain described in JP-A Nos. 2000-187322 and 2002-62698 Alkali-soluble resins and alkali-soluble resins having an amide group in the side chain described in JP-A No. 2001-242612 are preferred because they have an excellent balance of film strength, sensitivity, and developability.
In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups as described in JP 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.

In addition, an acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in EP 993966, EP 1204000, JP-A-2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) of the binder polymer is preferably 1 or more, more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
As the radical polymerization initiator used in synthesizing the polymer used in the present invention, known compounds such as azo initiators and peroxide initiators can be used.

The weight average molecular weight (Mw) of the binder is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint of good dispersibility of the pigment.
The content of the binder is preferably 0.01% by mass to 40% by mass and more preferably 5% by mass to 30% by mass based on the pigment. When the content of the binder is less than 0.01% by mass, the pigment dispersibility is insufficient and the effect of improving the brightness is low. Moreover, when it exceeds 40 mass%, the viscosity of the polymerizable composition obtained will become high, thixotropy will be expressed, and coating suitability will become low.

The binder (D) used in the present invention is more preferably a binder having a double bond, particularly an unsaturated double bond, from the viewpoint of improving sensitivity.
In the binder having an unsaturated double bond, the unsaturated equivalent is preferably less than 3,000, more preferably less than 1,500, and most preferably less than 600 from the viewpoint of improving photosensitivity.
Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.
By making the unsaturated equivalent of the dispersed resin less than 3,000, that is, by increasing the number of unsaturated double bonds in the dispersed resin molecule, the photopolymerizability and sensitivity are improved, and the support is improved by improving the polymerizability. Adhesion is also improved, and a tapered or rectangular pattern tends to be obtained, which is preferable.
The lower limit of the unsaturated equivalent is preferably 150. By suppressing the unsaturated equivalent to 150 or more, it is preferable in that the increase in viscosity at the time of dispersion of the pigment is suppressed and a composition having better dispersion stability during storage tends to be obtained.

  Examples of the binder having an unsaturated double bond include glycidyl group-containing unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether, and allyl alcohol, 2-hydroxy acrylate, 2-hydroxy methacrylate, and the like on carboxyl group-containing resins. Resins reacted with unsaturated alcohol, carboxyl group-containing resins having hydroxyl groups, unsaturated compounds containing free isocyanate groups, resins obtained by reacting unsaturated acid anhydrides, addition reaction products of epoxy resins and unsaturated carboxylic acids Resin in which basic acid anhydride is reacted, Resin in which hydroxyl group-containing polymerizable monomer is reacted with addition reaction product of conjugated diene copolymer and unsaturated dicarboxylic acid anhydride, elimination reaction is caused by base treatment and is unsaturated A resin having a specific functional group that gives a group is synthesized, and the resin is subjected to base treatment Resin or the like to produce an unsaturated group can be cited as typical resin between.

  Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate or allyl glycidyl ether, or a resin obtained by polymerizing a hydroxyl group-containing (meth) acrylic ester compound (meth) acrylic. Resin obtained by reacting (meth) acrylic acid ester having a free isocyanate group such as acid-2-isocyanatoethyl, resin having a structural unit represented by the following general formulas (21) to (23), and removing by base treatment A resin or the like in which an unsaturated group is generated by synthesizing a resin having a specific functional group that causes a release reaction and gives an unsaturated group, and performing a base treatment on the resin is more preferable.

  The binder having an unsaturated double bond is preferably a polymer compound having at least one selected from structural units represented by any of the following general formulas (21) to (23) as an unsaturated double bond portion. .

In the general formulas (21) to (23), A ¹ , A ² , and A ³ each independently represent an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and R ²¹ represents a substituent. It represents an alkyl group that may have. G ¹ , G ² , and G ³ each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents an alkyl group which may have a substituent. R ^{1 to} R ²⁰ each independently represents a monovalent organic group.

In the general formula (21), R ^{1 to} R ³ each independently represents a monovalent organic group, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ¹ , R ² is preferably a hydrogen atom, and R ³ is preferably a hydrogen atom or a methyl group.
R ^{4 to} R ⁶ each independently represents a monovalent organic group, and examples of R ⁴ include a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, An ethyl group is preferred. R ⁵ and R ⁶ may each independently have a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. A good aryl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable. Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ¹ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and X represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Here, examples of R ²¹ and R ²² include an alkyl group which may have a substituent.
G ¹ represents a divalent organic group, but an alkylene group which may have a substituent is preferable. More preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be present may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, or cyclo that may have a substituent having 3 to 10 carbon atoms. An alkylene group and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferable in terms of performance such as strength and developability.

Preferable examples of the substituent in G ^1, which except for the hydroxyl group hydrogen atoms among the groups bonded to a hetero atom, for example, an amino group, a thiol group, those containing no carboxyl group.

In the general formula (22), R ^{7 to} R ⁹ each independently represents a monovalent organic group, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ⁷ , R ⁸ is preferably a hydrogen atom, and R ⁹ is preferably a hydrogen atom or a methyl group.
R ^{10 to} R ¹² each independently represents a monovalent organic group. Specific examples of the organic group include a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, and a nitro group. , A cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, substituted An alkylsulfonyl group which may have a group, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may have a substituent, a substituent The aryl group which may have is preferable.
Here, examples of the substituent that can be introduced include those listed in the general formula (21).

A ² each independently represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, where R ²¹ is a hydrogen atom, an alkyl group that may have a substituent, or the like. Can be mentioned.
G ² represents a divalent organic group, but an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent for G ^2, those except the hydroxyl group hydrogen atoms among the groups bonded to a hetero atom, for example, an amino group, a thiol group, those containing no carboxyl group.
Y represents an oxygen atom, a sulfur atom, -N ^{(R 23)} - represents a or phenylene group which may have a substituent. Here, examples of R ²³ include a hydrogen atom and an alkyl group which may have a substituent.

In the general formula (23), R ^{13 to} R ¹⁵ each independently represents a monovalent organic group, and examples thereof include a hydrogen atom and an alkyl group which may have a substituent. Among them, R ¹³ , R ¹⁴ is preferably a hydrogen atom, and R ¹⁵ is preferably a hydrogen atom or a methyl group.
R ^{16 to} R ²⁰ each independently represents a monovalent organic group, and R ^{16 to} R ²⁰ are, for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, or a cyano group. An alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, and a substituent. An alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, an alkyl group that may have a substituent, and a substituent Preferred aryl groups are preferred. Examples of the substituent that can be introduced include those listed in the general formula (1).
A ³ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and Z represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Examples of R ²¹ and R ²² include the same as those in general formula (21).

G ³ represents a divalent organic group, and an alkylene group which may have a substituent is preferable. Preferably, it has an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, and a substituent which has 6 to 20 carbon atoms. Aromatic group, etc. may be mentioned. Among them, a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cycloalkylene which may have a substituent having 3 to 10 carbon atoms. Group, and an aromatic group which may have a substituent having 6 to 12 carbon atoms is preferable in terms of performance such as strength and developability.
Here, the substituent in G ³ is preferably a group in which a hydrogen atom is bonded to a heteroatom, excluding a hydroxyl group, for example, a group not containing an amino group, a thiol group, or a carboxyl group.

  The structural unit represented by the general formulas (21) to (23) is preferably a compound contained in one molecule in a range of 20 mol% or more and less than 95 mol% from the viewpoint of improving curability and reducing development residue. More preferably, it is 25-90 mol%. More preferably, it is the range of 30 mol% or more and less than 85 mol%.

  The synthesis of the polymer compound having the structural unit represented by the general formulas (21) to (23) is based on the synthesis method described in paragraphs [0027] to [0057] of JP-A-2003-262958. Can be done. Among them, the synthesis method 1) in the same publication is preferable, and this is shown in the following (1).

(1) A structure in which a compound represented by the following general formula (24) is used as a copolymerization component, a proton is extracted using a base, L is eliminated, and the structure represented by the general formula (21). A method for obtaining a desired polymer compound having

In the general formula (24), L represents an anionic leaving group, and preferred examples include a halogen atom and a sulfonate ester. ^{R 3 ~R 6, A 1,} G 1, and for X have the same meanings as ^{R 3 ~R 6, A 1,} G 1, and X in the general formula (21), in order to rise to elimination reaction As the base to be used, either an inorganic compound or an organic compound may be used. Details and preferred embodiments of this method are described in paragraphs [0028] to [0033] of JP-A No. 2003-262958.

  Preferred bases of inorganic compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like. Bases of organic compounds include sodium methoxide, sodium ethoxide, potassium. Examples thereof include metal alkoxides such as t-butoxide, organic amine compounds such as triethylamine, pyridine and diisopropylethylamine.

  Specific examples of the polymer compound having the structural units represented by the general formulas (21) to (23) include the following polymer compounds 1 to 17.

[(E) solvent]
The polymerizable composition of the present invention preferably contains (E) a solvent.
(E) The solvent is not particularly limited as long as it satisfies the solubility of each component of the polymerizable composition and the applicability of the polymerizable composition, but is preferably selected in consideration of safety. Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and lactic acid. 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, 2-oxypropion acid 2-oxypropionic acid alkyl esters such as til and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate) Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, methyl isobutyl ketone;
Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc .;
Alcohol solvents such as ethyl alcohol, isopropyl alcohol and n-propyl alcohol are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

  (E) 20 mass%-95 mass% are preferable with respect to the total solid of a polymeric composition, and, as for content of a solvent, 25 mass%-90 mass% are more preferable. When the amount of the solvent is within the above range, the pigment can be uniformly dispersed, which is advantageous in terms of dispersion stability after dispersion.

[Other ingredients]
In addition to the components (A) and (B) and optional components (C) to (E), the polymerizable composition of the present invention includes components such as a sensitizer and a polymerization inhibitor, and others. These additives are preferably contained as necessary.

-(F) Sensitizer-
The polymerizable composition of the present invention preferably contains (F) a sensitizer together with the polymerization initiator containing (A) the specific oxime compound which is the polymerization initiator of the present invention.
Examples of the sensitizer that can be used in the present invention include spectral sensitizing dyes, dyes or pigments that absorb light from a light source and interact with a polymerization initiator.

  Preferred spectral sensitizing dyes or dyes include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thianes). Carbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), phthalocyanines ( For example, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll, chlorophyllin, central metal) Conversion chlorophyll), metal complexes (for example, the following compound), anthraquinones, such as (anthraquinone) squaryliums, include, for example, (squarylium), and the like.

  More preferable examples of spectral sensitizing dyes or dyes include those described in paragraph numbers [0144] to [0202] of JP-A-2006-78749, for example.

  A sensitizer may be used independently or may use 2 or more types together. The molar ratio of the total polymerization initiator (including the specific oxime compound and a polymerization initiator other than the specific oxime compound) contained in the polymerizable composition to the sensitizing dye is 100: 0 to 1:99, more preferably. Is from 90:10 to 10:90, most preferably from 80:20 to 20:80.

-(G) Co-sensitizer-
To the polymerizable composition of the present invention, a known compound having an action such as further improving sensitivity or suppressing polymerization inhibition by oxygen may be added as a co-sensitizer.

  Examples of the co-sensitizer include phosphorus compounds (such as diethyl phosphite) described in JP-A-6-250387, Si—H and Ge—H compounds described in Japanese Patent Application No. 6-191605, and the like.

  When using a co-sensitizer, it is appropriate to use 0.01 mass part-50 mass parts with respect to 1 mass part of the total amount of the polymerization initiator contained in the polymeric composition of this invention. .

-(H) Polymerization inhibitor-
The polymerizable composition of the present invention comprises a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the polymerizable composition. It is desirable to add. As thermal polymerization inhibitors, 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-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the total solid content of the polymerizable composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

-(I) Other additives-
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, other plasticizers, and a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added.

  Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

  Further, for the purpose of improving the film strength (printing durability), which will be described later, a UV initiator, a thermal crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed on the support using the polymerizable composition of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

The method for producing the color filter of the present invention includes:
On the support, a polymerizable composition layer forming step for forming a polymerizable composition layer using the polymerizable composition of the present invention, an exposure step for exposing the polymerizable composition layer through a mask, A development step of developing the polymerizable composition layer after exposure to form a colored pattern.

Specifically, the polymerizable composition of the present invention is applied (for example, applied) on a support (substrate) directly or via another layer to form a polymerizable composition layer (polymerizable composition). Physical layer forming step), exposing through a predetermined mask pattern, curing only the light-irradiated coating film portion (exposure step), and developing with a developing solution (developing step), each color (three colors or four) The color filter of the present invention can be manufactured by forming a pattern-like film composed of (color) pixels.
Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

[Polymerizable composition layer forming step]
In the polymerizable composition layer forming step, a polymerizable composition layer is formed on the support using the polymerizable composition of the present invention.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these glasses, imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  Examples of the method for applying the polymerizable composition for a color filter of the present invention on a support include a method by coating and a method by transfer. For example, in the case of a coating method, slit coating, inkjet method, spin coating, Various coating methods such as cast coating, roll coating, and screen printing can be applied. Further, in the case of the transfer method, a transfer material provided with a polymerizable composition layer using the polymerizable composition of the present invention on a temporary support, and an intermediate layer and a thermoplastic resin layer as necessary is used as a support. The polymerizable composition of the present invention can be applied on the support by transferring it onto the support.

As an application | coating film thickness (for example, coating film thickness) of the polymerizable composition for color filters, 0.1 micrometer-10 micrometers are preferable, 0.2 micrometer-5 micrometers are more preferable, 0.2 micrometer-3 micrometers are still more preferable.
Moreover, when manufacturing the color filter for solid-state image sensors, as a coating film thickness of the polymerizable composition for color filters, 0.35 micrometer-1.5 micrometers are preferable from a viewpoint of resolution and developability, and 0. 40 μm to 1.0 μm is more preferable.

  The color filter polymerizable composition coated on the support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a polymerizable composition layer.

[Exposure process]
In the exposure step, the polymerizable composition layer formed in the polymerizable composition layer forming step is exposed through a mask. Thereby, only the coating film part irradiated with light can be hardened.
The exposure is preferably performed by irradiation with radiation. The radiation that can be used for exposure is radiation capable of irradiating radiation at wavelengths of 365 nm and 405 nm, in which the polymerization initiator containing the specific oxime compound (A), which is the polymerization initiator of the present invention, exhibits particularly excellent sensitivity. In particular, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is more preferably ^5mJ / cm ^{2 ~1500mJ} / cm 2 is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7- Concentration of organic alkaline compound such as undecene is 0.001-1
An alkaline aqueous solution diluted with pure water so as to be 0% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In addition, in the manufacturing method of the color filter of this invention, after performing the polymeric composition layer formation process, the exposure process, and the image development process which were mentioned above, the formed colored pattern is heated and / or exposed as needed. A curing step for curing may be included.

  By repeating the colored polymerizable composition layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

Since the color filter of the present invention uses the polymerizable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance. It is possible to form a high-resolution pattern that is excellent in sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. That is, the color filter of the present invention is preferably applied to a solid-state image sensor.
The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

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

[Example 1-1]
<Preparation and Evaluation of Polymerizable Composition 1>
The polymerizable composition 1 was prepared as follows and the sensitivity was evaluated.
(A) As a specific example of the specific oxime compound, 0.08 mmol of the above-mentioned specific oxime compound A-1 (hereinafter also simply referred to as “compound A-1”), (B) 1 g of pentaerythritol tetraacrylate as a radical polymerizable monomer (D) A uniform composition containing 1 g of polymethyl methacrylate (manufactured by Aldrich, molecular weight ca.996000) as a binder and 16 g of cyclohexanone as a solvent (E) was prepared. Using the obtained composition as a coating solution, this was coated on a glass plate with a spin coater and dried at 40 ° C. for 10 minutes to form a coating film having a thickness of 1.5 μm. A 21√2 step tablet (Grayscale film manufactured by Dainippon Screen Mfg. Co., Ltd.) is placed on this coating film, and the light of a 500 mW high-pressure mercury lamp manufactured by Ushio Electric is passed through a heat ray cut filter. After exposure for 30 seconds, development was performed by impregnation in toluene for 60 seconds. When the number of steps completely cured and insolubilized corresponding to the step tablet was evaluated as sensitivity, the sensitivity was 9 steps.
In addition, a sensitivity step number shows that a sensitivity is so high that a number is large.

[Example 1-2 to Example 1-8, Comparative Example 1-1 to Comparative Example 1-4]
In Example 1-1, 0.08 mmol of compound A-1 used as the specific oxime compound was added to each compound shown in Table 3 (specific oxime compounds A-2 to A-8 and comparative compounds 1 to 4): 0. Polymerizable compositions 2 to 12 were prepared in exactly the same manner as in Example 1-1, except that each was replaced with 08 mmol. Furthermore, the number of sensitivity steps was evaluated for the polymerizable compositions 2 to 12 in the same manner as in Example 1-1.
The evaluation results of Example 1-1 to Example 1-8 and Comparative Example 1-1 to Comparative Example 1-4 are shown in Table 1 below.

In Table 1, details and chemical formulas of the comparative compounds (Comparative Compounds 1 to 4) are as follows.
Comparative compound 1 is IRGACURE OXE01 (manufactured by Ciba Specialty Chemicals), comparative compound 2 is IRGACURE OXE02 (manufactured by Ciba Specialty Chemicals), and comparative compound 3 is IRGACURE 369 (manufactured by Ciba Specialty Chemicals). The chemical formulas of Comparative Compound 1 to Comparative Compound 3 are shown below.

  Comparative compound 4 is a compound having the following chemical formula.

[Example 2-1]
[1. Preparation of polymerizable composition S-1]
As a polymerizable composition for forming a color filter, a negative polymerizable composition S-1 containing a colorant (pigment) was prepared, and a color filter was produced using this.

1-1. Preparation of pigment dispersion (P1) C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with CI Pigment Yellow 219, and 10 parts by mass (solid content conversion: about 4.4 by dispersbyk: manufactured by BYK Corporation, solid content concentration: 45.1% by mass) as a dispersant. 51 parts by mass) and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).

  With respect to the obtained pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

1-2. Preparation of Polymerizable Composition A-1 (Coating Liquid) Components of the following composition S-1 were mixed and dissolved to prepare a polymerizable composition S-1.

<Composition S-1>
-Pigment dispersion (P1) [(C) containing colorant] 600 parts by mass-Binder (polymer compound P) [(D) binder] 200 parts by mass (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, mol (Ratio: 80/10/10, Mw: 10,000)
・ Dipentaerythritol hexaacrylate (C-X) 60 parts by mass [(B) radical polymerizable monomer]
Compound A-1 [(A) specific oxime compound] 60 parts by mass Propylene glycol monomethyl ether acetate 1,000 parts by mass [(E) solvent]
・ Surfactant (trade name: Tetranic 150R1, BASF) 1 part by mass ・ γ-methacryloxypropyltriethoxysilane 5 parts by mass

[2. (Production of color filter)
2-1. Formation of Polymerizable Composition Layer The polymerizable composition S-1 containing the pigment obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slit coating under the following conditions, and then kept as it was for 10 minutes. Then, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a polymerizable composition coating film (polymerizable composition layer).

(Slit application conditions)
Gap at the opening of the coating head tip: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure and Development Thereafter, the polymerizable composition layer was exposed in a pattern using a 2.5 kW ultra-high pressure mercury lamp. The entire surface of the polymerizable composition layer after the exposure was covered with a 10% aqueous solution of an organic developer (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds.

2-3. Heat treatment Thereafter, pure water was sprayed onto the polymerizable composition layer in a shower to wash away the developer, and then heated in an oven at 220 ° C. for 1 hour (post-bake). Thereby, a color filter having a colored pattern on the glass substrate was obtained.

[3. (Performance evaluation)
Storage stability and exposure sensitivity of the polymerizable composition, developability when a colored pattern is formed on a glass substrate using the polymerizable composition, coloring of the obtained colored pattern with heating, substrate adhesion, and The pattern cross-sectional shape was evaluated as follows. The evaluation results are summarized in Table 2.

3-1. Storage Stability of Polymerizable Composition After storing the polymerizable composition S-1 at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria.
-Criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

3-2. Exposure Sensitivity of Polymerizable Composition Polymerizable composition S-1 was spin-coated on a glass substrate and then dried to form a coating film having a thickness of 1.0 μm. The spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds. Next, the obtained coating film was 10 mJ / cm by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having a super high pressure mercury lamp using a test photomask having a line width of 2.0 μm. It exposed with various exposure amount of ^{2 ~1600mJ} / cm ^2. Next, using a 60% CD-2000 (Fuji Film Electronics Materials Co., Ltd.) developer, the exposed coating film was developed under conditions of 25 ° C. and 60 seconds. Then, after rinsing with running water for 20 seconds, spray drying was performed to complete patterning.
Evaluation of exposure sensitivity evaluated the minimum exposure amount that the film thickness after the development of the area irradiated with light in the exposure process was 95% or more with respect to the film thickness 100% before exposure as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

3-3. Developability, pattern cross-sectional shape, substrate adhesion After developing the substrate surface and cross-sectional shape after post-baking in “2-3. Property, substrate adhesion, and pattern cross-sectional shape were evaluated. Details of the evaluation method are as follows.

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability. The evaluation criteria are as follows.
-Evaluation criteria-
○: Residue was not confirmed at all in the unexposed area. Δ: Residue was slightly confirmed at the unexposed area, but there was no practical problem. confirmed

<Coloring evaluation with forced heating over time>
The polymerizable composition layer (colored pattern) after exposure and development was heated on a hot plate at 200 ° C. for 1 hour, and the color difference ΔEab ^* before and after the heating was calculated based on the following criteria: MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. It was evaluated with.
-Evaluation criteria-
○: ΔEab ^* ≦ 5
Δ: 5 <ΔEab ^* <8
×: ΔEab ^* ≧ 8

<Board adhesion>
The substrate adhesion was evaluated based on the following criteria by observing whether or not a pattern defect occurred.
-Evaluation criteria-
○: No pattern defects were observed Δ: Pattern defects were hardly observed, but partial defects were observed x: Remarkably many pattern defects were observed

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was observed and evaluated. The cross-sectional shape of the pattern is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred. The results are shown in Table 2 below.

[Example 2-2 to Example 2-15, Comparative Example 2-1 to Comparative Example 2-4]
In composition S-1 used for preparation of polymerizable composition S-1 in Example 2-1, 60 parts by mass of compound A-1 (specific oxime compound) was replaced with each compound and amount shown in Table 2 below. Moreover, the binder and the radical polymerizable monomer are replaced with the compounds and amounts shown in Table 2 below, and further about Example 2-8 to Example 2-10 and Example 2-12 to Example 2-15, The polymerizable compositions S-2 to S-15 and S′-1 to S ′ were the same as in Example 2-1, except that the sensitizers and cosensitizers shown in Table 2 below were added. -4 was prepared to obtain a color filter.
Furthermore, each color filter of Example 2-2 to Example 2-15 and Comparative Example 2-1 to Comparative Example 2-4 was evaluated in the same manner as in Example 2-1. The results are shown in Table 2.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 2 are the compounds shown below.

  From the results in Table 2, it can be seen that the polymerizable composition of each Example containing the specific oxime compound (Compound A-1 to Compound A-15) is excellent in storage stability (time stability). In addition, these polymerizable compositions have high exposure sensitivity, developability when a colored pattern of a color filter is used for forming, and the resulting colored pattern is not colored with heating, and also has substrate adhesion and pattern. It turns out that it is excellent in all of cross-sectional shapes.

[Example 3-1]
[1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
-Composition of resist solution-
Propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts by mass Ethyl lactate 36.67 parts by mass Binder (polymer compound Q) 30.51 parts by mass [benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate] Copolymer (Molar ratio = 60/22/18) 40% PGMEA solution]
Dipentaerythritol hexaacrylate (polymerizable compound CX) 12.20 parts by mass Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass Fluorosurfactant 0.83 parts by mass (F-475, Dainippon Ink & Chemicals, Inc.)
・ 0.586 parts by weight of photopolymerization initiator (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

[2. Fabrication of silicon wafer substrate with undercoat layer]
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

[3. Preparation of polymerizable composition T-1] A compound of the following composition T-1 was mixed and dissolved to prepare a polymerizable composition T-1 containing a colorant (dye).

<Composition T-1>
・ Cyclohexanone [(E) solvent] 80 parts by mass I. Acid Blue 108 [(C) Colorant] 7.5 parts by mass / C.I. I. Solvent Yellow 162 [(C) Colorant] 2.5 parts by mass / radically polymerizable monomer (C—Y) 7.0 parts by mass [3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate; B) Radical polymerizable monomer]
Compound A-1 [(A) specific oxime compound] 2.5 parts by mass Glycerol propoxylate 0.5 parts by mass (number average molecular weight Mn: 1500, molar extinction coefficient ε = 0)

[4. Evaluation of Storage Stability of Polymerizable Composition T-1 (Coating Solution)]
After the polymerizable composition T-1 was stored at room temperature for 1 month, the degree of precipitation of foreign matters was visually evaluated according to the following criteria. The results are shown in Table 3 below.
-Criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

[5. Production and Evaluation of Color Filter Using Polymerizable Composition T-1]
3 above. The polymerizable composition T-1 prepared in the above 2. It was applied on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1) to form a photocurable coating film. Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.9 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), irradiation was performed at an exposure dose of 10 to 1,600 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

A silicon wafer substrate on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 rpm by a rotating device, while being pure from above the rotation center. Water was supplied in a shower form from the ejection nozzle to perform rinsing, and then spray-dried.
As described above, a color filter having a colored pattern formed on the substrate was obtained.

<Exposure sensitivity and pattern size>
The minimum exposure amount in which the film thickness after development of the region irradiated with light in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.
In addition, the size of the colored pattern was measured using a length measurement SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The closer the pattern size is to 2 μm, the better the curability and the better the sensitivity.
The results are shown in Table 3 below.

<Developability, coloring over time, substrate adhesion, pattern cross-sectional shape>
The evaluation of developability, coloring over time, substrate adhesion, and pattern cross-sectional shape was evaluated based on the evaluation method and evaluation criteria performed for Example 2-1. The results are shown in Table 3 below.

[Example 3-2 to Example 3-9 and Comparative Example 3-1 to Comparative Example 3-4]
For Example 3-2 to Example 3-8 and Comparative Example 3-1 to Comparative Example 3-4, in Example 3-1, the composition T-1 used for the preparation of the polymerizable composition T-1 In the same manner as in Example 3-1, except that 2.5 parts by mass of compound A-1 (specific oxime compound) in the above was replaced by the respective compounds and amounts shown in Table 3 below, polymerizable composition T- 2 to T-8 and T′-1 to T′-4 were prepared to obtain color filters.
For Example 3-9, 2.5 parts by mass of Compound A-1 (specific oxime compound) in Composition T-1 used for the preparation of the polymerizable composition T-1 in Example 3-1 are shown in the table below. Example 3-1, except that each sensitizer and co-sensitizer shown in Table 3 below were added in the types and amounts shown in Table 3 below instead of the compounds and amounts shown in Table 3. Thus, a polymerizable composition T-9 was prepared to obtain a color filter.
Furthermore, the same evaluation as in Example 3-1 was performed on the color filters of Example 3-2 to Example 3-9 and Comparative Example 3-1 to Comparative Example 3-4. The results are shown in Table 3.

  The sensitizer A3 and the co-sensitizer F3 shown in Table 3 are the compounds described above.

[Example 3-10]
A compound having the following composition U-1 was mixed and dissolved to prepare a polymerizable composition U-1 containing a colorant (pigment).

<Composition U-1>
-Ethyl 3-ethoxypropionate [(E) solvent] 17.9 mass parts-C.I. I. Pigment Red 254 dispersion 26.7 parts by mass (solid content: 15% by mass, pigment content in the solid content: 60%) [(C) Colorant]
・ C. I. Pigment Yellow 139 dispersion 17.8 parts by mass (solid content: 15% by mass, pigment content in the solid content: 60%) [(C) Colorant]
-Radical polymerizable monomer (CY) 3.5 parts by mass [3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate, (B) radical polymerizable monomer]
Compound A-1 ((A) specific oxime compound) 0.5 part by mass Benzyl methacrylate / methacrylic acid copolymer 2.0 part by mass (molar ratio = 70/30) [(D) binder]

[Examples 3-11 to 3-20 and Comparative Examples 3-5 to 3-8]
About Example 3-11 to Example 3-17 and Comparative Example 3-5 to Comparative Example 3-8, the composition U-1 used for the preparation of the polymerizable composition U-1 in Example 3-10 Polymeric composition U was carried out in the same manner as in Example 3-10, except that 0.5 part by mass of compound A-1 (specific oxime compound) was changed to the respective compounds and amounts shown in Table 4 below. -2 to U-8 and U'-1 to U'-4 were prepared.
About Example 3-18 to Example 3-20, the compound A-1 (specific oxime compound) 0. 0 in the composition U-1 used for the preparation of the polymerizable composition U-1 in Example 3-10 was used. Except for adding 5 parts by mass to the respective compounds and amounts shown in Table 4 below, and further adding the sensitizers and co-sensitizers shown in Table 4 below in the types and amounts shown in Table 4 below, In all the same manner as in Example 3-10, polymerizable compositions U-9 to U-11 were prepared.

  The obtained polymerizable compositions U-2 to U-11 and U'-1 to U'-4 were evaluated in the same manner as in Example 3-1. The results are shown in Table 4.

  Note that sensitizers A1 and A3 and co-sensitizers F2 and F3 shown in Table 4 are the compounds described above.

[Example 3-21]
A compound having the following composition V-1 was mixed and dissolved to prepare a polymerizable composition V-1 containing a colorant (pigment).

<Composition V-1>
-Ethyl 3-ethoxypropionate [(E) solvent] 17.9 mass parts-Colorant C.I. I. PigmentRed 254 dispersion 33.34 parts by mass (solid content: 15% by mass, pigment content in the solid content: 60%) [(C) Colorant]
-Colorant C.I. I. Pigment Yellow 139 dispersion 22.23 parts by mass (solid content: 15% by mass, pigment content in the solid content: 60%) [(C) Colorant]
-Radical polymerizable monomer (CY) 2.5 parts by mass [3: 7 mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate, (B) radical polymerizable monomer]
Compound A-1 ((A) specific oxime compound) 0.5 part by mass Benzyl methacrylate / methacrylic acid copolymer 2.0 part by mass (molar ratio = 70/30) [(D) binder]

[Example 3-22 to Example 3-28, and Comparative Example 3-9 to Comparative Example 3-12]
In Example 3-21, 0.5 part by mass of compound A-1 (specific oxime compound) in composition V-1 used for preparation of polymerizable composition V-1 was replaced with each compound 0 shown in Table 5 below. Polymeric compositions V-2 to V-8 and V′-1 to V′-4 were prepared in the same manner as in Example 3-21 except that the amount was changed to 0.5 parts by mass.

  The obtained polymerizable compositions V-1 to V-8 and V'-1 to V'-4 were evaluated in the same manner as in Example 3-1. The results are shown in Table 5.

From the results of Tables 3 to 5, the polymerizable composition of each Example containing the specific oxime compounds (Compounds A-1 to A-21) is excellent in storage stability (time stability). I understand. In addition, these polymerizable compositions have high exposure sensitivity, developability when a colored pattern of a color filter is used for forming, and the resulting colored pattern is not colored with heating, and also has substrate adhesion and pattern. It turns out that it is excellent in all of cross-sectional shapes.
Further, as is apparent from Table 5, it can be seen that even when the pigment content is high, the exposure sensitivity is excellent.

[Example 4]
<Production of full-color color filter>
A full-color color filter having a colored pattern obtained using the following RGB colored colored polymerizable composition and a black matrix was produced.

-Colored polymerizable composition-
As the polymerizable composition for green (G), the polymerizable composition T-1 used in Example 3-1 was used.
For the polymerizable composition T-1, pigments (CI Acid Blue 108 and CI Solvent Yellow 162) were used, blue pigments (CI Pigment Blue 15: 6, and CI Pigment Violet). A polymerizable composition Z-1 for blue (B) was prepared in the same manner except that the mixture was changed to a 30/70 [mass ratio] mixture with No. 23).
Moreover, the said polymeric composition U-1 used in Example 3-10 was used as a polymeric composition for red (R).

  First, a black matrix is formed on a glass substrate by a conventional method, and 2 μm square green (in the same manner as described in Example 3-1, using the polymerizable composition T-1 on the black matrix ( A colored pattern of G) was formed. Further, a 2 μm square red (R) and blue (B) pattern was sequentially formed in the same manner as performed with the green (G) polymerizable composition T-1 to produce a color filter for a solid-state imaging device.

  About the obtained color filter, when the cross-sectional shape and the board | substrate adhesiveness were evaluated about the coloring pattern of each RGB color and the black matrix pattern by the method similar to Example 3-1, all were rectangular and the defect | deletion of a pattern also occurred. It was found that the adhesiveness was excellent.

[Example 5]
<Production of solid-state image sensor>
When the color filter obtained in Example 4 was incorporated into a solid-state imaging device, it was confirmed that the solid-state imaging device had high resolution and excellent color separation.

Claims (12)

A compound represented by the following general formula (1) and having a polymerization initiation function.

[In the general formula (1), A represents an oxygen atom or a sulfur atom, and R ¹ represents an alkenyl group, an aryl group, a heterocyclic group, —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). Represents. R ² represents —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² may combine with each other to form a ring. R ³ represents an alkyl group or an aryl group. ] A polymerization initiator containing a compound represented by the following general formula (1) and having a polymerization initiation function.

[In the general formula (1), A represents an oxygen atom or a sulfur atom, and R ¹ represents an alkenyl group, an aryl group, a heterocyclic group, —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). Represents. R ² represents —CN, —COOR ⁴ , or —CON (R ⁴ R ⁵ ). R ⁴ and R ⁵ each independently represents an alkyl group, an aryl group, or a heterocyclic group. R ¹ and R ² may combine with each other to form a ring. R ³ represents an alkyl group or an aryl group. ]   (A) A polymerizable composition comprising at least a polymerization initiator represented by the general formula (1) and containing a compound having a polymerization initiation function, and (B) a radical polymerizable monomer.   Furthermore, (C) A coloring agent is contained, The polymeric composition of Claim 3 characterized by the above-mentioned.   Furthermore, (D) binder is contained, The polymeric composition of Claim 3 or Claim 4 characterized by the above-mentioned.   The polymerizable composition according to claim 4 or 5, wherein the colorant (C) is a pigment or a dye.   7. The polymerizable composition according to claim 6, wherein a solid content of the pigment or the dye is 50% by mass to 80% by mass with respect to a total solid content of the polymerizable composition.   The polymerizable composition according to claim 3, wherein the (B) radical polymerizable monomer has an acid group.   The polymerizable composition according to any one of claims 5 to 8, wherein the (D) binder has a double bond.   It has a coloring pattern formed using the polymeric composition of any one of Claims 4-9, The color filter characterized by the above-mentioned. A polymerizable composition layer forming step of forming a polymerizable composition layer on the support using the polymerizable composition according to any one of claims 4 to 9,
An exposure step of exposing the polymerizable composition layer through a mask;
A development step of developing the polymerizable composition layer after exposure to form a colored pattern;
A method for producing a color filter, comprising:   A solid-state imaging device comprising the color filter according to claim 10.