JP2018205445A - Photosensitive composition, cured film, display device, and method for forming patterned cured film - Google Patents

Abstract

To provide a photosensitive composition that can form a black cured film having excellent insulating performance and substrate adhesion irrespective of having excellent light blocking performance, a cured film obtained by curing the photosensitive composition, a display device having the cured film, and a method for forming a patterned cured film using the photosensitive composition.SOLUTION: A photosensitive composition contains (B) a photopolymerization initiator, and (C) carbon black of 30 mass% or more of the total solid content. The photosensitive composition contains, as (A) a crosslink component, a siloxane compound having two or more polymerizable carbon-carbon double bonds, in its structure.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive composition, a cured film obtained by curing the photosensitive composition, a display device including the cured film, and a method for forming a patterned cured film using the photosensitive composition described above. And about.

  A display panel in an image display device such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which a pair of electrodes are formed facing each other. A color filter having pixels of red (R), green (G), blue (B) and the like is formed inside one substrate. In this color filter, in order to prevent color mixing of different colors in each pixel or to conceal the electrode pattern, the color filter is usually arranged in a matrix so as to partition the pixels of R, G, and B colors. A black matrix is formed.

  Generally, the color filter is formed by a lithography method. Specifically, first, a black photosensitive composition is applied to a substrate, exposed and developed to form a black matrix. Then, for each of the photosensitive compositions of red (R), green (G), and blue (B), coating, exposure, and development are repeated to form a pattern of each color at a predetermined position, thereby forming a color filter. Form.

As a method for forming a black matrix when forming a color filter, a method using a negative photosensitive resin composition has been proposed.
For example, Patent Document 1 discloses carbon black, hydrophobic silica fine particles, and the like as a black photosensitive resin composition that is a raw material for a black matrix that can achieve both high light-shielding properties and low reflectance at low cost. A blended negative photosensitive resin composition is shown.

Japanese Patent Laying-Open No. 2015-161815

  From the viewpoint of improving the image quality of an image display device, the black matrix is desired to have a higher light shielding property. Examples of a method for improving the light shielding property of the black matrix formed using the photosensitive resin composition described in Patent Document 1 include a method for increasing the content of carbon black in the photosensitive resin composition. However, when the content of carbon black in the photosensitive resin composition as described in Patent Document 1 is increased, there is a problem in that the insulating property and the adhesion to the substrate are lowered with respect to the formed cured film. is there.

  The present invention has been made in view of the above-described problems, and has a photosensitive composition capable of forming a black cured film having excellent insulating properties and adhesion to a substrate despite excellent light shielding properties. An object of the present invention is to provide a cured film obtained by curing the photosensitive composition, a display device including the cured film, and a method for forming a patterned cured film using the photosensitive composition described above. .

  In the photosensitive composition containing (B) a photopolymerization initiator and 30% by mass or more of (C) carbon black in the total solid content, (A) as a crosslinking component, It has been found that the above problem can be solved by blending a siloxane compound having two or more polymerizable carbon-carbon double bonds, and the present invention has been completed. More specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive composition comprising (A) a crosslinking component, (B) a photopolymerization initiator, and (C) carbon black,
(A) The crosslinking component is represented by the following formulas (a1) to (a4):
M unit: R ¹ R ² R ³ SiO _1/2 (a1)
D unit: R ⁴ R ⁵ SiO _2/2 (a2)
T unit: R ⁶ SiO _3/2 (a3)
Q unit: SiO _4/2 (a4)
(In the formulas (a1) to (a4), R ^{1 to} R ⁶ are each independently a group represented by R ⁷ — or R ⁷ —O—, and R ⁷ is a group represented by the formula (a1) to the formula (It is a monovalent organic group bonded to the silicon atom in (a3) by a C—Si bond or bonded to the oxygen atom in R ⁷ —O— by a C—O bond.)
A siloxane compound containing one or more structural units selected from M units, D units, T units, and Q units represented by:
The siloxane compound has two or more carbon-carbon double bonds in its structure, and the siloxane compound contains two or more structural units selected from M units, D units, T units, and Q units,
The content of (C) carbon black in the total solid content of the photosensitive composition is 30% by mass or more,
When the amount of silicon atoms (% by mass) and the amount of carbon atoms (% by mass) in the cured product of the photosensitive composition were measured under the following measurement conditions, the ratio of the amount of silicon atoms (% by mass) / the amount of carbon atoms (% by mass) was It is a photosensitive composition which is 0.05 or more.

(Measurement condition)
The photosensitive composition is coated on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film. XPS is measured on the surface of the cured film, the peak area of each element is obtained, and the mass ratio of each element is calculated.

  The second aspect of the present invention is a cured film obtained by curing the photosensitive composition according to the first aspect.

  A 3rd aspect of this invention is a display apparatus provided with the cured film concerning a 2nd aspect.

According to a fourth aspect of the present invention, there is provided a step of forming a coating film by applying the photosensitive composition according to the first aspect;
A step of selectively exposing the coating film;
Developing the exposed coating film, and forming a patterned cured film.

  According to the present invention, a photosensitive composition capable of forming a black cured film having excellent insulating properties and adhesion to a substrate in spite of excellent light shielding properties, and curing the photosensitive composition. A cured film, a display device including the cured film, and a method for forming a patterned cured film using the photosensitive composition described above can be provided.

≪Photosensitive composition≫
The photosensitive composition contains (A) a crosslinking component, (B) a photopolymerization initiator, and (C) carbon black. The content of (C) carbon black in the photosensitive composition is such that the content of (C) carbon black in the total solid content of the photosensitive composition is 30% by mass or more. For this reason, the cured film which is excellent in light-shielding property can be formed using a photosensitive composition.

Moreover, the (A) crosslinking component contained in the photosensitive composition is represented by the following formulas (a1) to (a4):
M unit: R ¹ R ² R ³ SiO _1/2 (a1)
D unit: R ⁴ R ⁵ SiO _2/2 (a2)
T unit: R ⁶ SiO _3/2 (a3)
Q unit: SiO _4/2 (a4)
(In the formulas (a1) to (a4), R ^{1 to} R ⁶ are each independently a group represented by R ⁷ — or R ⁷ —O—, and R ⁷ is a group represented by the formula (a1) to the formula (It is a monovalent organic group bonded to the silicon atom in (a3) by a C—Si bond or bonded to the oxygen atom in R ⁷ —O— by a C—O bond.)
A siloxane compound containing one or more structural units selected from an M unit, a D unit, a T unit, and a Q unit.
The siloxane compound has two or more carbon-carbon double bonds in its structure, and the siloxane compound contains two or more structural units selected from M units, D units, T units, and Q units. .
When the photosensitive composition contains the above siloxane compound as the crosslinking component (A), a cured film excellent in insulation and adhesion to the substrate can be easily formed.

Furthermore, when the silicon atom weight (mass%) and the carbon atom weight (mass%) in the cured product of the photosensitive composition were measured under the following measurement conditions, the silicon atom weight (mass%) / carbon atom weight (mass%) The ratio is 0.05 or more. The ratio is preferably 0.06 or more, more preferably 0.07 or more, even more preferably 0.08 or more, particularly preferably 0.09 or more, and most preferably 0.10 or more.
(Measurement condition)
The photosensitive composition is coated on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film. XPS is measured on the surface of the cured film, the peak area of each element is obtained, and the mass ratio of each element is calculated.

In order to improve the adhesion between the substrate and the cured film, (A) a siloxane compound as a crosslinking component is prepared by changing the siloxane compound in the photosensitive composition, (C) carbon black, and (D) binder resin described later. When the ratio of the amount of silicon atom (mass%) / carbon atom weight (mass%) in the cured product of the photosensitive composition is 0.05 or more, the siloxane compound is (C ) It sufficiently acts on carbon black and (D) binder resin described later, and can sufficiently improve the adhesion between the substrate and the cured film.
Further, when the ratio of silicon atom weight (mass%) / carbon atom weight (mass%) is 0.05 or more, (A) the siloxane compound as a crosslinking component sufficiently acts on the surface of (C) carbon black, A cured film having excellent insulating properties can be formed.

<(A) Crosslinking component>
The (A) crosslinking component is a component having a carbon-carbon double bond that can be polymerized by a photopolymerization initiator (B) described later. (A) The crosslinking component is represented by the following formulas (a1) to (a4):
M unit: R ¹ R ² R ³ SiO _1/2 (a1)
D unit: R ⁴ R ⁵ SiO _2/2 (a2)
T unit: R ⁶ SiO _3/2 (a3)
Q unit: SiO _4/2 (a4)
(In the formulas (a1) to (a3), R ^{1 to} R ⁶ are each independently a group represented by R ⁷ — or R ⁷ —O—, and R ⁷ is a group represented by the formula (a1) to the formula (It is a monovalent organic group bonded to the silicon atom in (a3) by a C—Si bond or bonded to the oxygen atom in R ⁷ —O— by a C—O bond.)
A siloxane compound containing one or more structural units selected from an M unit, a D unit, a T unit, and a Q unit. Such a siloxane compound has two or more carbon-carbon double bonds in its structure.
Although the photosensitive composition includes the combination of (A) the crosslinking component and (C) carbon black that is 30% by mass or more based on the total solid content of the photosensitive composition, the photosensitive composition has excellent light shielding properties. Therefore, it is possible to form a black cured film excellent in insulation and adhesion to the substrate.

In the above formulas (a1) to (a3), R ^{1 to} R ⁶ are each independently a group represented by R ⁷ — or R ⁷ —O—. R ⁷ is a monovalent organic group, and is bonded to the silicon atom in the formulas (a1) to (a3) by a C—Si bond or is bonded to the oxygen atom in R ⁷ —O—. Join by joining.

The organic group as R ⁷ is not particularly limited as long as the above conditions are satisfied. R ⁷ may contain a heteroatom such as O, N, S, P, B, or a halogen atom.
Preferable examples when the organic group as R ⁷ does not have a carbon-carbon double bond that can be polymerized by (B) a photopolymerization initiator include alkyl groups having 1 to 20 carbon atoms, carbon atoms A cycloalkyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, Examples thereof include aromatic acyl groups having 7 to 20 carbon atoms. Any of these groups may have a substituent. The type and number of substituents are not particularly limited as long as the object of the present invention is not impaired.

  Preferred examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 3 to 10 carbon atoms. A cycloalkoxy group, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted phenylthio group, an optionally substituted benzoyl group, and an optionally substituted phenoxycarbonyl group A benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a substituent Naphthoxy group which may have, naphthoyl group which may have substituent, naphthoxycarbonyl group which may have substituent, naphthoyloxy group which may have substituent, and substituent A naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, an organic group of 1 or 2; Examples include substituted amino groups, hydroxyl groups, mercapto groups, halogen atoms, nitro groups, and cyano groups.

Preferable specific examples of the organic group as R ⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. And alkyl groups having 1 to 6 carbon atoms such as n-hexyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, naphthalen-1-yl group, and naphthalen-2-yl group Aromatic hydrocarbon groups such as acetyl group, propionyl group, butanoyl group, pentanoyl group, etc., saturated aliphatic acyl groups having 2 to 6 carbon atoms; benzoyl group, naphthalen-1-ylcarbonyl group, naphthalene-2- An aromatic acyl group such as an ylcarbonyl group may be mentioned.
Among these, a methyl group, an ethyl group, a phenyl group, a methoxy group, an ethoxy group, and a phenoxy group are preferable.

Preferable specific examples of the M unit having no carbon-carbon double bond include (CH ₃ ) ₃ SiO _1/2 , (CH ₃ CH ₂ ) (CH ₃ ) ₂ SiO _1/2 , (CH ₃ CH ₂ ) Trialkyl units such as ₂ (CH ₃ ) SiO _1/2 , (CH ₃ CH ₂ ) ₃ SiO _1/2 ; Triaryl units such as (C ₆ H ₅ ) ₃ SiO _1/2 ; (C ₆ H ₅ ) Diaryl monoalkyl units such as ₂ (CH ₃ ) SiO _1/2 , (C ₆ H ₅ ) ₂ (CH ₃ CH ₂ ) SiO _1/2 ; (C ₆ H ₅ ) (CH ₃ ) ₂ SiO _{1 / 2} , monoaryldialkyl units such as (C ₆ H ₅ ) (CH ₃ CH ₂ ) ₂ SiO _1/2 ; (CH ₃ O) ₃ SiO _1/2 , (CH ₃ CH ₂ O) (CH ₃ O) ₂ SiO _1/2 , (CH ₃ CH ₂ O) ₂ (CH ₃ O ) Trialkoxy units such as SiO _1/2 , (CH ₃ CH ₂ O) ₃ SiO _1/2 ; Triaryloxy units such as (C ₆ H ₅ O) ₃ SiO _1/2 ; (C ₆ H ₅ O) Diaryloxymonoalkoxy units such as ₂ (CH ₃ O) SiO _1/2 , (C ₆ H ₅ O) ₂ (CH ₃ CH ₂ O) SiO _1/2 ; (C ₆ H ₅ O) (CH ₃ O) Monoaryloxydialkoxy units such as ₂ SiO _1/2 , (C ₆ H ₅ O) (CH ₃ CH ₂ O) ₂ SiO _1/2 ; (CH ₃ O) ₂ (CH ₃ ) SiO _1/2 , ( _{CH 3 O) 2 (CH 3} CH 2) SiO 1/2, (CH 3 CH 2 O) 2 (CH 3) SiO 1/2, (CH 3 CH 2 O) 2 (CH 3 CH 2) SiO 1 / dialkoxyalkyl monoalkyl units ₂ such; (CH _{3 ) 2 (C 6 H 5)} SiO 1/2, (CH 3 CH 2 O) 2 (C 6 H 5) dialkoxy monoaryl units _{SiO 1/2, etc.; (CH 3 O) (C} 6 H 5) Monoalkoxydiaryl units such as ₂ SiO _1/2 , (CH ₃ CH ₂ O) (C ₆ H ₅ ) ₂ SiO _1/2 ; (C ₆ H ₅ O) (CH ₃ ) ₂ SiO _1/2 , (C _{6 H 5 O) (CH 3} CH 2) 2 mono aryloxy dialkyl units _{SiO 1/2, etc.; (C 6 H 5 O)} 2 (CH 3) SiO 1/2, (C 6 H 5 O) 2 ( Diaryloxymonoalkyl units such as CH ₃ CH ₂ ) SiO _1/2 ; monoaryloxydiaryl units such as (C ₆ H ₅ O) (C ₆ H ₅ ) ₂ SiO _1/2 ; (C ₆ H ₅ O) ₂ Dia, such as (C ₆ H ₅ ) SiO _1/2 Examples include a reeloxy monoaryl unit.

Preferable specific examples of the D unit having no carbon-carbon double bond include (CH ₃ ) ₂ SiO _2/2 , (CH ₃ CH ₂ ) (CH ₃ ) SiO _2/2 , (CH ₃ CH ₂ ) dialkyl unit such _{2 SiO 2/2; (C 6 H} 5) diaryl units such as _{2 SiO 2/2; (C 6 H} 5) (CH 3) SiO 2/2, (C 6 H 5) (CH ₃ CH ₂₎ monoaryl monoalkyl units such as _{SiO 2/2; (CH 3 O)} 2 SiO 2/2, (CH 3 CH 2 O) (CH 3 O) SiO 2/2, (CH 3 CH 2 O ) Dialkoxy units such as ₂ SiO _2/2 ; Diaryloxy units such as (C ₆ H ₅ O) ₂ SiO _2/2 ; (C ₆ H ₅ O) (CH ₃ O) SiO _2/2 , (C _{6 H 5 O) (CH 3 CH} 2 O) Monoari such _{SiO 2/2} Oxy mono alkoxy _{units; (CH 3 O) (CH} 3) SiO 2/2, (CH 3 O) (CH 3 CH 2) SiO 2/2, (CH 3 CH 2 O) (CH 3) SiO 2 / ₂ , _{monoalkoxymonoalkyl} units such as (CH ₃ CH ₂ O) (CH ₃ CH ₂ ) SiO _2/2 ; (CH ₃ O) (C ₆ H ₅ ) SiO _2/2 , (CH ₃ CH ₂ O) Monoalkoxymonoaryl units such as (C ₆ H ₅ ) SiO _2/2 ; (C ₆ H ₅ O) (CH ₃ ) SiO _2/2 , (C ₆ H ₅ O) (CH ₃ CH ₂ ) SiO _{2 /} Monoaryloxymonoalkyl units such as ₂ ; monoaryloxymonoaryl units such as (C ₆ H ₅ O) (C ₆ H ₅ ) SiO _{2/2 and the} like.

Preferable specific examples of the T unit having no carbon-carbon double bond include monoalkyl units such as (CH ₃ ) SiO _3/2 and (CH ₃ CH ₂ ) SiO _3/2 ; (C ₆ H ₅ ) _Monoaryl units such as SiO _3/2 ; Monoalkoxy units such as (CH ₃ O) SiO _3/2 , (CH ₃ CH ₂ O) SiO _3/2 ; (C ₆ H ₅ O) SiO _3/2 etc. And the like.

Preferable examples when R ⁷ is a group having a carbon-carbon double bond include an alkenyl group having 2 to 10 carbon atoms and an aromatic group substituted with an alkenyl group having 2 to 4 carbon atoms. A hydrocarbon group, a heterocyclic group substituted with an alkenyl group having 2 to 4 carbon atoms, an alkyl group having 2 to 10 carbon atoms substituted with an acryloyloxy group, and a carbon atom substituted with a methacryloyloxy group 2 to 10 alkyl groups, aromatic hydrocarbon groups substituted with acryloyloxy groups, aromatic hydrocarbon groups substituted with methacryloyloxy groups, heterocyclic groups substituted with acryloyloxy groups, substituted with methacryloyloxy groups A heterocyclic group formed.

Preferable specific examples when R ⁷ is a group having a carbon-carbon double bond include a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, a 5-hexenyl group, and a 4-vinylphenyl group. , 3-vinylphenyl group, 2-vinylphenyl group, 2-acryloyloxyethyl group, 2-methacryloyloxyethyl group, 3-acryloyloxy n-propyl group, 3-methacryloyloxy n-propyl group. In these, a vinyl group, an allyl group, 3-acryloyloxy n-propyl group, and 3-methacryloyloxy n-propyl group are more preferable.

  The total amount of M units, D units, and T units including a group having a carbon-carbon double bond in all structural units of the siloxane compound is preferably 5 mol% or more and 70 mol% or less, and preferably 10 mol% or more and 50 mol% or less. The following is more preferable, and 15 mol% or more and 30 mol% or less is particularly preferable.

Preferable examples of the M unit having a vinyl group as a group having a carbon-carbon double bond include units represented by the following formula.

Preferable examples of the M unit having an allyl group as a group having a carbon-carbon double bond include units represented by the following formula.

Preferable examples of the M unit having a 3-acryloyloxy n-propyl group as the group having a carbon-carbon double bond include units represented by the following formulae.

Preferable examples of the M unit having a 3-methacryloyloxy n-propyl group as a group having a carbon-carbon double bond include units represented by the following formula.

As a suitable example of D unit which has a vinyl group as a group which has a carbon-carbon double bond, the unit represented by a following formula is mentioned.

As a suitable example of D unit which has an allyl group as a group which has a carbon-carbon double bond, the unit represented by a following formula is mentioned.

As a suitable example of the M unit having a 3-acryloyloxy n-propyl group or a 3-methacryloyloxy n-propyl group as a group having a carbon-carbon double bond, a unit represented by the following formula may be mentioned.

Preferable examples of the T unit having a vinyl group, an allyl group, a 3-acryloyloxy n-propyl group, or a 3-methacryloyloxy n-propyl group as a group having a carbon-carbon double bond are represented by the following formulae. Units.

  The M unit represented by the formula (a1), the D unit represented by the formula (a2), the T unit represented by the formula (a3), and the Q unit represented by the formula (a4) described above. A siloxane compound having a unit selected from the following can be produced by hydrolytic condensation of silane compounds represented by the following formulas (a-I) to (a-IV) according to a conventional method.

Silane compound giving M units: R ¹ R ² R ³ SiR ⁸ (a-I)
Silane compound giving D unit: R ⁴ R ⁵ SiR ⁸ ₂ (a-II)
Silane compound giving T unit: R ⁶ SiR ⁸ ₃ (a-III)
Silane compound giving Q unit: SiR ⁸ ₄ (a-IV)
In the above formulas (a-I) to (a-IV), R ^{1 to} R ⁶ are the same as R ^{1 to} R ⁶ in formulas (a1) to (a4), and R ⁸ is a silanol group by hydrolysis. Represents a group that generates

  It does not specifically limit as group which produces | generates a silanol group by hydrolysis, It can select from a well-known group suitably. Examples of the group that generates a silanol group by hydrolysis include an alkoxy group such as a methoxy group, an ethoxy group, an n-propyloxy group, and an isopropyloxy group; a phenoxy group; a halogen atom such as a chlorine atom and a bromine atom; and an isocyanate group. It is done.

The above siloxane compounds are represented by the following formulas (a1a), (a2a), (a3a), and (a4):
(R ⁷ O) ₃ SiO _1/2 ... (A1a)
_{^{(R 7 O) 2 SiO 2/2}} ··· (a2a)
(R ⁷ O) SiO _3/2 (a3a)
SiO _4/2 (a4)
(In Formula (a1a), Formula (a2a), and Formula (a3a), R ⁷ is a monovalent organic group bonded to an oxygen atom in R ⁷ —O— by a C—O bond.)
It is preferable that 1 or more types of structural units I selected from the structural unit represented by these are included.
When the siloxane compound contains the structural unit I, it is easier to form a black cured film having excellent insulation and adhesion to the substrate.

The siloxane compound further includes the following formula (a1b), formula (a2b), and formula (a3b):
(R ⁷ O) ₂ R ⁷ SiO _1/2 ... (A1b)
(R ⁷ O) R ⁷ SiO _2/2 (a2b)
R ⁷ SiO _3/2 (a3b)
(In formula (a1b), formula (a2b), and formula (a3b), is R ⁷ bonded to the silicon atom in formula (a1b), formula (a2b), and formula (a3b) by a C—Si bond? , R ⁷ —O— is a monovalent organic group bonded to the oxygen atom by a C—O bond.)
One or more structural units II selected from the structural units represented by: and / or the following formulas (a1c) and (a2c):
(R ⁷ O) R ⁷ ₂ SiO _1/2 ... (A1c)
R ⁷ ₂ SiO _2/2 (a2c)
(In Formula (a1c) and Formula (a2c), R ⁷ is bonded to the silicon atom in Formula (a1c) and Formula (a2c) with a C—Si bond, or is bonded to the oxygen atom in R ⁷ —O—. (It is a monovalent organic group bonded by a C—O bond.)
It is preferable that 1 or more types of structural units III selected from the structural units represented by these are included.
When the siloxane compound contains the structural unit II and / or the structural unit III together with the structural unit I, a black cured film excellent in insulation and adhesion to the substrate can be more easily formed.

When the siloxane compound includes the structural unit II and / or the structural unit III together with the structural unit I, the molar amount of (the structural unit I) / (the structural unit I, the structural unit II, and the structural unit III in the siloxane compound) The value of the sum of the values is preferably 0.25 or more.
When the value of (molar amount of structural unit I) / (sum of molar amounts of structural unit I, structural unit II, and structural unit III) is 0.25 or more, the insulation and adhesion to the substrate are excellent. It is particularly easy to form a black cured film.
The value of (molar amount of structural unit I) / (sum of molar amounts of structural unit I, structural unit II, and structural unit III) is preferably 0.30 or more, more preferably 0.40 or more, and 0.50 or more. Is particularly preferred.
The upper limit value of (molar amount of structural unit I) / (sum of molar amounts of structural unit I, structural unit II, and structural unit III) can be appropriately set, and is preferably 0.90 or less, for example. Is 0.85 or less.

As a preferable example of the siloxane compound described above, it is composed of (CH ₃ O) SiO _3/2 (T unit), (CH ₃ ) SiO _3/2 (T unit), and a unit of the following formula (T unit). A siloxane compound is mentioned. Here, (CH ₃ O) SiO _3/2 (T unit) corresponds to the structural unit I. Further, (CH ₃ ) SiO _3/2 (T unit) and the unit of the following formula (T unit) correspond to the structural unit II.

In such a siloxane compound, the content of (CH ₃ O) SiO _3/2 (T unit) is preferably 25 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 70 mol% or less in all the structural units. 40 mol% or more and 60 mol% or less is particularly preferable.
In the siloxane compound, the content of the structural unit of the above formula having a 3-methacryloyloxy n-propyl group is preferably 5 mol% or more and 70 mol% or less, and preferably 10 mol% or more and 50 mol% in all the structural units. The following is more preferable, and 15 mol% or more and 30 mol% or less is particularly preferable.

  The molecular weight of the siloxane compound is not particularly limited as long as the object of the present invention is not impaired. The weight average molecular weight (Mw) in terms of polystyrene of the siloxane compound is preferably 750 or more and 6000 or less, more preferably 800 or more and 5000 or less, and particularly preferably 1000 or more and 3000 or less.

  In the photosensitive composition, the content of the siloxane compound as the crosslinking component (A) is preferably 5% by mass or more, more preferably 5% by mass or more and 30% by mass or less, based on the total solid content of the photosensitive composition. 5 mass% or more and 20 mass% or less are more preferable, and 5 mass% or more and 15 mass% or less are especially preferable.

<(B) Photopolymerization initiator>
(B) It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used.

  (B) Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl]. 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, Non, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), (9-ethyl-6-nitro-9H-carbazole-3) -Yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Butyl aminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-yl Amylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobe Zoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p '-Bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9 -Acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan- 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloro) Romethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4) -Methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2- Bromo-4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. Among oxime-based photopolymerization initiators, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime and ethanone are particularly preferable. , 1- [9-Ethyl-6- (pyrrol-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), and 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)].

（Ｒ^ｂ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、
ｎ１は０以上４以下の整数であり、
ｎ２は０、又は１であり、
Ｒ^ｂ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、
Ｒ^ｂ３は、水素原子、又は炭素原子数１以上６以下のアルキル基である。） As the photopolymerization initiator, it is also preferable to use an oxime compound represented by the following formula (b1).

(R ^b1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group;
n1 is an integer of 0 to 4,
n2 is 0 or 1,
R ^b2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent,
R ^b3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

In the formula (b1), R ^b1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when R ^b1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, Examples include an amino group substituted with an mino group, 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When n1 is an integer of 2 or more and 4 or less, R ^b1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent that the substituent further has.

When R ^b1 is an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Further, when R ^b1 is an alkyl group, it may be linear or branched. Specific examples in the case where R ^b1 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^b1 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^b1 is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Further, when R ^b1 is an alkoxy group, it may be linear or branched. Specific examples when R ^b1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^b1 is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^b1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples of when R ^b1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples in the case where R ^b1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and the like.

When R ^b1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when R ^b1 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^b1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^b1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^b1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ^b1 is a phenylalkyl group, the number of carbon atoms is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When R ^b1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples in the case where R ^b1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of when R ^b1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ^b1 is a phenylalkyl group or a naphthylalkyl group, R ^b1 may further have a substituent on the phenyl group or naphthyl group.

When R ^b1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^b1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^b1 is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. A saturated aliphatic acyl group having 2 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted benzoyl group, and an optionally substituted carbon atom having 7 or more carbon atoms A phenylalkyl group having 20 or less, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and Heterocyclyl group etc. are mentioned. Specific examples of these suitable organic groups are the same as those for R ^b1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b1 further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms A monoalkylamino group having a dialkylamino group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^b1 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^b1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^b1 , an alkyl group having 1 to 6 carbon atoms, 1 carbon atom, and the like because it is chemically stable, has few steric hindrances, and is easy to synthesize an oxime ester compound. A group selected from the group consisting of an alkoxy group having 6 or less and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferred, an alkyl having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred. .

Position R ^b1 is bonded to the phenyl group, the phenyl group R ^b1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. N1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.

R ^b2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. When R ^b2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^b2 , the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon atom. A cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbon atom A saturated aliphatic acyloxy group of 2 or more and 20 or less, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, and a substituent A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, and a carbon atom having 7 to 20 carbon atoms which may have a substituent An alkenyl group, an optionally substituted naphthyl group, an optionally substituted naphthoxy group, an optionally substituted naphthoyl group, an optionally substituted naphthoxycarbonyl group, A naphthyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent; Examples thereof include a heterocyclylcarbonyl group, an amino group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. .

When R ^b2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cyclohexane having 3 to 10 carbon atoms. An alkyl group, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted phenyl group, and an optionally substituted benzoyl group A phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, and a substituent. A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl which may have a substituent And a heterocyclylcarbonyl group which may have a substituent and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. With respect to an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with one or two organic groups , R ^b1 .

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the phenyl group or the carbazolyl group in R ^b2 further have a substituent include alkyl having 1 to 6 carbon atoms An alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic group having 2 to 7 carbon atoms; Selected from the group consisting of an acyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group. A benzoyl group substituted by a group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; 1 to 6 carbon atoms Examples include dialkylamino groups having the following alkyl groups; morpholin-1-yl groups; piperazin-1-yl groups; halogens; nitro groups; When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the phenyl group or carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1 or more and 4 or less are preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^b2 , a group represented by the following formula (b2) or (b3) is preferable, and a group represented by the following formula (b2) is more preferable from the viewpoint of easily obtaining a photopolymerization initiator having excellent sensitivity. A group represented by the following formula (b2) in which A is S is particularly preferable.

（Ｒ^ｂ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０以上４以下の整数である。）

(R ^b4 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, A is S or O, and n3 is an integer of 0 or more and 4 or less. .)

（Ｒ^ｂ５及びＲ^ｂ６は、それぞれ、１価の有機基である。）

(R ^b5 and R ^b6 are each a monovalent organic group.)

When R ^b4 in the formula (b2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. In the formula (b2), when R ^b4 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and an alkoxy group having 2 to 7 carbon atoms. Saturated aliphatic acyl group; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of the following alkyl groups, morpholin-1-yl group, piperazin-1-yl group, and phenyl group; mono having an alkyl group having 1 to 6 carbon atoms Alkylamino group; dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl group; piperazin-1-yl group; halogen A nitro group; a cyano group;

In R ^b4 , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group A nitro group, a benzoyl group; a naphthoyl group; a 2-methylphenylcarbonyl group; a 4- (piperazin-1-yl) phenylcarbonyl group; and a 4- (phenyl) phenylcarbonyl group.

In the formula (b2), n3 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. If n3 is 1, binding position of R ^b4, relative bond which the phenyl group R ^b4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

R ^b5 in formula (b3) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferred examples of R ^b5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 carbon atoms. 20 or less or less alkoxycarbonyl group, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted A phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent; Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^b5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^b6 in formula (b3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of the group suitable as R ^b6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. And a heterocyclyl group which may be used. Among these groups, R ^b6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b4 , R ^b5 , or R ^b6 further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, 1 carbon atom An alkoxy group having 6 or less carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, carbon atoms A monoalkylamino group having 1 to 6 alkyl groups, a dialkylamino group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and A cyano group etc. are mentioned. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b4 , R ^b5 , or R ^b6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, 1 or more and 4 or less are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b4 , R ^b5 , or R ^b6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^b3 in formula (b1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^b3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

Among the oxime ester compounds represented by the formula (b1), the following PI-1 to PI-42 are particularly preferable compounds.

A compound having the following structure is also preferable as the oxime ester compound represented by the formula (b1). A compound having the following structure is commercially available as NCI-831 (manufactured by ADEKA).

  Moreover, the oxime ester compound represented by a following formula (b4) is also preferable as a photoinitiator.

（Ｒ^ｂ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｂ８及びＲ^ｂ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｂ８とＲ^ｂ９とは相互に結合して環を形成してもよく、Ｒ^ｂ１０は１価の有機基であり、Ｒ^ｂ１１は、水素原子、置換基を有してもよい炭素原子数１以上１１以下のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０以上４以下の整数であり、ｎ５は０又は１である。）

(R ^b7 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^b8 and R ^b9 are each a chain alkyl group which may have a substituent, or a cyclic organic which may have a substituent. R ^b8 and R ^b9 may be bonded to each other to form a ring, R ^b10 is a monovalent organic group, R ^b11 has a hydrogen atom and a substituent. An alkyl group having 1 to 11 carbon atoms, or an aryl group which may have a substituent, n4 is an integer of 0 to 4 and n5 is 0 or 1.)

  Here, as the oxime compound for producing the oxime ester compound of the formula (b4), a compound represented by the following formula (b5) is suitable.

（Ｒ^ｂ７、Ｒ^ｂ８、Ｒ^ｂ９、Ｒ^ｂ１０、ｎ４、及びｎ５は、式（ｂ４）と同様である。）

(R ^b7 , R ^b8 , R ^b9 , R ^b10 , n4, and n5 are the same as in the formula (b4).)

In formulas (b4) and (b5), R ^b7 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^b7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _n5 — on the fluorene ring in the formula (b4). In formula (b4), the bonding position of R ^{b7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (b4) has one or more R ^b7 , one of the one or more R ^b7 is a fluorene ring because synthesis of the compound represented by the formula (b4) is easy. Bonding at the 2-position is preferable. If R ^b7 is plural, R ^b7 may be different even in the same.

When R ^b7 is an organic group, R ^b7 is not particularly limited as long as the object of the present invention is not ^{impaired, and} is appropriately selected from various organic groups. Preferred examples when R ^b7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, Examples include a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^b7 is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ^b7 is an alkyl group, it may be linear or branched. Specific examples when R ^b7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^b7 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^b7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Further, when R ^b7 is an alkoxy group, it may be linear or branched. Specific examples when R ^b7 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^b7 is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^b7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. Specific examples when R ^b7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^b7 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^b7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the saturated aliphatic acyl group or the saturated aliphatic acyloxy group preferably has 2 to 21 carbon atoms, and more preferably 2 to 7 carbon atoms. Specific examples when R ^b7 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^b7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^b7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^b7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ^b7 is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. When R ^b7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less. Specific examples when R ^b7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ^b7 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ^b7 is a phenylalkyl group or a naphthylalkyl group, R ^b7 may further have a substituent on the phenyl group or naphthyl group.

When R ^b7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, or such monocycles are fused with each other or with such a monocycle and a benzene ring. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done. When R ^b7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^b7 is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R ^b7 is a heterocyclyl group.

When R ^b7 is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, A saturated aliphatic acyl group having 2 to 21 carbon atoms, an optionally substituted phenyl group, an optionally substituted benzoyl group, and an optionally substituted carbon atom having 7 to 20 carbon atoms; The following phenylalkyl groups, naphthyl groups which may have substituents, naphthyl groups which may have substituents, naphthylalkyl groups having 11 to 20 carbon atoms which may have substituents, and heterocyclyl Groups and the like. Specific examples of these suitable organic groups are the same as those for R ^b7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

^Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b7 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms A monoalkylamino group having a dialkylamino group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^b7 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^b7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^b7 is preferably a nitro group or a group represented by R ^b12 —CO— because the sensitivity tends to be improved. R ^b12 is not particularly limited as long as the object of the present invention is not ^impaired , and can be selected from various organic groups. Examples of a group suitable as R ^b12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. The heterocyclyl group which may be sufficient is mentioned. Among these groups, ^Rb12 is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group.
Moreover, it is preferable that R ^b7 is a hydrogen atom because transparency tends to be good. When R ^b7 is a hydrogen atom and R ^b10 is a group represented by the following formula (b4a) or (b4b), the transparency tends to be better.

In formula (b4), R ^b8 and R ^b9 each represent a chain alkyl group that may have a substituent, a cyclic organic group that may have a substituent, or a hydrogen atom. R ^b8 and R ^b9 may be bonded to each other to form a ring. Among these groups, R ^b8 and R ^b9 are preferably chain alkyl groups which may have a substituent. When R ^b8 and R ^b9 are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ^b8 and R ^b9 are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more, 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. preferable. Specific examples in the case where R ^b8 and R ^b9 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Group, isononyl group, n-decyl group, isodecyl group and the like. When R ^b8 and R ^b9 are alkyl groups, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^b8 and R ^b9 are a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. . In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples when R ^b7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferred examples when R ^b7 is a heterocyclyl group. When R ^b7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

  When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When R ^b8 and R ^b9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^b8 and R ^b9 are cyclic organic groups, the substituent that the cyclic organic group may have is the same as in the case where R ^b8 and R ^b9 are chain alkyl groups.

When R ^b8 and R ^b9 are aromatic hydrocarbon groups, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond? A group formed by condensation of a plurality of benzene rings is preferred. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^b8 and R ^b9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ^b8 and R ^b9 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles and a benzene ring. And a condensed heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done.

R ^b8 and R ^b9 may be bonded to each other to form a ring. The group formed by the ring formed by R ^b8 and R ^b9 is preferably a cycloalkylidene group. When R ^b8 and R ^b9 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, and more preferably a 5-membered ring.

When the group formed by combining R ^b8 and R ^b9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine A ring, a pyrazine ring, and a pyrimidine ring.

Examples of suitable groups among R ^b8 and R ^b9 described above include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the linear alkylene group for A ¹ is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ^b8 and R ^b9 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that R ^b8 and R ^b9 have as a substituent.

Preferred specific examples of R ^b8 and R ^b9 include an alkyl group such as an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n − Cyanoalkyl groups such as an nyl group, a 6-cyano-n-hexyl group, a 7-cyano-n-heptyl group, and an 8-cyano-n-octyl group; a 2-phenylethyl group, a 3-phenyl-n-propyl group Phenylalkyl such as 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group Groups: 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n- Heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopent Cycloalkylalkyl groups such as ru-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n -Pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxy Alkoxycarbonylalkyl groups such as rubonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro -N-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo -N-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoro Examples thereof include a propyl group and a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among R ^b8 and R ^b9 , preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta A fluoro-n-pentyl group;

Examples of suitable organic groups for R ^b10 are the same as R ^b7 , alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, substituents. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent Group, an optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ^b7 . R ^b10 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ^b7 may have.

Among organic groups, as R ^b10 , an alkyl group, a cycloalkyl group, an ^optionally substituted phenyl group, or a cycloalkylalkyl group, or an optionally substituted phenylthio group on an aromatic ring. Alkyl groups are preferred. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

Further, as R ^b10 , a group represented by —A ³ —CO—O—A ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

Preferable examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl. Group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Preferred examples of the group represented by —A ³ —CO—O—A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl -n- propyl group, and 3-phenoxycarbonyl -n- propyl group and the like.

（式（ｂ４ａ）及び（ｂ４ｂ）中、Ｒ^ｂ１３及びＲ^ｂ１４はそれぞれ有機基であり、ｎ６は０以上４以下の整数であり、Ｒ^ｂ１３及びＲ^ｂ１４がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｂ１３とＲ^ｂ１４とが互いに結合して環を形成してもよく、ｎ７は１以上８以下の整数であり、ｎ８は１以上５以下の整数であり、ｎ９は０以上（ｎ８＋３）以下の整数であり、Ｒ^ｂ１５は有機基である。） ^Having described ^{R b10,} as the ^{R b10,} preferably a group represented by the following formula (b4a) or (B4b).

(In the formula (b4a) and ^{(b4b), R b13} and ^{R b14} are each an organic group, n6 is an integer from 0 to 4 ^{inclusive, R b13} and ^{R b14} are present in adjacent positions on the benzene ring In this case, R ^b13 and R ^b14 may combine with each other to form a ring, n7 is an integer of 1 to 8, n8 is an integer of 1 to 5, and n9 is 0 or more (n8 + 3). (It is the following integer, and R ^b15 is an organic group.)

Examples of the organic groups for ^{R b13} and ^{R b14} in the formula (b4a) ^is the same as ^{R b7.} R ^b13 is preferably an alkyl group or a phenyl group. When R ^b13 is an alkyl group, the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, and most preferably 1. That is, R ^b13 is most preferably a methyl group. When R ^b13 and R ^b14 are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. A group represented by the formula ^(b4a), preferred examples of the groups and ^{R b13} and ^{R b14} form a ring, and naphthalene-1-yl group, 1,2,3,4 And tetrahydronaphthalen-5-yl group. In the above formula (b4a), n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

In the above formula (b4b), R ^b15 is an organic group. ^Examples of the organic group include the same groups as those described for R ^b7 . Of the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As R ^b15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

  In the formula (b4b), n8 is an integer of 1 to 5, preferably 1 to 3, and more preferably 1 or 2. In the above formula (b4b), n9 is 0 or more (n8 + 3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (b4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (b4), R ^b11 represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be present when R ^b11 is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that R ^b7 may have when it is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (b4), ^Rb11 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, or the like. Among these, a methyl group or a phenyl group is more preferable.

Preferable specific examples of the compound represented by the formula (b4) include the following PI-43 to PI-83.

  (B) Content of a photoinitiator is 0.5 mass% or more and 30 mass% or less with respect to the mass (whole solid content) of the photosensitive composition except the mass of the (S) organic solvent mentioned later. It is preferably 1% by mass or more and 20% by mass or less. (B) By making content of a photoinitiator into said range, the photosensitive composition which cannot produce the defect of a pattern shape easily can be obtained.

  Moreover, you may combine a photoinitiator adjuvant with the (B) photoinitiator. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2- Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetra-mercapto acetate, thiol compounds such as 3-mercapto propionate. These photoinitiation assistants can be used alone or in combination of two or more.

<(C) Carbon black>
The photosensitive composition contains (C) carbon black as a light shielding material. The content of (C) carbon black in the photosensitive composition is 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more in the total solid content of the photosensitive composition. When the photosensitive composition contains (C) carbon black in such an amount, a cured film having excellent light shielding properties can be formed.
(C) Although the upper limit of content of carbon black is not specifically limited, 75 mass% or less is preferable in the total solid of a photosensitive composition, 70 mass% or less is more preferable, and 60 mass% or less is especially preferable.

  The type of carbon black is not particularly limited. As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, lamp black, can be used, for example. Resin-coated carbon black may also be used.

  As the carbon black, carbon black subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity according to the Bronsted definition. Specific examples of the acidic group include a carboxy group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into the carbon black may form a salt. The cation that forms a salt with the acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ion, potassium ion, lithium ion, and ammonium ion are preferable.

  Among the carbon blacks that have been treated to introduce acidic groups as described above, in view of achieving high resistance of a light-shielding cured film formed using the photosensitive composition, a carboxylic acid group or a carboxylic acid group is used. Carbon black having at least one functional group selected from the group consisting of sulfonic acid groups and sulfonic acid groups is preferred.

The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using sulfite, bisulfite, or the like.
2) A method of diazo coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method of performing deprotection after performing a Friedel-Crafts reaction on carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

  Among these methods, the method 2) is preferred because the acidic group introduction treatment is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzene sulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

  The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. The number of moles of acidic groups introduced into carbon black is preferably 1 mmol or more and 200 mmol or less, and more preferably 5 mmol or more and 100 mmol or less with respect to 100 g of carbon black.

Carbon black introduced with acidic groups may be coated with a resin.
When a photosensitive composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. In addition, the bad influence with respect to the dielectric constant of the light-shielding cured film formed using a photosensitive composition does not produce especially by the coating process by resin. Examples of resins that can be used to coat carbon black include thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, poly Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1% by mass or more and 30% by mass or less with respect to the total of the mass of the carbon black and the mass of the resin.

In order to uniformly disperse (C) carbon black described above in the photosensitive composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. Among these, it is preferable to use an acrylic resin dispersant.
In addition, corrosive gas caused by the dispersant may be generated from the cured film. For this reason, it is also an example of a preferable aspect that (C) carbon black is dispersed without using a dispersant.

(C) The carbon black is preferably added to the photosensitive composition after preparing a dispersion in which the carbon black is dispersed at an appropriate concentration in the presence or absence of a dispersant.
In addition, in this specification, it can define as a value also including this dispersing agent about the usage-amount of the above-mentioned (C) carbon black.

<(C ') Other light shielding agent>
The photosensitive composition may contain (C ′) other light shielding agent other than (C) carbon black, together with (C) carbon black.

  (C ') As other light-shielding agents, for example, perylene pigments can be used. Specific examples of the perylene pigment include the perylene pigment represented by the following formula (c-1), the perylene pigment represented by the following formula (c-2), and the following formula (c-3). Perylene pigments. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

式（ｃ−１）中、Ｒ^ｃ１及びＲ^ｃ２は、それぞれ独立に炭素原子数１以上３以下のアルキレン基を表し、Ｒ^ｃ３及びＲ^ｃ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In formula (c-1), R ^c1 and R ^c2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^c3 and R ^c4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, Or represents an acetyl group.

式（ｃ−２）中、Ｒ^ｃ５及びＲ^ｃ６は、それぞれ独立に、炭素原子数１以上７以下のアルキレン基を表す。

In formula (c-2), R ^c5 and R ^c6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｃ−３）中、Ｒ^ｃ７及びＲ^ｃ８は、それぞれ独立に、水素原子、炭素原子数１以上２２以下のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｃ７及びＲ^ｃ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (c-3), R ^c7 and R ^c8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and containing a heteroatom of N, O, S, or P. Also good. When R ^c7 and R ^c8 are alkyl groups, the alkyl group may be linear or branched.

  Examples of the compound represented by the above formula (c-1), the compound represented by the formula (c-2), and the compound represented by the formula (c-3) include, for example, JP-A-62-17353. Can be synthesized using the method described in JP-B 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

  In order to satisfactorily disperse the perylene pigment in the photosensitive composition, the average particle size of the perylene pigment is preferably 10 nm or more and 1000 nm or less.

  In addition, as the (C ′) other light-shielding agent, a lactam pigment may be included. As a lactam pigment, the compound represented by a following formula (c-4) is mentioned, for example.

In formula (c-4), ^Xc represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and ^Rc9 each independently represents a hydrogen atom, a methyl group, a nitro group, or methoxy. Group, a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, R ^c10 independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ^c11 each independently represents a hydrogen atom. Represents a methyl group or a chlorine atom.
The compound represented by Formula (c-4) can be used alone or in combination of two or more.
R ^c9 is preferably bonded to the 6-position of the dihydroindolone ring from the viewpoint of easy production of the compound represented by formula (c-4), and R ^c11 is bonded to the 4-position of the dihydroindolone ring. It is preferable to do this. From the same viewpoint, R ^c9 , R ^c10 , and R ^c11 are preferably hydrogen atoms.
The compound represented by the formula (c-4) has EE, ZZ, and EZ isomers as geometric isomers, and may be any one of these compounds, or these geometric isomers. It may be a mixture of
The compound represented by the formula (c-4) can be produced, for example, by the methods described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

  In order to satisfactorily disperse the lactam pigment in the photosensitive composition, the average particle size of the lactam pigment is preferably 10 nm to 1000 nm.

Furthermore, (C ′) fine particles containing silver tin (AgSn) alloy as a main component (hereinafter referred to as “AgSn alloy fine particles”) can be used as other light shielding agents. The AgSn alloy fine particles may be composed mainly of an AgSn alloy, and may contain, for example, Ni, Pd, Au, etc. as other metal components.
The average particle diameter of the AgSn alloy fine particles is preferably 1 nm to 300 nm.

When the AgSn alloy is represented by the chemical formula AgxSn, the x range in which a chemically stable AgSn alloy is obtained is 1 ≦ x ≦ 10, and the x range in which chemical stability and blackness are simultaneously obtained is 3 ≦ x ≦ 4.
Here, when the mass ratio of Ag in the AgSn alloy is determined in the range of x,
When x = 1, Ag / AgSn = 0.4762
In the case of x = 3, 3 · Ag / Ag3Sn = 0.7317
When x = 4, 4 · Ag / Ag4Sn = 0.7843
When x = 10, 10 · Ag / Ag10Sn = 0.008
It becomes.
Therefore, this AgSn alloy becomes chemically stable when Ag is contained in an amount of 47.6% to 90% by mass, and when Ag is contained in an amount of 73.17% to 78.43% by mass, Chemical stability and blackness can be obtained effectively with respect to the amount.

  The AgSn alloy fine particles can be produced using a normal fine particle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze drying method, and a hydrothermal synthesis method.

Although the AgSn alloy fine particles have high insulation properties, depending on the application of the photosensitive composition, the surface may be covered with an insulating film in order to further improve the insulation properties. As a material for such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, an insulating metal oxide such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), etc. is preferably used. It is done.
In addition, as the organic polymer compound, an insulating resin such as polyimide, polyether, polyacrylate, polyamine compound, or the like is preferably used.

The thickness of the insulating film is preferably 1 nm or more and 100 nm or less, and more preferably 5 nm or more and 50 nm or less in order to sufficiently enhance the surface insulation of the AgSn alloy fine particles.
The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable because an insulating film having a uniform thickness can be formed at a relatively low temperature.

(C ′) As the other light-shielding agent, the above-described perylene pigment, lactam pigment, AgSn alloy fine particles may be used alone, or a combination thereof may be used.
In addition, the black pigment may contain a pigment having a hue such as red, blue, green, and yellow for the purpose of adjusting the color tone. The pigment of the other hue of the black pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as a pigment having another hue of a black pigment. The amount of the pigment having another hue of the black pigment used is preferably 15% by mass or less, and more preferably 10% by mass or less based on the total mass of the black pigment.

In the photosensitive composition, a dye may be further combined with (C) carbon black or a combination of (C) carbon black and (C ′) another light-shielding agent. This dye may be appropriately selected from known materials.
Examples of the dye applicable to the photosensitive composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. be able to.
Moreover, about these dyes, it can disperse | distribute to an organic solvent etc. by rake-forming (chlorination), and this can be used as a (D) coloring agent.
In addition to these dyes, for example, JP 2013-225132 A, JP 2014-178477 A, JP 2013-137543 A, JP 2011-38085 A, JP 2014-197206 A, and the like. The dyes described can also be preferably used.

  The content of (C ′) other light shielding agent is not particularly limited as long as the object of the present invention is not impaired. The content of (C ′) other light-shielding agent is such that the total amount of (C) carbon black and (C ′) other light-shielding agent is 75% by mass or less in the total solid content of the photosensitive composition. An amount of 70% by mass or less is more preferable, and an amount of 60% by mass or less is particularly preferable.

<(D) Binder resin>
The photosensitive composition may contain (D) binder resin. (D) The binder resin may be an alkali-soluble resin soluble in a basic solution or a resin insoluble in a basic solution, and preferably contains an alkali-soluble resin.

  (D) The resin insoluble in the basic solution that can be used as the binder resin is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the resin insoluble in the basic solution include, for example, a homopolymer or copolymer of an acrylate ester represented by methyl (meth) acrylate.

(D) The alkali-soluble resin that is preferably used as the binder resin will be described.
Here, in this specification, the alkali-soluble resin refers to a resin having a functional group (for example, a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, etc.) having alkali solubility in the molecule.

Examples of the resin suitable as the alkali-soluble resin include (D1) a resin having a cardo structure (hereinafter also referred to as “(D1) cardo resin”).
When a resin having a (D1) cardo structure is used as the alkali-soluble resin, it is easy to obtain a photosensitive composition having excellent resolution, and it is easy to form a cured film that does not flow excessively by heating using the photosensitive composition.

[(D1) resin having cardo structure]
(D1) As the resin having a cardo structure, a resin having a cardo skeleton in the structure and having a predetermined alkali solubility can be used. The cardo skeleton refers to a skeleton in which a second ring structure and a third ring structure are bonded to one ring carbon atom constituting the first ring structure. The second annular structure and the third annular structure may be the same structure or different structures.
A typical example of a cardo skeleton is a skeleton in which two aromatic rings (for example, a benzene ring) are bonded to the 9-position carbon atom of a fluorene ring.

  (D1) The cardo resin is not particularly limited, and a conventionally known resin can be used. Among these, a resin represented by the following formula (d-1) is preferable.

In formula (d-1), ^Xd represents a group represented by the following formula (d-2). m1 represents an integer of 0 or more and 20 or less.

In the formula (d-2), R ^d1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^d2 independently represents a hydrogen atom or a methyl group. R ^d3 independently represents a linear or branched alkylene group, m2 represents 0 or 1, and W ^d represents a group represented by the following formula (d-3).

In formula (d-2), R ^d3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 6 carbon atoms. Are particularly preferred, with ethane-1,2-diyl, propane-1,2-diyl and propane 1,3-diyl being most preferred.

Ring A ^d in the formula (d-3) shows the aliphatic ring optionally having an aromatic ring condensed with even well substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.
Specific examples include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The aromatic ring that may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, a benzene ring and a naphthalene ring are preferable.

Preferable examples of the divalent group represented by the formula (d-3) include the following groups.

The divalent group X ^d in the formula (d-1) is obtained by reacting a tetracarboxylic dianhydride that gives a residue Z ^d with a diol compound represented by the following formula (d-2a) ( D1) Introduced into cardo resin.

In formula (d-2a), R ^d1 , R ^d2 , R ^d3 , and m2 are as described for formula (d-2). For ring ^{A d} in the formula (d-2a), it is as described for formula (d-3).

The diol compound represented by the formula (d-2a) can be produced, for example, by the following method.
First, after substituting the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (d-2b) with a group represented by —R ^d3 —OH according to a conventional method, if necessary, An epoxy compound represented by the following formula (d-2c) is obtained by glycidylation using epichlorohydrin or the like.
Next, the diol compound represented by the formula (d-2a) is obtained by reacting the epoxy compound represented by the formula (d-2c) with acrylic acid or methacrylic acid.
In formula (d-2b) and formula (d-2c), R ^d1 , R ^d3 , and m2 are as described for formula (d-2). For ring ^{A d} in the formula (d-2b) and Formula (d-2c), it is as described for formula (d-3).
In addition, the manufacturing method of the diol compound represented by Formula (d-2a) is not limited to said method.

Preferable examples of the diol compound represented by the formula (d-2b) include the following diol compounds.

In the above formula (d-1), R ^d0 is a hydrogen atom or a group represented by —CO—Y ^d —COOH. Here, ^{Y d} represents the residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-). Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(d-1), Z d represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (d-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride Products, biphenyl ether tetracarboxylic dianhydride and the like.
Moreover, in said formula (d-1), m1 shows the integer of 0-20.

（式（ｄ−４）中、Ｒ^ｄ４、Ｒ^ｄ５、及びＲ^ｄ６は、それぞれ独立に、水素原子、炭素原子数１以上１０以下のアルキル基及びフッ素原子からなる群より選択される１種を示し、ｍ３は、０以上１２以下の整数を示す。）

(In Formula (d-4), R ^d4 , R ^d5 , and R ^d6 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom. M3 represents an integer of 0 or more and 12 or less.)

The alkyl group that can be selected as R ^{d4 in} formula (d-4) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms included in the alkyl group within this range, the heat resistance of the resulting carboxylic acid ester can be further improved. When R ^d4 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 4 or less, from the viewpoint of easily obtaining a cardo resin excellent in heat resistance. 1 to 3 is particularly preferable.
When R ^d4 is an alkyl group, the alkyl group may be linear or branched.

R ^{d4 in} formula (d-4) is more preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, from the viewpoint of easily obtaining a cardo resin having excellent heat resistance. R ^{d4 in} formula (d-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.
The plurality of R ^d4 in the formula (d-4) are preferably the same group because preparation of a highly pure tetracarboxylic dianhydride is easy.

M3 in Formula (d-4) represents an integer of 0 or more and 12 or less. By making the value of m3 12 or less, purification of tetracarboxylic dianhydride can be facilitated.
In view of easy purification of tetracarboxylic dianhydride, the upper limit of m3 is preferably 5, and more preferably 3.
From the viewpoint of the chemical stability of tetracarboxylic dianhydride, the lower limit of m3 is preferably 1, and more preferably 2.
M3 in formula (d-4) is particularly preferably 2 or 3.

The alkyl group having 1 to 10 carbon atoms that can be selected as R ^d5 and R ^{d6 in} formula (d-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as R ^d4. .
R ^d5 and R ^d6 are each a hydrogen atom or 1 to 10 carbon atoms (preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, from the viewpoint that purification of tetracarboxylic dianhydride is easy. More preferably, it is an alkyl group of 1 or more and 4 or less, particularly preferably 1 or more and 3 or less, and particularly preferably a hydrogen atom or a methyl group.

  Examples of the tetracarboxylic dianhydride represented by the formula (d-4) include norbornane-2-spiro-α-cyclopentanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride (also known as “norbornane-2-spiro-2′-cyclopentanone-5′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -Tetracarboxylic dianhydride "), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2 ''-(methylnorbornane) -5,5 '', 6,6 ''-tetra Carboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride (also known as “norbornane- 2-spiro-2'-siku Hexanone-6′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride ”), methylnorbornane-2-spiro-α-cyclohexanone-α′-spiro- 2 ″-(methylnorbornane) -5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α′-spiro-2 ″ -norbornane -5,5 '', 6,6 ''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 '' -Tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride Product, norbornane-2- Pyro-α-cyclooctanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α ′ Spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α′-spiro-2 ″ -norbornane-5 , 5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 '' -Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride Thing, norbornane-2-spiro -Α-cyclotridecanone-α'-spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclotetradecanone- α′-spiro-2 ″ -norbornane-5,5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α′-spiro-2 ′ '-Norbornane-5,5' ', 6,6' '-tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclopentanone) -α'-spiro-2' '-norbornane-5 , 5 ″, 6,6 ″ -tetracarboxylic dianhydride, norbornane-2-spiro-α- (methylcyclohexanone) -α′-spiro-2 ″ -norbornane-5,5 ″, 6 6 ''-tetracarboxylic dianhydride Etc. The.

  (D1) The weight average molecular weight of the cardo resin is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, and further preferably 2000 or more and 10,000 or less. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

[(D2) acrylic resin]
In addition to (D1) cardo resin, (D2) acrylic resin can be suitably used as the alkali-soluble resin. (D2) As acrylic resin, what contains the structural unit derived from (meth) acrylic acid and / or the structural unit derived from other monomers, such as (meth) acrylic acid ester, can be used. (Meth) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylic acid ester is represented by the following formula (d-5), and is not particularly limited as long as the object of the present invention is not impaired.

In the above formula (d-5), R ^d7 is a hydrogen atom or a methyl group, and R ^d8 is a monovalent organic group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

The substituent other than the hydrocarbon group in the organic group of R ^d8 is not particularly limited as long as the effect of the present invention is not impaired, and is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, or a cyanato group. , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxy group, carboxylate group, acyl group, acyloxy group, sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, hydroxyimino group, alkyl ether group, an alkyl thioether group, an aryl ether group, aryl thioether group, an amino group (-NH _2, -NHR, -NRR ': R and R 'Each independently represents a hydrocarbon group). The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

R ^d8 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. When these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

  When the alkyl group is linear or branched, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec -Pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, An isodecyl group etc. are mentioned.

  When the alkyl group is an alicyclic group or a group containing an alicyclic group, suitable alicyclic groups contained in the alkyl group include a monocyclic alicyclic group such as a cyclopentyl group and a cyclohexyl group, And an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Moreover, (D2) acrylic resin may be obtained by polymerizing monomers other than (meth) acrylic acid ester. Examples of such monomers include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These monomers can be used alone or in combination of two or more.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether. Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenyl Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  (D2) The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from another monomer in the acrylic resin are not particularly limited as long as the object of the present invention is not impaired. (D2) The amount of the structural unit derived from (meth) acrylic acid in the acrylic resin is preferably 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 30% by mass or less with respect to the mass of the acrylic resin. Is more preferable.

  (D2) The weight average molecular weight of the acrylic resin is preferably 2000 or more and 50000 or less, and more preferably 5000 or more and 30000 or less. By setting it as the above range, there is a tendency that the film forming ability of the photosensitive composition and the developability after exposure are easily balanced.

[(D3) Novolac resin)]
As the alkali-soluble resin, (D3) novolak resin can also be preferably used.
(D3) As the novolak resin, various novolak resins conventionally blended in photosensitive resin compositions can be used. (D3) The novolak resin is preferably one obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst.

(Phenols)
(D3) Examples of phenols used in producing the novolak resin include phenol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2 Xylenols such as 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol; 2-isopropyl Alkylphenols such as phenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; 2,3,5-trimethylphenol, and 3,4,5 -Trimethylphe Trialkylphenols such as alcohol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phloroglicinol; alkyl polyphenols such as alkylresorcin, alkylcatechol, and alkylhydroquinone (any The alkyl group also has 1 to 4 carbon atoms.); Α-naphthol; β-naphthol; hydroxydiphenyl; These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol and p-cresol are preferable, and it is more preferable to use m-cresol and p-cresol in combination. In this case, various characteristics such as heat resistance of the cured film formed using the photosensitive composition can be adjusted by adjusting the blending ratio of the two.
The blending ratio of m-cresol and p-cresol is not particularly limited, but the molar ratio of m-cresol / p-cresol is preferably 3/7 or more and 8/2 or less. By using m-cresol and p-cresol in such a ratio, it is easy to obtain a photosensitive composition capable of forming a cured film having excellent heat resistance.

Moreover, the novolak resin manufactured combining m-cresol and 2,3,5-trimethylphenol is also preferable. When such a novolak resin is used, it is particularly easy to obtain a photosensitive composition that can form a cured film that hardly flows excessively by heating during post-baking.
The blending ratio of m-cresol and 2,3,5-trimethylphenol is not particularly limited, but the molar ratio of m-cresol / 2,3,5-trimethylphenol is 70/30 or more and 95/5 or less. Is preferred.

(Aldehydes)
(D3) Examples of aldehydes used when producing a novolak resin include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

(Acid catalyst)
(D3) Examples of the acid catalyst used in preparing the novolak resin include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; formic acid, oxalic acid, acetic acid, diethylsulfuric acid, and paratoluene And organic acids such as sulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone or in combination of two or more.

(Molecular weight)
(D3) The polystyrene-reduced weight average molecular weight (Mw; hereinafter, also simply referred to as “weight average molecular weight”) of the novolak resin is from the viewpoint of resistance to flow caused by heating of the cured film formed using the photosensitive composition. The lower limit is preferably 2000, more preferably 5000, particularly preferably 10,000, even more preferably 15000, most preferably 20000, the upper limit is preferably 50000, more preferably 45000, still more preferably 40000, and most preferably 35000.

  (D3) As the novolak resin, those having different weight average molecular weights in terms of polystyrene can be used in combination. By using a combination of different weight average molecular weights, it is possible to balance the developability of the photosensitive composition and the heat resistance of a cured film formed using the photosensitive composition.

  (D) It is preferable that content of binder resin is 10 mass% or more and 65 mass% or less with respect to the mass of the whole solid content of a photosensitive composition, and it is more preferable that it is 15 mass% or more and 50 mass% or less. preferable. By setting it as said range, it is easy to obtain the resin composition excellent in developability.

<(E) Photopolymerizable monomer>
The photosensitive composition may contain (E) a photopolymerizable monomer. The (E) photopolymerizable monomer is a compound having a carbon-carbon double bond that can be polymerized by the action of the (B) photopolymerization initiator, and is particularly limited as long as it is a compound other than the above-described (A) crosslinking component. Not.
Such (E) photopolymerizable monomers include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl Examples include (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (that is, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate), methylenebis (meth) acrylamide, (meth) acrylamide Examples thereof include polyfunctional monomers such as methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

As these (E) photopolymerizable monomers, from the viewpoint of increasing the adhesion of the cured product to the substrate and the strength of the cured product, a polyfunctional monomer having three or more functional groups can be used. The above polyfunctional monomers can be used, and polyfunctional monomers having 5 or more functional groups can be used.
Specifically, when a polyfunctional monomer having five or more functions is used, it is possible to improve the adhesion of the substrate. Typically, dipentaerythritol penta (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate is used.

  (E) Content in the photosensitive composition of a photopolymerizable monomer is not specifically limited in the range which does not inhibit the objective of this invention. However, from the viewpoint of more remarkably expressing the effect of the present invention, the content of the (E) photopolymerizable monomer in the photosensitive composition is 50% by mass or less based on the mass of the (A) crosslinking component. It is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and most preferably 0% by mass.

<(S) Organic solvent>
The photosensitive composition preferably contains (S) an organic solvent for improving coatability and adjusting viscosity.

  (S) Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -N-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono- n-butyl ether, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Ether acetates; Other ethers such as lenglycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate Alkyl lactates such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl -3-Methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate , Ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate etc. Esters; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N, N-diethylacetamide N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-yl Dazorijinon, pyridine, and N, N, N ', N'- tetramethylurea nitrogen-containing polar organic solvent; and the like.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above such as benzyl acetate are more preferred.
Moreover, it is also preferable that the (S) organic solvent contains a nitrogen-containing polar organic solvent in terms of the solubility of each component and (C) the dispersibility of pigments such as carbon black. As the nitrogen-containing polar organic solvent, N, N, N ′, N′-tetramethylurea or the like can be used.
These solvents can be used alone or in combination of two or more.

  The content of the (S) organic solvent is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. The viscosity of the photosensitive composition is preferably 5 cp or more and 500 cp or less, more preferably 10 cp or more and 50 cp or less, and further preferably 20 cp or more and 30 cp or less. Moreover, it is preferable that solid content concentration is 5 to 100 mass%, and it is more preferable that it is 15 to 50 mass%.

<Other ingredients>
The photosensitive composition may contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, an antifoaming agent, and an epoxy compound as necessary. Any additive can be used as the additive.
Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the antifoaming agent include silicone and fluorine. Compounds and the like.

<Method for preparing photosensitive composition>
The photosensitive composition demonstrated above is obtained by mixing each said component each predetermined amount, and mixing uniformly with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become a more uniform thing.

  The cured film formed using the photosensitive composition demonstrated above is excellent in light-shielding property, and is excellent in insulation and the adhesiveness to a board | substrate. For this reason, said photosensitive composition is used suitably in the formation application of the black matrix in the color filter with which the display panel for various display apparatuses is provided.

Since the cured film formed using the photosensitive composition is excellent in insulation and light shielding properties, it is preferably used as a light shielding material for the lead-out wiring in the touch panel. By forming the cured film as a light-shielding material on the lead wiring in the touch panel using the above photosensitive composition, it is difficult to visually recognize the lead wiring from the user side of the touch panel.
For this reason, said photosensitive composition is used suitably in the formation use of the light-shielding material of the lead-out wiring in a touch panel.

The photosensitive composition preferably has a surface resistance value of 1.0 × 10 ¹² Ω / □ or more when a cured film is formed under the following conditions. The following curing conditions are quite severe conditions in which the cured film is exposed to a high temperature for a long time. By using the photosensitive composition, it is possible to form a cured film that has a resistance value that hardly changes even under such severe conditions and that has high reliability in terms of insulation performance.
(Curing conditions)
The photosensitive composition is applied on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 250 ° C. for 300 minutes to obtain a cured film.
Further, the surface resistance value when the cured film is formed under the same conditions is more preferably 1.0 × 10 ¹³ Ω / □ or more, and further preferably 1.0 × 10 ¹⁴ Ω / □ or more. . The upper limit is not particularly limited, but is, for example, 1.0 × 10 ¹⁸ Ω / □ or less.

Furthermore, the photosensitive composition preferably has an optical density of 2.8 / μm or more when a cured film is formed under the following conditions. Thereby, the cured film which has higher light-shielding property is realizable.
(Curing conditions)
The photosensitive composition is coated on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film.
Further, the optical density when the cured film is formed under the same conditions is more preferably 3.0 / μm or more, and further preferably 3.2 / μm or more. Although an upper limit is not specifically limited, For example, it is 5.0 / micrometer or less.

≪Method for producing cured film≫
As a method for producing a cured film, a conventionally known method for producing a cured film using a photosensitive composition containing a photopolymerizable compound can be employed without any particular limitation.

As a suitable manufacturing method of the cured film,
A step of forming a coating film by applying a photosensitive composition;
A step of selectively exposing the coating film;
And a step of developing the exposed coating film.
By such a method, a cured film patterned into a desired shape is formed.
The patterned cured film formed by development may be further baked.

  In addition, although the formation method of the patterned cured film is demonstrated here, naturally by exposing the coating-film whole surface. It is also possible to form a cured film that is not patterned.

  In order to form a cured film using the photosensitive composition, first, the photosensitive composition is applied on a substrate selected according to the use of the cured film to form a coating film. The method for forming the coating film is not particularly limited. For example, the coating film is formed using a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. Is called.

  The applied photosensitive composition is dried as necessary to form a coating film. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at a temperature of 80 ° C. or higher and 120 ° C. or lower, preferably 90 ° C. or higher and 100 ° C. or lower, for 60 seconds or longer and 120 seconds or shorter; Examples include a method of leaving at room temperature for several hours to several days, and (3) a method of removing the solvent by placing it in a warm air heater or infrared heater for several tens of minutes to several hours.

Next, the coating film is exposed. The exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. The exposure is performed position-selectively by, for example, a method of performing exposure through a negative mask. Energy dose to be irradiated may differ depending on the composition of the photosensitive composition, preferably for example, about 40 mJ / cm ² or more 200 mJ / cm ² or less.
When exposure is performed on the entire surface of the coating film, an unpatterned cured film having a shape corresponding to the shape of the coating film is formed.

  When the coating film is exposed in a position-selective manner, the exposed film is developed with a developing solution, whereby the unexposed portion is dissolved and removed in the developing solution to form a patterned cured film. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. The developer is appropriately selected according to the composition of the photosensitive composition. As the developer, for example, a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, or a quaternary ammonium salt can be used.

If desired, the patterned cured film is then baked (post-baked). The baking temperature is not particularly limited, but is preferably 180 ° C. or higher and 250 ° C. or lower, and more preferably 220 ° C. or higher and 230 ° C. or lower. The baking time is typically 10 minutes or longer and 90 minutes or shorter, and preferably 20 minutes or longer and 60 minutes or shorter.
By baking as described above, a cured film of the photosensitive composition can be obtained.

The cured film formed in this way is excellent in light-shielding properties, and excellent in insulation and adhesion to the substrate, so it can be suitably used as a black matrix in color filters provided in display panels for various display devices. Is done.
Moreover, since the cured film formed using said photosensitive composition is excellent in insulation and light-shielding property, it is preferably used as a light-shielding material of the lead-out wiring in a touch panel. By forming the cured film as a light-shielding material on the lead wiring in the touch panel using the above photosensitive composition, it is difficult to visually recognize the lead wiring from the user side of the touch panel.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

In Examples, as (A) crosslinking component (component (A)), (CH ₃ O) SiO _3/2 (T unit) 57 mol% and (CH ₃ ) SiO _3/2 (T unit) 21 mol% And a siloxane compound (weight average molecular weight: 1900) comprising 22 mol% of the following formula (T unit).
Here, (CH ₃ O) SiO _3/2 (T unit) corresponds to the structural unit I described above. Further, (CH ₃ ) SiO _3/2 (T unit) and the unit of the following formula (T unit) correspond to the structural unit II described above.
That is, (A) In the siloxane compound that is a crosslinking component, the value of (molar amount of structural unit I) / (sum of molar amounts of structural unit I, structural unit II, and structural unit III) is 0.57.

  In the comparative example, dipentaerythritol hexaacrylate was used as (E) photopolymerizable monomer ((E) component) instead of (A) the crosslinking component.

In Examples and Comparative Examples, NCI-831 (manufactured by ADEKA) having the following structure was used as the (B) photopolymerizable compound (component (B)).

In Examples and Comparative Examples, a carbon black dispersion (manufactured by Daido Kasei Kogyo Co., Ltd.) was used as (C) carbon black (component (C)).
In addition, in Table 1 of this Example item, the numerical value is described about the total value of solid content of this pigment and a dispersing agent.

  In Examples and Comparative Examples, as D binder resin (component (D)), resin D-1 obtained in Preparation Example 1 below and acrylic binder resin D-2 were used.

[Preparation Example 1]
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula which is a colorless and transparent solid.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin D-1. The disappearance of the acid anhydride group was confirmed by IR spectrum.

[Example 1 and Comparative Example 1]
Each of the components listed in Table 1 and 0.1 part by mass of a fluorosurfactant were dissolved and dispersed in (S) an organic solvent so that the solid content concentration was 19% by mass. The photosensitive composition of the example and the comparative example was obtained. (S) As the organic solvent, a mixed solvent of 30% by mass of 3-methoxybutyl acetate, 20% by mass of cyclohexanone, and 50% by mass of propylene glycol monomethyl ether acetate was used.

About the photosensitive composition of Example 1, the cured film was created according to the following measurement conditions, and the amount of silicon atoms (mass%) and the amount of carbon atoms (mass%) in the surface of the cured film were analyzed. As a result of analysis, the ratio of the amount of silicon atoms (% by mass) / the amount of carbon atoms (% by mass) on the surface of the cured film was 0.11 (average value obtained by measuring three points).
(Measurement condition)
The photosensitive composition was applied on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film. . XPS was measured for the surface of this cured film, the peak area of each element was determined, and the mass ratio of each element was calculated.

Using the obtained photosensitive resin composition, the surface resistance value, the optical density (OD value), and the adhesion were evaluated according to the following methods. These evaluation results are shown in Table 1.
(Surface resistance measurement)
The photosensitive composition was applied on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 250 ° C. for 300 minutes to obtain a cured film. . About the obtained cured film, the surface resistance value was measured.
(Optical density measurement)
The photosensitive composition was applied on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film. . The resulting cured film was measured for optical density.
(Adhesion evaluation)
The photosensitive composition was applied on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film. . About the obtained cured film, it left still for 2 hours on the conditions of temperature: 121 degreeC, humidity: 100%, and pressure: 2 atmosphere, and adhesiveness was evaluated by the cross-cut method (tape test). About this evaluation, it performed based on the evaluation of 0B-5B according to the standard of ASTM D-3359.

According to Table 1, from Example 1, the content of (C) carbon black in the total solid content of the photosensitive composition is 30% by mass or more, and the amount of silicon atoms in the cured product of the photosensitive composition ( (Mass%) / carbon atomic weight (mass%) ratio is 0.05 or more, and a photosensitive composition containing a siloxane compound having a predetermined structure as the crosslinking component (A) has high optical density and surface resistance, It turns out that the cured film which is excellent in the adhesiveness to a board | substrate can be formed.
On the other hand, from Comparative Example 1, the content of (C) carbon black in the total solid content of the photosensitive composition is 30% by mass or more, and (E) a siloxane having a predetermined structure while containing a photopolymerizable monomer When a photosensitive composition containing no compound as the crosslinking component (A) is used, it can be seen that even if a cured film having a high optical density can be formed, only a cured film having low surface resistance and poor adhesion to the substrate can be formed. .

Claims (12)

A photosensitive composition comprising (A) a crosslinking component, (B) a photopolymerization initiator, and (C) carbon black,
The (A) crosslinking component is represented by the following formulas (a1) to (a4):
M unit: R ¹ R ² R ³ SiO _1/2 (a1)
D unit: R ⁴ R ⁵ SiO _2/2 (a2)
T unit: R ⁶ SiO _3/2 (a3)
Q unit: SiO _4/2 (a4)
(In the formulas (a1) to (a4), R ^{1 to} R ⁶ are each independently a group represented by R ⁷ — or R ⁷ —O—, and R ⁷ is a group represented by the formula (a1) to the formula (It is a monovalent organic group bonded to the silicon atom in (a3) by a C—Si bond or bonded to the oxygen atom in R ⁷ —O— by a C—O bond.)
A siloxane compound containing one or more structural units selected from M units, D units, T units, and Q units represented by:
The siloxane compound has two or more carbon-carbon double bonds in its structure, and the siloxane compound contains two or more structural units selected from M units, D units, T units, and Q units. ,
The content of the (C) carbon black in the total solid content of the photosensitive composition is 30% by mass or more,
When the amount of silicon atoms (mass%) and the amount of carbon atoms (mass%) in the cured product of the photosensitive composition are measured under the following measurement conditions, the ratio of silicon atom weight (mass%) / carbon atom weight (mass%) The photosensitive composition whose is 0.05 or more.
(Measurement condition)
The photosensitive composition is coated on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film. XPS is measured on the surface of the cured film, the peak area of each element is obtained, and the mass ratio of each element is calculated.   The photosensitive composition of Claim 1 whose content of the said siloxane compound in the total solid of the said photosensitive composition is 5 mass% or more.   Furthermore, the photosensitive composition of Claim 1 or 2 containing (D) binder resin. The siloxane compound has the following formula (a1a), formula (a2a), formula (a3a), and formula (a4):
(R ⁷ O) ₃ SiO _1/2 ... (A1a)
_{^{(R 7 O) 2 SiO 2/2}} ··· (a2a)
(R ⁷ O) SiO _3/2 (a3a)
SiO _4/2 (a4)
(In Formula (a1a), Formula (a2a), and Formula (a3a), R ⁷ is a monovalent organic group bonded to an oxygen atom in R ⁷ —O— by a C—O bond.)
The photosensitive composition of any one of Claims 1-3 containing the 1 or more types of structural unit I selected from the structural unit represented by these. The siloxane compound further includes the following formula (a1b), formula (a2b), and formula (a3b):
(R ⁷ O) ₂ R ⁷ SiO _1/2 ... (A1b)
(R ⁷ O) R ⁷ SiO _2/2 (a2b)
R ⁷ SiO _3/2 (a3b)
(In formula (a1b), formula (a2b), and formula (a3b), is R ⁷ bonded to the silicon atom in formula (a1b), formula (a2b), and formula (a3b) by a C—Si bond? , R ⁷ —O— is a monovalent organic group bonded to the oxygen atom by a C—O bond.)
One or more structural units II selected from the structural units represented by: and / or the following formulas (a1c) and (a2c):
(R ⁷ O) R ⁷ ₂ SiO _1/2 ... (A1c)
R ⁷ ₂ SiO _2/2 (a2c)
(In Formula (a1c) and Formula (a2c), R ⁷ is bonded to the silicon atom in Formula (a1c) and Formula (a2c) with a C—Si bond, or is bonded to the oxygen atom in R ⁷ —O—. (It is a monovalent organic group bonded by a C—O bond.)
One or more structural units III selected from structural units represented by:
The photosensitivity according to claim 4, wherein a value of (molar amount of structural unit I) / (sum of molar amounts of structural unit I, structural unit II, and structural unit III) in the siloxane compound is 0.25 or more. Composition.   The photosensitive composition of any one of Claims 1-5 used in order to form a black matrix.   The photosensitive composition of any one of Claims 1-5 used in order to form the light-shielding material of the lead-out wiring in a touch panel. The photosensitive composition of any one of Claims 1-7 whose surface resistance value when it is set as a cured film on the following conditions is 1.0 * 10 < ¹² > (omega | ohm) / square or more.
(Curing conditions)
The photosensitive composition is applied on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 250 ° C. for 300 minutes to obtain a cured film. The photosensitive composition of any one of Claims 1-8 whose optical density when it is set as a cured film on the following conditions is 2.8 / micrometer or more.
(Curing conditions)
The photosensitive composition is coated on a glass substrate so as to have a thickness of 1 μm, exposed at an exposure amount of ghi line of 50 mJ / cm ² , and then post-baked at 230 ° C. for 20 minutes to obtain a cured film.   The cured film formed by hardening the photosensitive composition of any one of Claims 1-9.   A display device comprising the cured film according to claim 10. A step of forming a coating film by applying the photosensitive composition according to any one of claims 1 to 9,
Exposing the coating film in a position-selective manner;
Developing the exposed coating film, and forming a patterned cured film.