CN106933032B - Black photosensitive resin composition and its application - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition and its application. The said photosensitive resin composition contains the alkali-soluble resin (A), the compound (B) which has an ethylenically unsaturated group, a photoinitiator (C), a solvent (D), and a black pigment (E). The black pattern formed by the black photosensitive resin composition of the present invention has the advantages of low dielectric constant and good linearity of the high-definition pattern.

Description

Black photosensitive resin composition and its application

technical field

The present invention relates to a black photosensitive resin composition and a black pattern formed by using the black photosensitive resin composition to manufacture color filters and liquid crystal display components; in particular, to provide a black photosensitive resin composition and In its application, the black pattern formed by the black photosensitive resin composition has the advantages of low dielectric constant and good linearity of the high-definition pattern.

Background technique

In recent years, with the vigorous development of various technologies of liquid crystal displays, and in order to improve the contrast ratio and display quality of liquid crystal displays, the color filters in the liquid crystal display are usually placed between stripes and dots. Set the black matrix. The black matrix can prevent defects such as a decrease in contrast ratio and a decrease in color purity caused by light leakage between pixels. In addition, in order to ensure a certain gap (cell gap) between the two substrates (such as a color filter and a TFT substrate), a spacer (spacer) is also used in display devices such as liquid crystal display devices and organic EL display devices. ).

Recently, in response to the further high-definition and high-brightness of color liquid crystal display devices, the industry has proposed active matrix liquid crystal display devices. COA), which is to set the color filter including the black matrix and the pixel layer on the side of the TFT component substrate; (2) the integrated black matrix method (black matrix on array; BOA), which only sets the black matrix on the TFT The module substrate side (refer to Japanese Patent Laid-Open No. 10-206888, Japanese Patent Laid-Open No. 2002-277899, etc.). The above-mentioned method does not need to obtain the edge aligned with the device, and therefore, compared with the general method of forming the black matrix and the pixel layer on the substrate opposite to the TFT device substrate, the aperture ratio can be increased and the brightness can be increased.

In response to this development, Japanese Patent Laid-Open No. 10-114873 and Japanese Patent Laid-Open No. 2002-311232 propose a resin black matrix, which will not cause a short circuit even if the resin black matrix is directly mounted on the TFT component substrate. , and can give a certain volume resistivity. The resin black matrices proposed in these patents use carbon black as a light-shielding component. Carbon black has absorption in a wide area and has very high optical opacity. Therefore, almost all resin black matrices use carbon black as an optical blocking component. However, the photosensitive resin composition used to form this resin black matrix has a dielectric constant. and the defects of poor straightness of high-definition patterns, which reduce the efficiency of the black matrix formed.

On the other hand, Japanese Patent Application Laid-Open No. 2011-170075 proposes that a light-shielding agent such as carbon black can be added to the spacer to obtain a black spacer with light-shielding activity.

A substrate having components formed thereon, such as a TFT substrate, is often used in display devices such as liquid crystal display devices. As far as the TFT substrate is concerned, the black stripe spacers must be formed on the component of the corresponding substrate, or on the component of another substrate opposite to the above-mentioned substrate. In order to consider the height of the component, the height of the black stripe spacer needs to be changed in the part formed by the component or in other parts. The black stripe spacer with different heights can be formed at one time by changing the exposure amount for forming the black stripe spacer. . Preferably, the above method is performed with a half-tone mask.

However, the black spacer obtained from the above-mentioned photosensitive resin composition has poor dielectric constant, and the linearity of the high-definition pattern is poor.

In summary, how to make the black pattern prepared from the black photosensitive resin composition, including the black matrix and the black spacer, have good dielectric constant and high-precision pattern linearity, so as to meet the current requirements of the industry, as follows: The present invention is an object of diligent research in the technical field to which the present invention pertains.

SUMMARY OF THE INVENTION

The present invention provides a black photosensitive resin composition containing a special photoinitiator and a black pigment to obtain a black pattern with a low dielectric constant and a high-definition pattern formed by the black photosensitive resin composition with excellent linearity. .

Therefore, the present invention provides a black photosensitive resin, which comprises:

Alkali-soluble resin (A);

A compound (B) having an ethylenically unsaturated group;

photoinitiator (C);

solvent (D); and

Black Pigment (E),

in:

The photoinitiator (C) comprises a first photoinitiator (C-1) having a structure represented by formula (C-I):

COR₁₆、OR₁₇、卤素、NO₂或

In formula (CI), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl,

COR ₁₆ , OR ₁₇ , halogen, NO ₂ or

取代的C₂-C₁₀烯基；or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other

Substituted C ₂ -C ₁₀ alkenyl;

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together -(CH ₂ ) _p -Y- (CH ₂ ) _q -;

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together

R₉、R₁₀、R₁₁及R₁₂彼此独立地为氢、C₁-C₂₀烷基，该C₁-C₂₀烷基未经取代或经一或多个以下基团取代：卤素、苯基、CN、OH、SH、C₁-C₄-烷氧基、(CO)OH或(CO)O(C₁-C₄烷基)；provided that at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with _one or more of _the following groups: halogen, benzene group, CN, OH, SH, C ₁ -C ₄ -alkoxy, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

COR₁₆或NO₂；or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein these substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ forms a 5- or 6-membered ring with one carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ as appropriate; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are

COR ₁₆ or NO ₂ ;

Y is O, S, _NR or a direct bond;

p is an integer 0, 1, 2, or 3;

q is an integer 1, 2 or 3;

X is CO or direct bond;

R ₁₃ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ or

Or R ₁₃ is C ₂ -C ₂₀ alkyl, which is mixed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO, or C ₂ -C ₁₂ alkenyl, which is uninterrupted or mixed with a or more O, CO, or NR ₂₆ , wherein the intervened C ₂ -C ₂₀ alkyl and the uninterrupted or intervened C ₂ -C ₁₂ alkenyl are unsubstituted or substituted with one or more halogens;

or R ₁₃ is C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl, or C ₃ -C ₁₀ cycloalkyl without or intervening one or more O, S, CO or NR ₂₆ ;

COR₁₆、CN、NO₂、卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、间杂有一或多个O、S、CO或NR_26-的C₂-C₂₀烷基；或其各经C₃-C₁₀环烷基或间杂有一或多个O、S、CO或NR₂₆的C₃-C₁₀环烷基取代；or R ₁₃ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

COR ₁₆ , CN, NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, S, CO or NR _26- ; or Each of which is substituted with C ₃ -C ₁₀ cycloalkyl or C ₃ -C ₁₀ cycloalkyl interspersed with one or more O, S, CO or NR ₂₆ ;

k is an integer from 1 to 10;

R ₁₄ is hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by one or more of the following Group substitution: halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or CN;

or R ₁₄ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, CN, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ;

or R ₁₄ is C ₃ -C ₂₀ heteroaryl, C ₁ -C ₈ alkoxy, benzyloxy or phenoxy, which benzyloxy and phenoxy are unsubstituted or substituted by one or more of the following groups Substituted: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and/or halogen;

R ₁₅ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN , NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, interspersed with one or A plurality of C2- _C20 alkyl groups of O, S, or NR ₂₆ ; or each substituted with _{a C1 - C20} alkyl group that is unsubstituted or substituted with one or more of _the following groups Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl oxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl without or with one or more O, CO or NR ₂₆ ;

苯基；或该C₁-C₂₀烷基是经苯基取代，该苯基是经卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、OR₁₇、SR₁₈或NR₁₉R₂₀取代；or R ₁₅ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ hetero Aryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ ,

phenyl; or the C ₁ -C ₂₀ alkyl is substituted with phenyl, the phenyl is halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ to replace;

Or R ₁₅ is C ₂ -C ₂₀ alkyl, intervening with one or more O, SO or SO ₂ , and the intervening C ₂ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups : halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted by OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is C ₂ -C ₂₀ alkanoyl or benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ unsubstituted or substituted with one or more OR ₁₇ naphthoyl or C ₃ -C ₁₄ heteroarylcarbonyl;

Or R ₁₅ is C ₂ -C ₁₂ alkoxycarbonyl, which is uninterrupted or interspersed with one or more O and the interspersed or uninterrupted C ₂ -C ₁₂ alkoxycarbonyl is unsubstituted or an or multiple hydroxyl substitutions;

or R ₁₅ is phenoxycarbonyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m -C ₁ -C ₆ alkyl, unsubstituted or C ₁ -C ₁₂ alkyl or SO ₂ - _C1 - _C6 alkyl-substituted S(O) _m -phenyl;

or R ₁₅ is SO ₂ O-phenyl, unsubstituted or substituted with C1-C12 alkyl; or diphenylphosphono or bis(C1-C4 alkoxy)-phosphono;

m is 1 or 2;

R' ₁₄ has one of the meanings given for R ₁₄ ;

R' ₁₅ has one of the meanings given for R ₁₅ ;

X ₁ is O, S, SO or SO ₂ ;

X ₂ is O, CO, S or a direct bond;

R ₁₆ is C6-C20 aryl or C3-C20 heteroaryl, each of which is unsubstituted or substituted with one or more of the following: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl interspersed with one or more O, S or NR ₂₆ ; or each substituted with one or more C ₁ -C ₂₀ alkyl, the C ₁ - _C20 alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl , C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₆ is hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with _one or more of _the following: halogen, phenyl, OH, SH, CN, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)- Phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

Or R ₁₆ is a C ₂ -C ₁₂ alkyl group, which is mixed with one or more O, S or NR ₂₆ ;

or R ₁₆ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl;

or R ₁₆ is SR ₁₈ substituted phenyl, wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring of the carbazole moiety to which the COR ₁₆ group is attached;

n is 1 to 20;

R ₁₇ is hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)- (C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ -( C ₁ -C ₄ haloalkyl), O(C ₁ -C ₄ haloalkyl) or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O;

Or R ₁₇ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S or NR ₂₆ ;

or R ₁₇ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkanoyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenoyl or C ₃ -C ₂₀ cycloalkyl without or with one or more O, S, CO or NR ₂₆ ;

or R ₁₇ is C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl, which is uninterrupted or interspersed with one or more O;

or R ₁₇ is benzoyl, which is unsubstituted or substituted with one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy;

or R ₁₇ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N(C ₁ -C ₁₂ alkane base) ₂ , diphenyl-amino or

所处的苯基或萘基环的其中一个碳原子的直接键；or R ₁₇ forms a bond to the group

A direct bond to one of the carbon atoms of the phenyl or naphthyl ring in which it is located;

R ₁₈ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein the C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkane radical or phenyl-C ₁ -C ₃ alkyl is uninterrupted or interspanned with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ;

or R ₁₈ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO) - phenyl or (CO)OR ₁₇ ;

Or R ₁₈ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ;

or R ₁₈ is (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ alkene acyl;

or R ₁₈ is benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkane base thio;

or R ₁₈ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ Haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N( C ₁ -C ₁₂ alkyl) ₂ , diphenylamine, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N(C ₁ - C ₈ alkyl) ₂ or

R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ - C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl, SO ₂ -(C ₁ - C ₄ haloalkyl) or benzoyl;

or R ₁₉ and R ₂₀ are phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzoyl or C ₁ -C ₁₂ alkoxy;

或未经间杂或间杂有一或多个O、S、CO或NR₁₇的C₃-C₂₀环烷基；Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₁₇ , and the 5-membered or 6-membered saturated or unsaturated ring Unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl,

Or C ₃ -C ₂₀ cycloalkyl without or with one or more O, S, CO or NR ₁₇ ;

卤素、NO₂、CN、苯基或未经间杂或间杂有一或多个O、S、CO或NR₁₇的C₃-C₂₀环烷基；or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ ,

halogen, NO ₂ , CN, phenyl or C ₃ -C ₂₀ cycloalkyl without or with one or more O, S, CO or NR ₁₇ ;

R ₂₁ and R ₂₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl;

Or R ₂₁ and R ₂₂ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₂₆ , and the 5-membered or 6-membered saturated or unsaturated ring Not fused or the 5- or 6-membered saturated or unsaturated ring is fused with a benzene ring;

R ₂₃ is hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, CO or NR ₂₆ , uninterrupted or interspersed with O , S, CO or C ₃ -C ₂₀ cycloalkyl of NR ₂₆ , or R ₂₃ is phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₀₈ or NR ₂₁ R ₂₂ ;

R ₂₄ is (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ is one of the meanings given for R ₁₉ and R ₂₀ ;

R ₂₅ is COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₅ is one of the meanings given for R ₁₇ ;

R ₂₆ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, mixed with one or more O or CO; or phenyl-C ₁ -C ₄ alkane radical, C3- _C8cycloalkyl , which is _{uninterrupted} or interspersed with one or more O or CO; or (CO) _R19 ; or phenyl, which is unsubstituted or substituted by one or more of the following Group substitution: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or

或

provided that at least one group is present in the molecule

or

The black pigment (E) comprises a first black pigment (E-1), wherein the first black pigment (E-1) comprises a compound having the formula (E-I), its geometric isomer, its salt or Salts of its geometric isomers:

In formula (EI), R ^1e and R ^6e are independently hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ^2e , R ^3e , R ^4e , R ^5e , R ^7e , R ^8e , R ^9e and R ^10e and all others independently of each other are hydrogen atom, halogen atom, R ^11e , COOH, COOR ^11e , COO-, CONH ₂ , CONHR ^11e , CONR ^11e R ^12e , CN, OH, OR ^11e , COCR ^11e , OOCNH ₂ , OOCNHR ^11e , OOCNR ^11e R ^12e , NO ₂ , NH ₂ , NHR ^11e , NR ^1le R ^12e , NHCOR ^12e , NR ^11e COR ^12e , N=CH ₂ , N=CHR ^11e , N=CR ^11e R ^12e , SH, SR ^11e , SOR ^11e , SO ₂ R ^11e , SO ₃ R ^11e , SO ₃ H, SO ₃ −, SO ₂ NH ₂ , SO ₂ ^{NHR 11e} , or SO ₂ ^{NR 11e} R ^12e ; At least one combination from the group consisting of R ^3e and R ^4e , R ^4e and R ^5e , R ^7e and R ^8e , R ^8e and R ^9e , and R ^9e and R ^10e is a direct bond with each other, or They are bonded to each other through oxygen atom, sulfur atom, NH or NR ^11e bridging; R ^11e and R ^12e are independently each other an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms. Alkenyl, cycloalkenyl having 3 to 12 carbons, or alkynyl having 2 to 12 carbons.

The present invention also provides a black pattern, which is formed by subjecting the aforementioned black photosensitive resin composition to pre-baking treatment, exposure treatment, development treatment and post-baking treatment.

The present invention further provides a liquid crystal display assembly including the aforementioned black pattern.

Detailed ways

The present invention provides a black photosensitive resin, which comprises:

Alkali-soluble resin (A);

A compound (B) having an ethylenically unsaturated group;

photoinitiator (C);

solvent (D); and

Black Pigment (E),

Wherein: the photoinitiator (C) comprises a first photoinitiator (C-1) having a structure represented by formula (C-I):

COR₁₆、OR₁₇、卤素、NO₂或

In formula (CI), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl,

COR ₁₆ , OR ₁₇ , halogen, NO ₂ or

取代的C₂-C₁₀烯基；or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other

Substituted C ₂ -C ₁₀ alkenyl;

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together -(CH ₂ ) _p -Y- (CH ₂ ) _q -;

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together

R₉、R₁₀、R₁₁及R₁₂彼此独立地为氢、C₁-C₂₀烷基，该C₁-C₂₀烷基未经取代或经一或多个以下基团取代：卤素、苯基、CN、OH、SH、C₁-C₄-烷氧基、(CO)OH或(CO)O(C₁-C₄烷基)；provided that at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with _one or more of _the following groups: halogen, benzene group, CN, OH, SH, C ₁ -C ₄ -alkoxy, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein these substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ forms a 5-membered or 6-membered ring with a carbon atom in the naphthyl ring via the group R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ as appropriate;

COR₁₆或NO₂；or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are

COR ₁₆ or NO ₂ ;

Y is O, S, _NR or a direct bond;

p is an integer 0, 1, 2, or 3;

q is an integer 1, 2 or 3;

X is CO or direct bond;

R ₁₃ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ or

Or R ₁₃ is C ₂ -C ₂₀ alkyl, which is mixed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO, or C ₂ -C ₁₂ alkenyl, which is uninterrupted or mixed with a or more O, CO, or NR ₂₆ , wherein the intervened C ₂ -C ₂₀ alkyl and the uninterrupted or intervened C ₂ -C ₁₂ alkenyl are unsubstituted or substituted with one or more halogens;

or R ₁₃ is C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl, or C ₃ -C ₁₀ cycloalkyl without or intervening one or more O, S, CO or NR ₂₆ ;

COR₁₆、CN、NO₂、卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、间杂有一或多个O、S、CO或NR_26-的C₂-C₂₀烷基；或其各经C₃-C₁₀环烷基或间杂有一或多个O、S、CO或NR₂₆的C₃-C₁₀环烷基取代；or R ₁₃ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

COR ₁₆ , CN, NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, S, CO or NR _26- ; or Each of which is substituted with C ₃ -C ₁₀ cycloalkyl or C ₃ -C ₁₀ cycloalkyl interspersed with one or more O, S, CO or NR ₂₆ ;

k is an integer from 1 to 10;

R ₁₄ is hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy or C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by one or more of the following Group substitution: halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or CN;

or R ₁₄ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, CN, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ;

or R ₁₄ is C ₃ -C ₂₀ heteroaryl, C ₁ -C ₈ alkoxy, benzyloxy or phenoxy, which benzyloxy and phenoxy are unsubstituted or substituted by one or more of the following groups Substituted: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl and/or halogen;

R ₁₅ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN , NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, interspersed with one or A plurality of C2- _C20 alkyl groups of O, S, or NR ₂₆ ; or each substituted with _{a C1 - C20} alkyl group that is unsubstituted or substituted with one or more of _the following groups Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl oxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl without or with one or more O, CO or NR ₂₆ ;

苯基；或该C₁-C₂₀烷基是经苯基取代，该苯基是经卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、OR₁₇、SR₁₈或NR₁₉R₂₀取代；or R ₁₅ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ hetero Aryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ ,

phenyl; or the C ₁ -C ₂₀ alkyl is substituted with phenyl, the phenyl is halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ to replace;

Or R ₁₅ is C ₂ -C ₂₀ alkyl, intervening with one or more O, SO or SO ₂ , and the intervening C ₂ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups : halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted by OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is C ₂ -C ₂₀ alkanoyl or benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ unsubstituted or substituted with one or more OR ₁₇ naphthoyl or C ₃ -C ₁₄ heteroarylcarbonyl;

Or R ₁₅ is C ₂ -C ₁₂ alkoxycarbonyl, which is uninterrupted or interspersed with one or more O and the interspersed or uninterrupted C ₂ -C ₁₂ alkoxycarbonyl is unsubstituted or an or multiple hydroxyl substitutions;

or R ₁₅ is phenoxycarbonyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m -C ₁ -C ₆ alkyl, unsubstituted or C ₁ -C ₁₂ alkyl or SO ₂ - _C1 - _C6 alkyl-substituted S(O) _m -phenyl;

or R ₁₅ is SO ₂ O-phenyl, unsubstituted or substituted with C ₁ -C ₁₂ alkyl; or diphenylphosphono or bis(C ₁ -C ₄ alkoxy)-phosphono;

m is 1 or 2;

R' ₁₄ has one of the meanings given for R ₁₄ ;

R' ₁₅ has one of the meanings given for R ₁₅ ;

X ₁ is O, S, SO or SO ₂ ;

X ₂ is O, CO, S or a direct bond;

R ₁₆ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN , NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl interspersed with one or more O, S or NR ₂₆ ; or each of them via one or more C ₁ -C ₂₀ alkyl Substituted, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₆ is hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with _one or more of _the following: halogen, phenyl, OH, SH, CN, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)- Phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

Or R ₁₆ is a C ₂ -C ₁₂ alkyl group, which is mixed with one or more O, S or NR ₂₆ ;

or R ₁₆ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl;

or R ₁₆ is SR ₁₈ substituted phenyl, wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring of the carbazole moiety to which the COR ₁₆ group is attached;

n is 1 to 20;

R ₁₇ is hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)- (C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ -( C ₁ -C ₄ haloalkyl), O(C ₁ -C ₄ haloalkyl) or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O;

Or R ₁₇ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S or NR ₂₆ ;

or R ₁₇ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkanoyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenoyl or C ₃ -C ₂₀ cycloalkyl without or with one or more O, S, CO or NR ₂₆ ;

or R ₁₇ is C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl, which is uninterrupted or interspersed with one or more O;

or R ₁₇ is benzoyl, which is unsubstituted or substituted with one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy;

or R ₁₇ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N(C ₁ -C ₁₂ alkane base) ₂ , diphenyl-amino or

所处的苯基或萘基环的其中一个碳原子的直接键；or R ₁₇ forms a bond to the group

A direct bond to one of the carbon atoms of the phenyl or naphthyl ring in which it is located;

R ₁₈ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein the C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkane radical or phenyl-C ₁ -C ₃ alkyl is uninterrupted or interspanned with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ;

or R ₁₈ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO) - phenyl or (CO)OR ₁₇ ;

Or R ₁₈ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ;

or R ₁₈ is (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ alkene acyl;

or R ₁₈ is benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkane base thio;

or R ₁₈ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ Haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N( C ₁ -C ₁₂ alkyl) ₂ , diphenylamine, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N(C ₁ - C ₈ alkyl) ₂ or

R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ - C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl, SO ₂ -(C ₁ - C ₄ haloalkyl) or benzoyl;

or R ₁₉ and R ₂₀ are phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzoyl or C ₁ -C ₁₂ alkoxy;

或未经间杂或间杂有一或多个O、S、CO或NR₁₇的C₃-C₂₀环烷基；Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₁₇ , and the 5-membered or 6-membered saturated or unsaturated ring Unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl,

Or C ₃ -C ₂₀ cycloalkyl without or with one or more O, S, CO or NR ₁₇ ;

卤素、NO₂、CN、苯基或未经间杂或间杂有一或多个O、S、CO或NR₁₇的C₃-C₂₀环烷基；or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ ,

halogen, NO ₂ , CN, phenyl or C ₃ -C ₂₀ cycloalkyl without or with one or more O, S, CO or NR ₁₇ ;

R ₂₁ and R ₂₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl;

Or R ₂₁ and R ₂₂ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₂₆ , and the 5-membered or 6-membered saturated or unsaturated ring is not fused or the 5- or 6-membered saturated or unsaturated ring is fused with a benzene ring;

R ₂₃ is hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, CO or NR ₂₆ , uninterrupted or interspersed with O , S, CO or C ₃ -C ₂₀ cycloalkyl of NR ₂₆ , or R ₂₃ is phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ;

R ₂₄ is (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ is one of the meanings given for R ₁₉ and R ₂₀ ;

R ₂₅ is COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₅ is one of the meanings given for R ₁₇ ;

R ₂₆ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, mixed with one or more O or CO; or phenyl-C ₁ -C ₄ alkane radical, C3- _C8cycloalkyl , which is _{uninterrupted} or interspersed with one or more O or CO; or (CO) _R19 ; or phenyl, which is unsubstituted or substituted by one or more of the following Group substitution: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or

或

provided that at least one group is present in the molecule

or

The black pigment (E) comprises a first black pigment (E-1), wherein the first black pigment (E-1) comprises a compound having the formula (E-I), its geometric isomer, its salt or Salts of its geometric isomers:

In formula (EI), R ^1e and R ^6e are independently hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ^2e , R ^3e , R ^4e , R ^5e , R ^7e , R ^8e , R ^9e and R ^10e and all others independently of each other are hydrogen atom, halogen atom, R ^11e , COOH, COOR ^11e , COO-, CONH ₂ , CONHR ^11e , CONR ^11e R ^12e , CN, OH, OR ^11e , COCR ^11e , OOCNH ₂ , OOCNHR ^11e , OOCNR ^11e R ^12e , NO ₂ , NH ₂ , NHR ^11e , NR ^11e R ^12e , NHCOR ^12e , NR ^11e COR ^12e , N=CH ₂ , N=CHR ^11e , N=CR ^11e R ^12e , SH, SR ^11e , SOR ^11e , SO ₂ R ^11e , SO ₃ R ^11e , SO ₃ H, SO ₃ −, SO ₂ NH ₂ , SO ₂ ^{NHR 11e} , or SO ₂ ^{NR 11e} R ^12e ; At least one combination from the group consisting of R ^3e and R ^4e , R ^4e and R ^5e , R ^7e and R ^8e , R ^8e and R ^9e , and R ^9e and R ^10e is a direct bond with each other, or They are bonded to each other through oxygen atom, sulfur atom, NH or NR ^11e bridging; R ^11e and R ^12e are independently each other an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a group having 2 to 12 carbon atoms. Alkenyl, cycloalkenyl having 3 to 12 carbons, or alkynyl having 2 to 12 carbons.

The alkali-soluble resin (A) according to the present invention may contain the resin (A-1) having an unsaturated group. Next, the alkali-soluble resin (A) may optionally contain other alkali-soluble resins (A-2).

The unsaturated group-containing resin (A-1) is formed by polymerizing a mixture. The mixture may contain an epoxy compound (a-1-1) having at least two epoxy groups and a compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. Furthermore, the mixture may optionally contain a carboxylic acid anhydride compound (a-1-3) and a compound (a-1-4) having an epoxy group.

The epoxy compound (a-1-1) having at least two epoxy groups includes a compound having a structure represented by the following formula (I), a compound having a structure represented by the following formula (II), and a combination of the above compounds :

In the formula (I), R ^1a to R ^4a each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons, a alkoxy group having 6 to 12 carbons An aryl group or an aralkyl group having 6 to 12 carbon atoms.

The compound having the structure shown in formula (I) may include a bisphenol fluorene compound having an epoxy group, wherein the bisphenol fluorene compound having an epoxy group may be a bisphenol fluorene compound with halogenated Propylene oxide (epihalohydrin) reaction derived.

Specific examples of the aforementioned bisphenol fluorene compound may include 9,9-bis(4-hydroxyphenyl)fluorene [9,9-bis(4-hydroxyphenyl)fluorene], 9,9-bis(4-hydroxy-3 -Methylphenyl) fluorene [9,9-bis(4-hydroxy-3-methylphenyl)fluorene], 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene [9,9-bis(4 -hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene[9,9-bis(4-hydroxy-3-bromophenyl)fluorene], 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene [9,9-bis(4-hydroxy-3-fluorophenyl)fluorene], 9,9-bis(4-hydroxy-3-methoxyphenyl) fluorene [ 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene [9,9-bis(4-hydroxy-3 , 5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene], 9, 9-bis(4-hydroxy-3,5-dibromophenyl) fluorene [9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene], similar compounds of bisphenol fluorene compounds, or the above compounds any combination of .

Specific examples of the aforementioned halogenated propylene oxide (epihalohydrin) may include 3-chloro-1,2-epoxypropylene (epichlorohydrin), 3-bromo-1,2-epoxypropylene (epibromohydrin), and similar compounds of halogenated propylene oxide , or any combination of the above compounds.

Specific examples of the bisphenol-based compound having an epoxy group may include (1) products manufactured by Nippon Steel Chemical, such as products with model ESF-300 or similar products; (2) products manufactured by Osaka Gas, such as : Products with model number PG-100 or EG-210, or similar products; (3) Goods manufactured by S.M.S Technology Co., such as products with model number SMS-F9PhPG, SMS-F9CrG or SMS-F914PG, or similar products.

In formula (II), R ^5a to R ^18a each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms; and a represents an integer of 0 to 10 .

The compound with the structure shown in formula (II) can be obtained by reacting the compound with the structure shown in the following formula (II-1) with halogenated propylene oxide in the presence of alkali metal hydroxide:

In formula (II-1), the definitions of R ^5a to R ^18a and a are as described above, and will not be repeated here.

The method for synthesizing the compound having the structure shown in the formula (II) is to first perform a condensation reaction on the compound having the structure shown in the following formula (II-1-1) and the phenolic compound in the presence of an acid catalyst , to form a compound having the structure shown in formula (II-1):

In formula (II-1-1), R ^19a and R ^20a each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms; A ₁ and A ₂ each independently represents a halogen atom, an alkyl group having 1 to 6 carbons, or an alkoxy group having 1 to 6 carbons. The above-mentioned alkyl group is preferably methyl group, ethyl group or tert-butyl group, and the alkoxy group is preferably methoxy group or ethoxy group.

Specific examples of the aforementioned phenolic compounds may include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butanol butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol , propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol, cyclohexylcresol or similar compounds of phenolic compounds. The phenolic compounds may be used alone or in combination.

The phenolic compound is used in an amount of 0.5 mol to 20 mol, and preferably 2 mol to 15 mol, based on 1 mol of the aforementioned compound having the structure represented by formula (II-1-1).

Specific examples of the above acid catalyst may include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous, zinc chloride (zinc chloride) or analogs of acid catalysts. This acid catalyst may be used alone or in combination.

Preferably, the acid catalyst can be p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or any combination of the above compounds.

The amount of the acid catalyst used is not particularly limited. The acid catalyst is used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the aforementioned compound having the structure represented by formula (IV-1-1).

The aforementioned condensation reaction can be carried out in the presence of no solvent or organic solvent, and a specific example of the organic solvent can be toluene, xylene, methyl isobutyl ketone or the like. thing. The organic solvent may be used alone or in combination.

Based on the total usage amount of the aforementioned compound having the structure shown in formula (II-1-1) and the phenolic compound is 100 parts by weight, the usage amount of the organic solvent is 50 parts by weight to 300 parts by weight, preferably 100 parts by weight parts by weight to 250 parts by weight.

The reaction temperature of the condensation reaction may be 40°C to 180°C, and the reaction time may be 1 hour to 8 hours.

After the condensation reaction is completed, neutralization treatment or water washing treatment may be selectively performed.

In the above-mentioned neutralization treatment, the pH value of the reacted solution is adjusted to 3 to 7, preferably 5 to 7.

The above-mentioned water washing treatment can be performed with a neutralizing agent. The neutralizing agent may be an alkaline substance, and specific examples of the neutralizing agent may include alkalis such as ammonia, sodium dihydrogen phosphate, sodium hydroxide or potassium hydroxide. Metal hydroxides; alkaline earth metal hydroxides such as calcium hydroxide or magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline Or organic amines such as phenylene diamine or any combination of the above compounds. These neutralizing agents may be used alone or in combination.

This water washing treatment can be carried out by a well-known method. For example, an aqueous solution containing a neutralizing agent is added to the reacted solution, and extraction is repeated. After neutralization or water washing, the unreacted phenolic compound and solvent in the solution can be removed by heating under reduced pressure and concentrated to obtain a compound having a structure as shown in formula (II-1).

After the condensation reaction is completed, an excess amount of halogenated propylene oxide is added, so that the halogenated propylene oxide and the compound having the structure shown in formula (II-1) are subjected to dehydrohalogenation reaction (dehydrohalogenation), and the compound having the structure shown in the formula (II-1) can be prepared The compound of the structure represented by formula (II).

Specific examples of the aforementioned halogenated propylene oxide may include 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane, or a combination of the above compounds.

Before the aforementioned dehydrohalogenation reaction, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide can be added in advance or added to the reaction solution during the reaction. The reaction temperature of the dehydrohalogenation reaction may be 20°C to 120°C, and the reaction time may be 1 hour to 10 hours.

In one embodiment, the aforementioned alkali metal hydroxide compound may be an aqueous solution. In this embodiment, when the aqueous alkali metal hydroxide solution is continuously added to the reaction system of the dehydrohalogenation reaction, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure to separate and remove water, And the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the dehydrohalogenation reaction, quaternary ammonium salts such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, and trimethyl benzyl ammonium chloride can be added into the reaction system to serve as a catalyst, and after reacting at 50° C. to 150° C. for 1 hour to 5 hours, the alkali metal hydroxide or its aqueous solution is added to the reaction system. Then, the reaction is carried out at 20°C to 120°C for 1 hour to 10 hours to perform dehydrohalogenation reaction.

The halogenated propylene oxide is used in an amount of 1 to 20 equivalents, and preferably 2 to 10 equivalents, based on 1 equivalent of the total number of hydroxyl groups in the aforementioned compound having the structure represented by the formula (II-1). . The alkali metal hydroxide used in the dehydrohalogenation reaction is used in an amount of 0.5 to 15 equivalents based on 1 equivalent of the total number of hydroxyl groups in the aforementioned compound having the structure shown in formula (II-1), and preferably 0.9 equiv to 11 equiv.

In order to make the above-mentioned dehydrohalogenation reaction proceed smoothly, an alcohol compound such as methanol or ethanol may be added to the reaction system. In addition, an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide can also be added to the reaction system.

When an alcohol compound is used, the total usage amount of the above-mentioned halogenated propylene oxide is 100 parts by weight, and the usage amount of the alcohol compound is 2 parts by weight to 20 parts by weight, and preferably 4 parts by weight to 15 parts by weight. When an aprotic polar solvent is used, the total usage amount of the halogenated propylene oxide is 100 parts by weight, and the usage amount of the aprotic polar solvent is 5 to 100 parts by weight, and preferably 10 parts by weight parts to 90 parts by weight.

After the aforementioned dehydrohalogenation reaction, the reaction system can be selectively washed with water. Then, in an environment with a temperature of 110° C. to 250° C. and a pressure of 1.3 kPa (10 mmHg) or less, the halogenated propylene oxide, the alcohol compound, and the aprotic polar solvent are removed.

In order to prevent the formed epoxy resin from having hydrolyzable halogens, the solution after dehydrohalogenation reaction can be added with solvents such as toluene, methyl isobutyl ketone, and alkalis such as sodium hydroxide or potassium hydroxide. Metal hydroxide aqueous solution, and dehydrohalogenation reaction is carried out again. In the aforementioned dehydrohalogenation reaction, based on the total number of equivalents of hydroxyl groups in the aforementioned compound having the structure shown in formula (II-1) is 1 equivalent, the amount of the alkali metal oxyhydroxide used is 0.01 equivalent to 0.3 equivalent, And it is preferably 0.05 equivalent to 0.2 equivalent. In addition, the reaction temperature of the dehydrohalogenation reaction may be 50°C to 120°C, and the reaction time may be 0.5 hours to 2 hours.

When the dehydrohalogenation reaction is completed, the salts in the reaction solution can be removed by steps such as filtration and water washing, and solvents such as toluene, methyl isobutyl ketone, etc. II) Compounds of the structure shown. Specific examples of the compound having the structure represented by the formula (II) include products manufactured by Nippon Kayaku Co., Ltd., whose models are NC-3000, NC-3000H, NC-3000S, NC-3000P, and the like.

The compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group can be selected from the group consisting of the following (1) to (3):

(1) Acrylic acid, methacrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxybutylsuccinic acid, 2-methacryloyloxyethylsuccinic acid Adipic acid, 2-methacryloyloxybutyladipic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methyl Acryloyloxypropylmaleic acid, 2-methacryloyloxybutylmaleic acid, 2-methacryloyloxypropylsuccinic acid, 2-methacryloyloxypropyladipic acid, 2- Methacryloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropylphthalic acid, 2-methacryloyloxybutylphthalic acid, or 2-methacryloyloxybutylhydrophthalic acid Compounds such as dicarboxylic acid;

(2) A compound obtained by reacting a (meth)acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein specific examples of the dicarboxylic acid compound may include adipic acid, succinic acid, maleic acid, or orthocarboxylic acid Compounds such as phthalic acid;

(3) A half-ester compound obtained by the reaction of a (meth)acrylate having a hydroxyl group with the following carboxylic acid anhydride compound (a-1-3; please refer to the content described later, which will not be repeated here), wherein the Specific examples of the hydroxy (meth)acrylate include 2-hydroxyethyl acrylate [(2-hydroxyethyl)acrylate], 2-hydroxyethyl methacrylate [(2-hydroxyethyl)methacrylate], 2-hydroxyethyl acrylate Propyl acrylate [(2-hydroxypropyl)acrylate], 2-hydroxypropyl methacrylate [(2-hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl)acrylate], 4-hydroxy Compounds such as butyl methacrylate [(4-hydroxybutyl) methacrylate] or pentaerythritol trimethacrylate.

The carboxylic acid anhydride compound (a-1-3) can be selected from a dicarboxylic acid anhydride compound, a tetracarboxylic acid anhydride compound, or any combination of the above-mentioned compounds.

The aforementioned dicarboxylic acid anhydride compounds may include, but are not limited to, butanedioic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydro Phthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic anhydride), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl-methylenetetrahydro Dibasic carboxylic anhydride compounds such as methyl endo-methylene tetrahydro phthalicanhydride, chlorendic anhydride, glutaric anhydride, or 1,3-dioxoisobenzofuran-5-carboxylic anhydride.

The aforementioned tetracarboxylic anhydride compounds may include, but are not limited to, tetracarboxylic anhydride compounds such as benzophenonetetracarboxylic dianhydride (BTDA), bismellitic dianhydride, or bisphenyl ether tetracarboxylic dianhydride.

Specific examples of the compound (a-1-4) having an epoxy group include glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and an unsaturated group-containing glycidyl ether compound , an unsaturated compound having an epoxy group or a combination of the above compounds.

Specific examples of the aforementioned glycidyl ether compound having an unsaturated group include products manufactured by Nagase Chemical Industry Co., Ltd., whose models are Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX -146, Denacol EX-171 and Denacol EX-192.

The resin (A-1) having an unsaturated group can be composed of an epoxy compound (a-1-1) having at least two epoxy groups having a structure as shown in formula (I) and having at least one carboxylic acid group and The compound (a-1-2) having at least one ethylenically unsaturated group is reacted to form a reaction product having a hydroxyl group. Then, the obtained reaction product is reacted with a carboxylic acid anhydride compound (a-1-3) to obtain a resin (A-1) having an unsaturated group of the present invention. The equivalent number of the acid anhydride group of the carboxylic acid anhydride compound (a-1-3) is 0.4 to 1 equivalent, and preferably 0.75 to 1 equivalent, based on the total equivalent number of hydroxyl groups of the aforementioned reaction product having a hydroxyl group. When a plurality of carboxylic acid anhydride compounds (a-1-3) are used, such carboxylic acid anhydride compounds (a-1-3) may be added sequentially or simultaneously to the reaction. When the carboxylic acid anhydride compound (a-1-3) includes a dicarboxylic acid anhydride compound and a tetracarboxylic acid anhydride compound, the equivalent ratio of the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound is 1/99 to 90/10, preferably 5/95 to 80/20. The operating temperature range for the above reaction is 50°C to 130°C.

The resin (A-1) having an unsaturated group can be composed of an epoxy compound (a-1-1) having at least two epoxy groups having a structure as shown in formula (II) and having at least one carboxylic acid group and The compound (a-1-2) having at least one ethylenically unsaturated group is reacted to form a reaction product having a hydroxyl group. Then, the obtained reaction product is reacted with a carboxylic acid anhydride compound (a-1-3) and/or a compound (a-1-4) having an epoxy group to obtain the resin having an unsaturated group of the present invention (A-1). The total equivalent number of epoxy groups in the epoxy compound (a-1-1) having at least two epoxy groups having a structure as represented by formula (II) is 1 equivalent, which has at least one carboxylic acid group The acid value equivalent number of the compound (a-1-2) and at least one ethylenically unsaturated group is 0.8 to 1.5 equivalents, and preferably 0.9 to 1.1 equivalents. The amount of the carboxylic acid anhydride compound (a-1-3) used is 10 to 100 mole percent, preferably 20 to 100 mole percent, based on the total amount of hydroxyl groups of the aforementioned reaction product with hydroxyl groups being 100 mole percent, And more preferably, it is 30 mol% to 100 mol%.

When preparing the aforementioned resin (A-1) having an unsaturated group, in order to accelerate the reaction rate, a basic compound is generally added to the reaction solution as a reaction catalyst. Specific examples of the reaction catalyst may include, but are not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride chloride) or benzyltriethylammonium chloride and other compounds. The aforementioned reaction catalysts may be used alone or in combination.

The total usage amount based on the aforementioned epoxy compound (a-1-1) having at least two epoxy groups and compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 In parts by weight, the reaction catalyst is used in an amount of 0.01 to 10 parts by weight, and preferably 0.3 to 5 parts by weight.

Next, in order to control the degree of polymerization of the aforementioned resin (A-1) having an unsaturated group, an inhibitor may be added to the reaction solution. Specific examples of the polymerization inhibitor may include, but are not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol) -di-t-butyl-p-cresol) or phenothiazine and other compounds. The polymerization inhibitor can be used alone or in combination.

The total usage amount based on the aforementioned epoxy compound (a-1-1) having at least two epoxy groups and compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 In parts by weight, the polymerization inhibitor is used in an amount of 0.01 to 10 parts by weight, and preferably 0.1 to 5 parts by weight.

Furthermore, when preparing the aforementioned resin (A-1) having an unsaturated group, a polymerization reaction solvent may be added to the reaction solution. Specific examples of the polymerization solvent may include but are not limited to alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; methyl ethyl ketone or cyclohexanone, etc. Ketones; aromatic hydrocarbons such as toluene or xylene; cellosolve compounds such as cellosolve or butyl cellosolve; carbital such as carbitol or butyl carbitol Compounds; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; poly(propylene glycol) alkyl ether compounds such as dipropylene glycol monomethyl ether [di(propylene glycol) methyl ether]; ethyl acetate, butyl acetate esters, acetate compounds such as ethylene glycol monoethylether acetate or propylene glycol methyl ether acetate; lactyl alkanes such as ethyl lactate or butyl lactate ester (alkyllactate) compounds; or dialkyl glycol ether compounds. The polymerization reaction solvent may be used alone or in combination.

The acid value of the resin (A-1) having an unsaturated group prepared by the present invention is 50 mgKOH/g to 150 mgKOH/g.

The weight average molecular weight of the resin (A-1) having an unsaturated group of the present invention is generally 600 to 10,000, preferably 800 to 8,000, and more preferably 1,000 to 6,000. The resin (A-1) having an unsaturated group may be a single resin, or two or more kinds of resins with different molecular weights may be used in combination.

Based on the usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount of the resin (A-1) having an unsaturated group is 30 parts by weight to 100 parts by weight, preferably 40 parts by weight to 100 parts by weight, And it is more preferably 50 to 100 parts by weight.

When the alkali-soluble resin (A) of the present invention contains the resin (A-1) having an unsaturated group, the black pattern obtained from the black photosensitive resin composition has better linearity of the high-definition pattern. .

The aforementioned other alkali-soluble resins (A-2) may include, but are not limited to, resins having a carboxylic acid group or a hydroxyl group. Specific examples of the other alkali-soluble resin (A-2) may be alkali-soluble resins such as acrylic resins, urethane resins, and novolak resins other than the aforementioned resin (A-1) having an unsaturated group.

Based on 100 parts by weight of the alkali-soluble resin (A), the other alkali-soluble resin (A-2) is used in an amount of 0 to 70 parts by weight, preferably 0 to 60 parts by weight, and more It is preferably 0 to 50 parts by weight.

The compound (B) having an ethylenically unsaturated group according to the present invention includes a first compound (B-1) having an ethylenically unsaturated group, and the first compound (B-1) having an ethylenically unsaturated group includes The compound represented by formula (B-I):

In formula (BI), R ^1b is a hydrogen atom or a methyl group, R ^2b is a hydrogen atom, an acryloyl group or a methacryloyl group, and b is an integer of 2 to 3.

In a specific example of the present invention, the first compound (B-1) having an ethylenically unsaturated group includes but is not limited to tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, pentaerythritol Nona(meth)acrylate or pentaerythritol ten(meth)acrylate or any combination of the above.

The amount of the first compound (B-1) having an ethylenically unsaturated group is 30 to 300 parts by weight, preferably 40 to 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). 250 parts by weight, and more preferably 50 parts by weight to 200 parts by weight.

When the first compound (B-1) having the ethylenically unsaturated group is used, the black pattern obtained from the black photosensitive resin composition has good high-definition pattern linearity.

In another specific example of the present invention, the compound (B) having an ethylenically unsaturated group may further comprise a second compound (B-2) having an ethylenically unsaturated group, which has an ethylenically unsaturated group The second compound (B-2) is selected from compounds having one ethylenically unsaturated group or compounds having two or more (including two) ethylenically unsaturated groups.

Specific examples of the compound having one ethylenically unsaturated group may include, but are not limited to, (meth)acrylamide, (meth)acryloylmorpholine, (meth)acrylic acid-7-amino group -3,7-Dimethyloctyl ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid -2-ethylhexyl ester, ethyldiethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, (meth)acrylate dimethylamine Ethyl (meth)acrylate, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl(methyl) ) acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate (meth)acrylate, (methyl) ) tetrabromophenyl acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, ( 2-Tribromophenoxyethyl Meth)acrylate, Ethyl 2-Hydroxy-(meth)acrylate, Propyl 2-Hydroxy-(meth)acrylate, Vinylcaprolactam, Nitrogen-vinylpyrrolidone, ( Phenoxyethyl meth)acrylate, Pentachlorophenyl (meth)acrylate, Pentabromophenyl (meth)acrylate, Polyethylene mono(meth)acrylate, Polypropylene mono(meth)acrylate esters or compounds such as bornyl (meth)acrylate. The compound having one ethylenically unsaturated group) can be used alone or in combination.

Specific examples of the compound having two or more (including two) ethylenically unsaturated groups may include, but are not limited to, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl) Isocyanate tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl) isocyanate tri(meth)acrylate, trimethylolpropyl tri(meth)acrylate, cyclic Trimethylolpropyl tri(meth)acrylate modified with ethylene oxide (EO), trimethylolpropyl tri(meth)acrylate modified with propylene oxide (PO), Tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylic acid ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate ) acrylate, di(trimethylolpropane)tetra(meth)acrylate, bisphenol A di(meth)acrylate modified by ethylene oxide, Oxypropane-modified bisphenol A di(meth)acrylate, ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide-modified hydrogenated bisphenol A di(meth)acrylate base) acrylate, propylene oxide modified glycerol tri(meth)acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, novolac polyglycidyl ether (methyl) Acrylates or any combination of the above. The compound having two or more (including two) ethylenically unsaturated groups may be used alone or in combination of two or more.

The second compound (B-2) having an ethylenically unsaturated group can preferably be trimethylolpropyl triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate or any combination of the above compounds.

Based on the usage amount of the alkali-soluble resin (A) being 100 parts by weight, the usage amount of the compound (B) having an ethylenically unsaturated group is 30 parts by weight to 300 parts by weight, preferably 40 parts by weight to 250 parts by weight, And it is more preferably 50 to 200 parts by weight.

The photoinitiator (C) of the present invention can be a substance that generates free radicals by irradiation, and the aforementioned substances having free radicals can initiate polymer-to-polymer, polymer-oligopolymer, or polymer-to-monomer The cross-linking reaction between them can form patterns with good mechanical strength (for example: black matrix or black spacers).

The photoinitiator (C) according to the present invention comprises a first photoinitiator (C-1) having a structure represented by formula (C-I), and secondly, the photoinitiator (C) may optionally include The second photoinitiator (C-2) of the structure represented by the formula (C-II) may optionally contain other photoinitiators (C-3), which will be described below.

The photoinitiator (C) according to the present invention comprises a photoinitiator (C-1) having a structure represented by the formula (C-I):

COR₁₆、OR₁₇、卤素、NO₂或

或R₁及R₂、R₂及R₃、R₃及R₄、R₅及R₆、R₆及R₇或R₇及R₈彼此独立地为经

取代的C₂-C₁₀烯基或R₁及R₂、R₂及R₃、R₃及R₄、R₅及R₆、R₆及R₇或R₇及R₈彼此独立地共同为-(CH₂)_P-Y-(CH₂)_q-；wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen, C ₁ -C ₂₀ alkyl,

COR ₁₆ , OR ₁₇ , halogen, NO ₂ or

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other

Substituted C ₂ -C ₁₀ alkenyl or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together -(CH ₂ ) _P -Y-(CH ₂ ) _q -;

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together

provided that at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with _one or more of _the following groups: halogen, benzene group, CN, OH, SH, C ₁ -C ₄ -alkoxy, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substituent OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ forms a 5- or 6-membered ring with a carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ;

COR₁₆或NO₂；or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are

COR ₁₆ or NO ₂ ;

Y is O, S, _NR or a direct bond;

p is an integer 0, 1, 2, or 3;

q is an integer 1, 2 or 3;

X is CO or direct bond;

R ₁₃ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1)2 or

Or R ₁₃ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO,

Or C ₂ -C ₁₂ alkenyl, which is uninterrupted or interspersed with one or more O, CO or NR ₂₆ , wherein interspersed C ₂ -C ₂₀ alkyl and uninterrupted or interspersed C ₂ -C _12Alkenyl is unsubstituted or substituted with one or more halogens;

or R ₁₃ is C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl, or C ₃ -C ₁₀ cycloalkyl without or intervening one or more O, S, CO or NR ₂₆ ;

COR₁₆、CN、NO₂、卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、间杂有一或多个O、S、CO或NR₂₆的C₂-C₂₀烷基；或其各经C₃-C₁₀环烷基或间杂有一或多个O、S、CO或NR₂₆的C₃-C₁₀环烷基取代；or R ₁₃ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

COR ₁₆ , CN, NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, S, CO or NR ₂₆ ; or Each is substituted with C ₃ -C ₁₀ cycloalkyl or C ₃ -C ₁₀ cycloalkyl interspersed with one or more O, S, CO or NR ₂₆ ;

k is an integer from 1 to 10;

R ₁₄ is hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy, or C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by one or more halogens , phenyl, C ₁ -C ₂₀ alkyl phenyl or CN substituted;

or R ₁₄ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, CN, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ;

or R ₁₄ is C ₃ -C ₂₀ heteroaryl, C ₁ -C ₈ alkoxy, benzyloxy or phenoxy, which benzyloxy and phenoxy are unsubstituted or substituted by one or more C ₁ - C ₆ alkyl, C ₁ -C ₄ haloalkyl and/or halogen substitution;

R ₁₅ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN , NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, interspersed with one or A plurality of C2- _C20 alkyl groups of O, S, or NR ₂₆ ; or each substituted with _{a C1 - C20} alkyl group that is unsubstituted or substituted with one or more of _the following groups Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl oxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl without or with one or more O, CO or NR ₂₆ ;

苯基；或该C₁-C₂₀烷基经苯基取代，该苯基经卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、OR₁₇、SR₁₈或NR₁₉R₂₀取代；or R ₁₅ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ hetero Aryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ ,

phenyl; or the C ₁ -C ₂₀ alkyl is substituted with phenyl which is substituted with halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

Or R ₁₅ is C ₂ -C ₂₀ alkyl, intervening with one or more O, SO or SO ₂ , and the intervening C ₂ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups : halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted by OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is C ₂ -C ₂₀ alkanoyl or benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ unsubstituted or substituted with one or more OR ₁₇ naphthoyl or C ₃ -C ₁₄ heteroarylcarbonyl;

Or R ₁₅ is C ₂ -C ₁₂ alkoxycarbonyl, which is uninterrupted or interspersed with one or more O and the interspersed or uninterrupted C ₂ -C ₁₂ alkoxycarbonyl is unsubstituted or substituted by one or Multiple hydroxyl substitutions;

or R ₁₅ is phenoxycarbonyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m -C ₁ -C ₆ alkyl, unsubstituted or C ₁ -C ₁₂ alkyl or SO ₂ - _C1 - _C6 alkyl-substituted S(O) _m -phenyl;

or R ₁₅ is SO ₂ O-phenyl, unsubstituted or substituted with C ₁ -C ₁₂ alkyl; or diphenylphosphono or bis(C ₁ -C ₄ alkoxy)-phosphono;

m is 1 or 2;

R' ₁₄ is one of the meanings given for R ₁₄ ;

R' ₁₅ is one of the meanings given for R ₁₅ ;

X ₁ is O, S, SO or SO ₂ ;

X ₂ is O, CO, S or a direct bond;

R ₁₆ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN , NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl interspersed with one or more O, S or NR ₂₆ ; or each of them via one or more C ₁ -C ₂₀ alkyl Substituted, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₆ is hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with _one or more of _the following: halogen, phenyl, OH, SH, CN, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)- Phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

Or R ₁₆ is a C ₂ -C ₁₂ alkyl group, which is mixed with one or more O, S or NR ₂₆ ;

or R ₁₆ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl;

or R ₁₆ is SR ₁₈ substituted phenyl, wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring to which the carbazole moiety of COR ₁₆ is attached;

n is 1 to 20;

R ₁₇ is hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), OCO)-(C ₂ -C ₄ ) alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl, SO ₂ -(C ₁ -C ₄ haloalkyl), O(C ₁ -C ₄ haloalkyl) or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O;

Or R ₁₇ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S or NR ₂₆ ;

or R ₁₇ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ -C ₈ alkanoyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenoyl or C ₃ -C ₂₀ cycloalkyl without or with one or more O, S, CO or NR ₂₆ ;

or R ₁₇ is C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl, which is not interspersed or interspersed with one or more O;

or R ₁₇ is benzoyl, which is unsubstituted or substituted with one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy;

or R ₁₇ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N(C ₁ -C ₁₂ alkane base) ₂ , diphenyl-amino or

的苯基或萘基环的一个碳原子的直接键；or R ₁₇ forms a bond to which has a group

A direct bond to one carbon atom of the phenyl or naphthyl ring;

R ₁₈ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl Or phenyl-C ₁ -C ₃ alkyl is not interspersed or interspersed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ;

or R ₁₈ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO) - phenyl or (CO)OR ₁₇ ;

Or R ₁₈ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ;

or R ₁₈ is (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ alkene acyl;

or R ₁₈ is benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkane base thio;

or R ₁₈ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ Haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N( C ₁ -C ₁₂ alkyl) ₂ , diphenylamine, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N(C ₁ - C ₈ alkyl) ₂ or

R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ - C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl, SO ₂ -(C ₁ - C ₄ haloalkyl) or benzoyl;

or R ₁₉ and R ₂₀ are phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzoyl or C ₁ -C ₁₂ alkoxy;

或C₃-C₂₀环烷基，该C₃-C₂₀环烷基未经间杂或间杂有一或多个O、S、CO或NR₁₇；Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₁₇ , and the 5-membered or 6-membered saturated or unsaturated ring Unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl,

or C ₃ -C ₂₀ cycloalkyl, which C ₃ -C ₂₀ cycloalkyl is not interspersed or interspersed with one or more O, S, CO or NR ₁₇ ;

卤素、NO₂、CN、苯基或C₃-C₂₀环烷基，该C₃-C₂₀环烷基未经间杂或间杂有一或多个O、S、CO或NR₁₇；or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, =O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ ,

Halogen, NO ₂ , CN, phenyl or C ₃ -C ₂₀ cycloalkyl, which C ₃ -C ₂₀ cycloalkyl is not interspersed or interspersed with one or more O, S, CO or NR ₁₇ ;

R ₂₁ and R ₂₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl;

Or R ₂₁ and R ₂₂ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₂₆ , and the 5-membered or 6-membered saturated or unsaturated ring Not fused or the 5- or 6-membered saturated or unsaturated ring is fused with a benzene ring;

R ₂₃ is hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, CO or NR ₂₆ , uninterrupted or interspersed with O , S, CO or C ₃ -C ₂₀ cycloalkyl of NR ₂₆ , or R ₂₃ is phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ is (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ is one of the meanings given for R ₁₉ and R ₂₀ ;

R ₂₅ is COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₅ is one of the meanings given for R ₁₇ ; R ₂₆ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkane base, C ₂ -C ₂₀ alkyl with one or more O or CO; or phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ without or with one or more O or CO cycloalkyl; or (CO)R ₁₉ ; or phenyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or

provided that at least one group is present in the molecule

The photoinitiator (C-1) having the structure represented by the formula (CI) is characterized in that it contains one or more annulated unsaturated rings on the carbazole moiety. In other words, at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ are

In one embodiment, the photoinitiator (C-1) having the structure represented by formula (CI), the C ₁ -C ₂₀ alkyl group is a straight chain or branched chain and is (for example) C ₁ -C ₁₈ -, C ₁ -C ₄ -, C ₁ -C ₁₂ -, C ₁ -C ₈ -, C ₁ -C ₈ - or C ₁ -C ₄ alkyl or C ₄ -C ₁₂ - or C ₄ -C ₈ alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl ylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosyl. C ₁ -C ₆ alkyl has the same meaning as given above for C ₁ -C ₂₀ alkyl and has the highest corresponding number of C atoms.

The unsubstituted or substituted _C1 - _C20 alkyl group containing one or more CC multiple bonds refers to an alkenyl group as explained below.

The C ₁ -C ₄ haloalkyl is C ₁ -C ₄ alkyl as defined above substituted with halogen as defined below. Alkyl groups are, for example, mono- or polyhalogenated until all H-atoms are replaced by halogen. It is, for example, CnHxHaly, where _x + _y = _2n +1 and Hal is a halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. C2 _- C4hydroxyalkyl refers to C2 _- C4alkyl substituted with one or _two O atoms _. Alkyl groups are straight or branched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl , 3-hydroxybutyl, 2,3-dihydroxypropyl or 2,4-dihydroxybutyl. A C ₂ -C ₁₀ alkoxyalkyl group is a C ₂ -C ₁₀ alkyl group interspersed with one O atom. C ₂ -C ₁₀ alkyl has the same meaning as given above for C ₁ -C ₂₀ alkyl and has the highest corresponding number of C atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl , Propoxypropyl.

The C ₂ -C ₂₀ alkyl group interspersed with one or more O, S, NR ₂₆ or CO is _interspersed with, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 or 2 times. If more than one meta-hetero group is present, they are of the same species or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylene groups). The alkyl groups are straight or branched. For example, the following structural units would exist: _-CH2 - _{CH2 -} O- _CH2CH3 , -[ _CH2CH2O ] _y - _{CH3 (} where y = ₁ to 9), -(CH2- CH ₂ O) ₇ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ ,- CH ₂ -CH ₂ -S-CH ₂ CH ₃ , -CH ₂ -CH(CH ₃ )-NR ₂₆ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -COO-CH ₂ CH ₃ or -CH ₂ - CH( _CH3 )-OCO- _{CH2 - CH2CH3} .

及相应环。其他实施例是诸如

(例如

)或

等结构、以及桥联或稠合环系统，举例而言，该术语亦是涵盖

等。The C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkyl and C ₃ -C ₈ cycloalkyl groups are to be understood in the context of the present application as alkyl groups comprising at least one ring. These are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. C ₃ -C ₁₀ cycloalkyl in the context of the present invention also includes bicyclic rings, in other words bridged rings, for example

and corresponding rings. Other embodiments are such as

(E.g

)or

isostructures, as well as bridged or fused ring systems, for example, the term also covers

Wait.

(例如

)、

等结构。The C ₃ -C ₂₀ cycloalkyl interspersed with O, S, CO, NR ₂₆ has the meanings given above, wherein at least one CH ₂ -group in the alkyl group is replaced by O, S, CO or NR ₂₆ . Examples are such as

(E.g

),

etc. structure.

等。The C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl is a C ₃ -C ₁₀ cycloalkyl as defined above substituted with one or more alkyl groups having up to 8 carbon atoms. Example is

Wait.

等。The C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl interspersed with one or more O is O inter-C ₃ as defined above substituted with one or more alkyl groups having up to 8 carbon atoms -C ₁₀ cycloalkyl. Example is

Wait.

The C ₁ -C ₁₂ alkoxy group is a C ₁ -C ₁₂ alkyl group substituted with one O atom. C ₁ -C ₁₂ alkyl has the same meaning as given above for C ₁ -C ₂₀ alkyl and has the highest corresponding number of C atoms. The C1 _{- C4alkoxy} is linear or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy or The third butoxy. C ₁ -C ₈ -alkoxy and C ₁ -C ₄ -alkoxy have the same meanings as described above and have the highest corresponding number of C atoms.

The C ₁ -C ₁₂ alkylthio group is a C ₁ -C ₁₂ alkyl group substituted with one S atom. C ₁ -C ₂₀ alkyl has the same meaning as given above for C ₁ -C ₂₀ alkyl and has the highest corresponding number of C atoms. The C ₁ -C ₄ alkylthio group is straight or branched chain, such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio group, isobutylthio group, tertiary butylthio group.

The phenyl-C ₁ -C ₃ alkyl group is, for example, benzyl, phenylethyl, α-methylbenzyl or α,α-dimethyl-benzyl, especially benzyl.

The phenyl-C ₁ -C ₃ alkoxy group is, for example, benzyloxy, phenylethoxy, α-methylbenzyloxy or α,α-dimethylbenzyloxy, especially benzyloxy .

The C ₂ -C ₁₂ alkenyl is mono- or polyunsaturated and is, for example, C ₂ -C ₁₀ -, C ₂ -C ₈ -, C ₂ -C ₅ -alkenyl, eg vinyl, allyl , methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl , 7-octenyl or dodecenyl, especially allyl. C ₂ -C ₅ alkenyl has the same meaning as given above for C ₂ -C ₁₂ alkenyl and has the highest corresponding number of C atoms.

The C ₂ -C ₁₂ alkenyl interspersed with one or more O, CO or NR ₂₆ is interspersed with O, S, NR ₂₆ or CO (for example) 1 to 9 times, 1 to 5 times, 1 to 3 times or 1 time or 2 times. If more than one meta-hetero group is present, they are of the same species or different. The two O atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylene groups). The alkenyl group is straight or branched and is as defined above. For example, the following structural units can be formed: -CH=CH-O- _CH2CH3 , -CH ₌ CH-O-CH= _CH2 , and the like.

The _C4 - _{C8cycloalkenyl} has one or more double bonds and is, for example, a _C4 - _C6 -cycloalkenyl or a _C6 - _C8 -cycloalkenyl. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

The C3 _{- C6alkenyloxy} is mono- or polyunsaturated straight-chain or branched and is one of the meanings given above for alkenyl, and the connecting oxy has the highest corresponding number of C atoms. Examples are allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.

The C2 _{- C12alkynyl} group is a mono- or polyunsaturated straight or branched chain and is, for example, a C2-C8-, _{C2 - C6-} or _{C2 - C4alkynyl} group. Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl , octynyl, etc.

The C2 _{- C20alkanoyl} is straight-chain or branched and is, for example, C2 _{- C18-} , C2- _C14- , C2 _{- C12-} , _{C2 - C8-} , _C2- C ₆ - or C ₂ -C ₄ alkanoyl or C ₄ -C ₁₂ - or C ₄ -C ₈ alkanoyl. Examples are acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, dodecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, Octadecyl and eicosyl, preferably acetyl. C ₁ -C ₈ alkanoyl has the same meaning as given above for C ₂ -C ₂₀ alkanoyl and has the highest corresponding number of C atoms.

The C ₂ -C ₁₂ alkoxycarbonyl is linear or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially methoxy carbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl or isobutoxycarbonyl, preferably methoxycarbonyl.

The C ₂ -C ₁₂ alkoxycarbonyl group interspersed with one or more Os is straight or branched. The two O atoms are separated by at least two methylene groups (ie, ethylene groups). The intervening alkoxycarbonyl group is unsubstituted or substituted with one or more hydroxy groups. The C ₆ -C ₂₀ aryloxycarbonyl group is, for example, phenyloxycarbonyl [=phenyl-O-(CO)-], naphthoxycarbonyl, anthracenyloxycarbonyl and the like. _C5 - _{C20heteroaryloxycarbonyl} is _C5 - _{C20heteroaryl} -O-CO-.

The C ₃ -C ₁₀ cycloalkylcarbonyl group is C ₃ -C ₁₀ cycloalkyl-CO-, wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms. The C ₃ -C ₁₀ cycloalkylcarbonyl group interspersed with one or more O, S, CO, NR ₂₆ refers to meta-heterocycloalkyl-CO-, wherein meta-heterocycloalkyl is as defined above.

The C ₃ -C ₁₀ cycloalkoxycarbonyl group is C ₃ -C ₁₀ cycloalkyl-O-(CO)-, wherein the cycloalkyl group has one of the meanings indicated above and has the highest corresponding number of C atoms. C ₃ -C ₁₀ cycloalkoxycarbonyl interspersed with one or more O, S, CO, NR ₂₆ refers to meta-heterocycloalkyl-O-(CO)-, wherein meta-heterocycloalkyl is as described above defined.

The C ₁ -C ₂₀ alkylphenyl group refers to a phenyl group substituted with one or more alkyl groups, wherein the sum of the C atoms is up to 20.

基、并四苯基、联伸三苯基等，尤其苯基或萘基，较佳为苯基。萘基是1-萘基或2-萘基。The _C6 - _C20 aryl group is, for example, phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl,

phenyl, naphthyl, triphenyl, etc., especially phenyl or naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

唏基、呫吨基、噻吨基、啡恶噻基、吡咯基、咪唑基、吡唑基、吡嗪基、嘧啶基、哒嗪基、中氮茚基、异吲哚基、吲哚基、吲唑基、嘌呤基、喹嗪基、异喹啉基、喹啉基、酞嗪基、萘啶基、喹恶啉基、喹唑啉基、啉基、喋啶基、咔唑基、β-咔啉基、菲啶基、吖啶基、萘嵌间二氮苯基、菲咯啉基、吩嗪基、异噻唑基、吩噻嗪基、异恶唑基、呋呫基、吩恶基、7-菲基、蒽醌-2-基(＝9，10-二侧氧基-9，10-二氢蒽-2-基)、3-苯并[b]噻吩基、5-苯并[b]噻吩基、2-苯并[b]噻吩基、4-二苯并呋喃基、4，7-二苯并呋喃基、4-甲基-7-二苯并呋喃基、2-呫吨基、8-甲基-2-呫吨基、3-呫吨基、2-啡恶噻基、2，7-啡恶噻基、2-吡咯基、3-吡咯基、5-甲基-3-吡咯基、2-咪唑基、4-咪唑基、5-咪唑基、2-甲基-4-咪唑基、2-乙基-4-咪唑基、2-乙基-5-咪唑基、1H-四唑-5-基、3-吡唑基、1-甲基-3-吡唑基、1-丙基-4-吡唑基、2-吡嗪基、5，6-二甲基-2-吡嗪基、2-中氮茚基、2-甲基-3-异吲哚基、2-甲基-1-异吲哚基、1-甲基-2-吲哚基、1-甲基-3-吲哚基、1，5-二甲基-2-吲哚基、1-甲基-3-吲唑基、2，7-二甲基-8-嘌呤基、2-甲氧基-7-甲基-8-嘌呤基、2-喹嗪基、3-异喹啉基、6-异喹啉基、7-异喹啉基、3-甲氧基-6-异喹啉基、2-喹啉基、6-喹啉基、7-喹啉基、2-甲氧基-3-喹啉基、2-甲氧基-6-喹啉基、6-酞嗪基、7-酞嗪基、1-甲氧基-6-酞嗪基、1，4-二甲氧基-6-酞嗪基、1，8-萘啶-2-基、2-喹恶啉基、6-喹恶啉基、2，3-二甲基-6-喹恶啉基、2，3-二甲氧基-6-喹恶啉基、2-喹唑啉基、7-喹唑啉基、2-二甲基胺基-6-喹唑啉基、3-啉基、6-啉基、7-啉基、3-甲氧基-7-啉基、2-喋啶基、6-喋啶基、7-喋啶基、6，7-二甲氧基-2-喋啶基、2-咔唑基、3-咔唑基、9-甲基-2-咔唑基、9-甲基-3-咔唑基、β-咔啉-3-基、1-甲基-β-咔啉-3-基、1-甲基-β-咔啉-6-基、3-菲啶基、2-吖啶基、3-吖啶基、2-萘嵌间二氮苯基、1-甲基-5-萘嵌间二氮苯基、5-菲咯啉基、6-菲咯啉基、1-吩嗪基、2-吩嗪基、3-异噻唑基、4-异噻唑基、5-异噻唑基、2-吩噻嗪基、3-吩噻嗪基、10-甲基-3-吩噻嗪基、3-异恶唑基、4-异恶唑基、5-异恶唑基、4-甲基-3-呋呫基、2-吩恶基、10-甲基-2-吩恶基等。In the context of the present invention, the C3 _{- C20} heteroaryl group comprises monocyclic or polycyclic ring systems, eg fused ring systems. Examples are thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthyl, furyl, dibenzofuranyl,

Sulfonyl, xanthyl, thioxanthyl, phenothiyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizine, isoindolyl, indolyl , indazolyl, purinyl, quinazinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxolinyl, quinazolinyl, olinyl, pteridyl, carbazolyl, β-Carboline, phenanthridine, acridine, rylene, phenanthroline, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furanyl, phen oxanyl, 7-phenanthrenyl, anthraquinone-2-yl (=9,10-di-oxy-9,10-dihydroanthracene-2-yl), 3-benzo[b]thienyl, 5- Benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2 -Xanthyl, 8-methyl-2-xanthyl, 3-xanthyl, 2-phenanthyl, 2,7-phenothiyl, 2-pyrrolyl, 3-pyrrolyl, 5- Methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5- Imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6- Dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indole base, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl , 2-methoxy-7-methyl-8-purinyl, 2-quinolinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 3-methoxy- 6-Isoquinolinyl, 2-quinolinyl, 6-quinolinyl, 7-quinolinyl, 2-methoxy-3-quinolinyl, 2-methoxy-6-quinolinyl, 6 -phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2 -quinoxolinyl, 6-quinoxolinyl, 2,3-dimethyl-6-quinoxolinyl, 2,3-dimethoxy-6-quinoxolinyl, 2-quinazolinyl , 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-olyl, 6-olyl, 7-olyl, 3-methoxy-7-olyl, 2 -Pteridyl, 6-pteridyl, 7-pteridyl, 6,7-dimethoxy-2-pteridyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2 -carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl, 1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6 -yl, 3-phenanthridine, 2-acridinyl, 3-acridinyl, 2-rylene, 1-methyl-5-rylene, 5-phenanthrene Linoyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phene Thiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazole base, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furanyl, 2-phenoxyl, 10-methyl-2-phenoxyl and the like.

The C3 _{- C20heteroaryl} is especially thienyl, benzo[b]thienyl, thianthyl, thioxanthyl, 1-methyl-2-indolyl or 1-methyl-3-indole group; especially thienyl.

The _C4 - _{C20heteroarylcarbonyl} is a C3 _{- C20heteroaryl} as defined above attached to the rest of the molecule via a CO group.

The substituted aryl (phenyl, naphthyl, _C6 - _C20 aryl or _C5 - _C20 heteroaryl) is respectively substituted 1 to 7 times, 1 to 6 times or 1 to 4 times, especially 1 times, 2 times or 3 times. Obviously, an aryl group as defined cannot have more substituents than the free positions at the aryl ring.

The substituent on the phenyl ring is preferably at position 4 on the phenyl ring or in a 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration .

The interstitial hetero group interspersed 1 or more times is interspersed (for example) 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times , 1 to 3 times or 1 time or 2 times (obviously, the number of interstitial atoms depends on the number of C atoms to be interspersed). One or more substituted substituted groups have, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3, or 1 or 2 identical or different substituents.

则形成(例如)以下结构(Ia)-I(i)：The group substituted with one or more of the defined substituents is one having one substituent or more substituents with the same or different definitions as given. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ independently of each other and together are

Then, for example, the following structures (Ia)-I(i) are formed:

Or (for example) structures such as (Id)-(Ih):

Preferred is structure (Ia).

The photoinitiator (C-1) having the structure represented by formula (C-I) is characterized in that at least one phenyl ring is fused with a carbazole moiety to form a "naphthyl" ring. That is, one of the above structures is given as a structure represented by the formula (C-I).

等结构。If R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together are -(CH ₂ ) _P -Y- (CH ₂ ) _q - then forms (for example) such as

etc. structure.

If the substituents OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ on the phenyl or naphthyl ring are bonded to the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ One carbon atom forms a 5- or 6-membered ring, and a structure containing 3 or more rings (including naphthyl rings) is obtained.

Example is

Wait.

的苯基或萘基环的一个碳原子的直接键，则形成(例如)诸如

等结构。If R ₁₇ forms a bond to a group having a

A direct bond to a carbon atom of the phenyl or naphthyl ring, then forms (for example) such as

etc. structure.

If R ₁₆ is SR ₁₈ substituted phenyl, wherein the group R ₁₉ represents a direct bond to the phenyl or naphthyl ring of the carbazole moiety to which the COR ₁₆ group is attached, forming, for example, such as

等结构。亦即，若R₁₆是经SR₁₈取代的苯基，其中基团R₁₈表示键结至其中连接有COR₁₆基团的咔唑部分的苯基或萘基环的直接键，则噻吨基部分与咔唑部分的一个苯基或萘基环一起形成。

etc. structure. That is, if R ₁₆ is SR ₁₈ substituted phenyl, wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring of the carbazole moiety to which the COR ₁₆ group is attached, then the thioxanthyl The moiety is formed with a phenyl or naphthyl ring of the carbazole moiety.

If R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally interspersed with O, S or NR ₁₇ , a saturated or unsaturated ring is formed, such as aziridine, pyrrole , thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine. Preferably, if R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring optionally interspersed with O, S or NR ₁₇ , then form an uninterrupted or interspersed O or unsaturated ring. A 5- or 6-membered saturated ring of NR ₁₇ , especially O.

)等。If R ₂₁ and R ₂₂ together with the N atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring optionally interspersed with O, S or NR ₂₆ , and the benzene ring is optionally condensed with the saturated or unsaturated ring, Then a saturated or unsaturated ring is formed, such as aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine or the corresponding ring-forming ring (E.g

)Wait.

If R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, the ring system comprises more than one ring (eg 2 or 3 rings) and one or more from the same or different species heteroatoms. Suitable heteroatoms are, for example, N, S, O or P, especially N, S or O. Examples are carbazole, indole, isoindole, indazole, purine, isoquinoline, quinoline, carboline, phenothiazine, and the like.

The term "and/or" or "or/and" in the context of the present invention means that not only one of the defined alternatives (substituents) can be present, but also a total of several defined alternatives (substituents), i.e. different A mixture of substitutes (substituents).

The term "at least" defines one or more, such as one or two or three, preferably one or both.

The term "optionally substituted" means that the group to which it refers is unsubstituted or substituted.

The term "optionally intervened" means that the group to which it refers is unintervened or intervened.

Throughout this specification and the claims below, unless the context requires otherwise, the word "comprise" or variations (eg, "comprises" or "comprising") should be understood to imply the inclusion of the integer or steps or groups of integers or groups of steps, but does not exclude any other integer or group of integers or groups of steps or groups of steps. The term "(meth)acrylate" in the context of this application refers to acrylates as well as the corresponding methacrylates.

The preferred ones indicated in the text for the compounds of the present invention in the context of the present invention refer to all claim categories, but also to claims directed to compositions, uses, methods, color filters, and the like.

The oxime esters of formula (CI) are prepared by methods described in the literature, for example by reacting the corresponding oxime with an acid halide, especially a chloride or an acid anhydride, in an inert solvent such as tert-butylmethane ether, tetrahydrofuran (THF) or dimethylformamide) in the presence of a base such as triethylamine or pyridine, or in a basic solvent such as pyridine. _In the following, as an example, the preparation of compounds of formula Ia, wherein R is an oxime ester group and X is a direct bond is [the reaction of compounds (Ib)-(Ih) is carried out starting from the appropriate oxime]:

R ₁ , R ₂ , R ₅ , R ₆ , R ₈ , R ₁₃ , R ₁₄ and R ₁₅ are as defined above, Hal means a halogen atom, especially Cl.

R ₁₄ is preferably methyl.

These reactions are well known to those skilled in the art and are typically carried out at temperatures from -15°C to +50°C, preferably 0 to 25°C.

When X is CO, the corresponding oxime is nitrosated by methylene nitrite with an alkyl nitrite such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, or isoamyl nitrite to synthesize. Then, esterification is carried out under the same conditions as described above:

Therefore, the present invention is also prepared by reacting the corresponding oxime compound with an acid halide of formula (a) or an acid anhydride of formula (b) in the presence of a base or a mixture of bases to prepare the compound having the structure represented by formula (C-I) as defined above Method of Photoinitiator (C-1).

wherein Hal is halogen, especially Cl, and R ₁₄ is as defined above.

The oximes required as starting materials can be obtained from standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992) or monographs (eg S.R. Sandler & W. Karo, Organicfunctional group preparations, Vol. 3, Academic Press ) can be obtained by various methods described in .

One of the most convenient methods is to react the aldehyde or ketone with hydroxylamine or a salt thereof, for example, in a polar solvent such as dimethylacetamide (DMA), aqueous DMA, ethanol or aqueous ethanol. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH-dependent and the base can be added at the beginning or continuously during the reaction. Basic solvents such as pyridine can also be used as bases and/or solvents or co-solvents. The reaction temperature is usually room temperature to the reflux temperature of the mixture, generally about 20°C to 120°C.

Corresponding ketone intermediates are prepared, for example, by methods described in the literature (eg, standard chemistry textbooks, eg, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992). In addition, the sequential Friedel-Crafts reaction can be effectively used to synthesize intermediates. Such reactions are well known to those skilled in the art.

Another convenient synthesis of oximes is the nitrosation of "active" methylenes with nitrous acid or alkyl nitrites. Alkaline conditions (as described in Organic Syntheses coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp. 199 and 840) and acidic conditions (as described in Organic Synthesis coll. Vol. V, p. 32 and pages 373, coll. vol. III, pp. 191 and 513, coll. vol. II, pp. 202, 204 and 363) both suitable for preparation for use in the present invention Oxime as starting material. Nitrous acid is generally produced from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, or isoamyl nitrite.

Another embodiment of the present invention is a photoinitiator (C-1) having a structure represented by the free formula (IA):

COR₁₆、OR₁₇、卤素、NO₂或

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen, C ₁ -C ₂₀ alkyl,

COR ₁₆ , OR ₁₇ , halogen, NO ₂ or

取代的C₂-C₁₀烯基；or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other

Substituted C ₂ -C ₁₀ alkenyl;

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together -(CH ₂ ) _P -Y- (CH ₂ ) _q -;

or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ or R ₇ and R ₈ independently of each other and together

R₉、R₁₀、R₁₁及R₁₂彼此独立地为氢、C₁-C₂₀烷基，该C₁-C₂₀烷基未经取代或经一或多个以下基团取代：卤素、苯基、CN、OH、SH、C₁-C₄-烷氧基、(CO)OH或(CO)O(C₁-C₄烷基)；provided that at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with _one or more of _the following groups: halogen, benzene group, CN, OH, SH, C ₁ -C ₄ -alkoxy, (CO)OH or (CO)O(C ₁ -C ₄ alkyl);

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other unsubstituted phenyl or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, CN, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, CN, OR ₁₇ , SR ₁₈ , SOR ₁₈ , SO ₂ R ₁₈ or NR ₁₉ R ₂₀ , wherein the substituent OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ forms a 5- or 6-membered ring with a carbon atom in the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ;

COR₁₆或NO₂；or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are

COR ₁₆ or NO ₂ ;

Y is O, S, _NR or a direct bond;

p is an integer 0, 1, 2, or 3;

q is an integer 1, 2 or 3;

X is CO or direct bond;

R ₁₃ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ or

Or R ₁₃ is C ₂ -C ₂₀ alkyl, which is mixed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO, or C ₂ -C ₁₂ alkenyl, which is not interspersed or interspersed with one or more A plurality of O, CO or NR ₂₆ , wherein the intervened C ₂ -C ₂₀ alkyl and the uninterrupted or intervened C ₂ -C ₁₂ alkenyl are unsubstituted or substituted with one or more halogens;

or R ₁₃ is C ₄ -C ₈ cycloalkenyl, C ₂ -C ₁₂ alkynyl or C ₃ -C ₁₀ cycloalkyl, which is not interspersed or interspersed with one or more O, S, CO or NR ₂₆ ;

COR₁₆、CN、NO₂、卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、C₂-C₂₀烷基，其间杂有一或多个O、S、CO或NR₂₆；或其各经C₃-C₁₀环烷基或间杂有一或多个O、S、CO或NR₂₆的C₃-C₁₀环烷基取代；or R ₁₃ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

COR ₁₆ , CN, NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, mixed with one or more O, S, CO or NR ₂₆ ; or Each of which is substituted with C ₃ -C ₁₀ cycloalkyl or C ₃ -C ₁₀ cycloalkyl interspersed with one or more O, S, CO or NR ₂₆ ;

k is an integer from 1 to 10;

R ₁₅ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN , NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ , SO-C ₁ -C ₁₀ alkyl, SO ₂ -C ₁ -C ₁₀ alkyl, interspersed with one or A plurality of C2- _C20 alkyl groups of O, S, or NR ₂₆ ; or each substituted with _{a C1 - C20} alkyl group that is unsubstituted or substituted with one or more of _the following groups Substitution: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryl oxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₈ cycloalkyl, uninterrupted or interspersed with one or more O, CO or NR ₂₆ ;

苯基；或该C₁-C₂₀烷基经苯基取代，该苯基经卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、OR₁₇、SR₁₈或NR₁₉R₂₀取代；或R₁₅是C₂-C₂₀烷基，其间杂有一或多个O、SO或SO₂，且该经间杂的C₂-C₂₀烷基未经取代或经一或多个以下基团取代：卤素、OR₁₇、COOR₁₇、CONR₁₉R₂₀、苯基或经OR₁₇、SR₁₈或NR₁₉R₂₀取代的苯基；or R ₁₅ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ hetero Aryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO(OC _k H _2k+1 ) ₂ ,

phenyl; or the C ₁ -C ₂₀ alkyl is substituted with phenyl which is substituted with halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ or R ₁₅ is C ₂ -C ₂₀ alkyl, which is mixed with one or more O, SO or SO ₂ , and the mixed C ₂ -C ₂₀ alkyl is unsubstituted or by one or more of the following groups Substitution: halogen, OR ₁₇ , COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl or phenyl substituted with OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ is C ₂ -C ₂₀ alkanoyl or benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₅ unsubstituted or substituted with one or more OR ₁₇ naphthoyl or C ₃ -C ₁₄ heteroarylcarbonyl;

Or R ₁₅ is C ₂ -C ₁₂ alkoxycarbonyl, which is uninterrupted or interspersed with one or more O and the interspersed or uninterrupted C ₂ -C ₁₂ alkoxycarbonyl is unsubstituted or substituted by one or Multiple hydroxyl substitutions;

or R ₁₅ is phenoxycarbonyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, C ₁ -C ₄ haloalkyl, phenyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₅ is CN, CONR ₁₉ R ₂₀ , NO ₂ , C ₁ -C ₄ haloalkyl, S(O) _m -C ₁ -C ₆ alkyl, unsubstituted or C ₁ - C ₁₂ alkyl or SO ₂ -C ₁ -C ₆ alkyl substituted S(O) _m -phenyl;

or R ₁₅ is SO ₂ O-phenyl, unsubstituted or substituted with C ₁ -C ₁₂ alkyl; or diphenylphosphono or bis(C ₁ -C ₄ alkoxy)-phosphono;

m is 1 or 2;

R' ₁₅ is one of the meanings given for R ₁₅ ;

X ₁ is O, S, SO or SO ₂ ;

X ₂ is O, CO, S or a direct bond;

R ₁₆ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl interspersed with one or more O, S or NR ₂₆ ; or each of them via one or more C ₁ -C ₂₀ Alkyl substituted, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ is hydrogen, unsubstituted or via C ₁ -C ₂₀ alkyl substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl, (CO)OH or (CO)O(C ₁ -C ₄ alkane or R ₁₆ is a C ₂ -C ₁₂ alkyl group interspersed with one or more O, S or NR ₂₆ ; or R ₁₆ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl;

or R ₁₆ is SR ₁₈ substituted phenyl, wherein the group R ₁₈ represents a direct bond to the phenyl or naphthyl ring of the carbazole moiety to which the COR ₁₆ group is attached;

n is 1 to 20;

R ₁₇ is hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)- (C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), SO ₂ -(C ₁ -C ₄ haloalkyl), O(C ₁ -C ₄ haloalkyl), C ₃ -C ₂₀ cycloalkyl or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O; or R ₁₇ is C ₂ -C ₂₀ alkyl interspersed with one or more of O, S or NR ₂₆ ; or R ₁₇ is (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₁ - _C8alkanoyl , C2 _{- C12alkenyl} , C3 _{- C6alkenoyl} or C3 _{- C20cycloalkyl} , which are not interspersed or interspersed with one or more O, S, CO or NR ₂₆ ;

or R ₁₇ is C ₁ -C ₈ alkyl-C ₃ -C ₁₀ cycloalkyl, which is not interspersed or interspersed with one or more O;

or R ₁₇ is benzoyl, which is unsubstituted or substituted with one or more C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy;

or R ₁₇ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, OH, C ₁ -C ₁₂ alkyl, C ₁ - C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N(C ₁ -C ₁₂ alkane base) ₂ , diphenyl-amino or

的苯基或萘基环的一个碳原子的直接键；or R ₁₇ forms a bond to which has a group

A direct bond to one carbon atom of the phenyl or naphthyl ring;

R ₁₈ is hydrogen, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl or phenyl-C ₁ -C ₃ alkyl, wherein C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl Or phenyl-C ₁ -C ₃ alkyl is not interspersed or interspersed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ;

or R ₁₈ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO) - phenyl or (CO)OR ₁₇ ;

Or R ₁₈ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; or R ₁₈ is (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O ) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₈ alkanoyl or C ₃ -C ₆ alkenoyl; or R ₁₈ is benzoyl, unsubstituted or substituted by one or more Substitution of the following groups: C ₁ -C ₆ alkyl, halogen, OH, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio;

or R ₁₈ is phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ Haloalkyl, C ₁ -C ₁₂ alkoxy, CN, NO ₂ , phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N( C ₁ -C ₁₂ alkyl) ₂ , diphenylamine, (CO)O(C ₁ -C ₈ alkyl), (CO)-C ₁ -C ₈ alkyl, (CO)N(C ₁ - C ₈ alkyl) ₂ or

R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₅ alkenyl, C ₃ - C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, SO ₂ -(C ₁ -C ₄ haloalkyl), C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl or benzoyl; or R ₁₉ and R ₂₀ are phenyl, naphthyl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, C ₁ -C ₁₂ alkyl, benzoyl or C ₁ -C ₁₂ alkoxy;

或C₃-C₂₀环烷基，该C₃-C₂₀环烷基未经间杂或间杂有一或多个O、S、CO或NR₁₇；或R₁₉及R₂₀与其所连接的N原子一起形成杂芳香族环系统，该环系统未经取代或经一或多个以下基团取代：C₁-C₂₀烷基、C₁-C₄卤代烷基、C₁-C₂₀烷氧基、＝O、OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、

卤素、NO₂、CN、苯基或C₃-C₂₀环烷基，该C₃-C₂₀环烷基未经间杂或间杂有一或多个O、S、CO或NR₁₇；Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₁₇ , and the 5-membered or 6-membered saturated or unsaturated ring Unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, =O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ , NO ₂ , halogen, C ₁ -C ₄ -haloalkyl, CN, phenyl,

or C ₃ -C ₂₀ cycloalkyl, the C ₃ -C ₂₀ cycloalkyl is not interspersed or interspersed with one or more O, S, CO or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached Heteroaromatic ring systems are formed which are unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₂₀ alkoxy, = O, OR ₁₇ , SR ₁₈ , NR ₂₁ R ₂₂ , (CO)R ₂₃ ,

Halogen, NO ₂ , CN, phenyl or C ₃ -C ₂₀ cycloalkyl, which C ₃ -C ₂₀ cycloalkyl is not interspersed or interspersed with one or more O, S, CO or NR ₁₇ ;

R ₂₁ and R ₂₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl or phenyl;

Or R ₂₁ and R ₂₂ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring without intervening or intervening O, S or NR ₂₆ , and the 5-membered or 6-membered saturated or unsaturated ring Not fused or the 5- or 6-membered saturated or unsaturated ring is fused with a benzene ring;

R ₂₃ is hydrogen, OH, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, CO or NR ₂₆ , uninterrupted or interspersed with O , S, CO or C ₃ -C ₂₀ cycloalkyl of NR ₂₆ , or R ₂₃ is phenyl, naphthyl, phenyl-C ₁ -C ₄ alkyl, OR ₁₇ , SR ₁₈ or NR ₂₁ R ₂₂ ; R ₂₄ is (CO)OR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₄ is one of the meanings given for R ₁₉ and R ₂₀ ;

R ₂₅ is COOR ₁₇ , CONR ₁₉ R ₂₀ , (CO)R ₁₇ ; or R ₂₅ is one of the meanings given for R ₁₇ ; R ₂₆ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkane Alkyl, C ₂ -C ₂₀ alkyl, which are mixed with one or more O or CO; or phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl, which are not mixed or mixed with one or more multiple O or CO; or (CO)R ₁₉ ; or phenyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkane base, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or

provided that at least one group is present in the molecule

)皆替换为相应游离肟基团

Preferred groups defined for the photoinitiator (C-1) of the structure represented by the formula (IA) correspond to those defined for the photoinitiator (C-1) of the structure represented by the formula (CI) as given below 1) given, only for each oxime ester group as defined (e.g.

) are replaced with corresponding free oxime groups

Each oxime ester group can exist in two configurations (Z) or (E). Isomers can be separated by conventional methods, but it is also possible to use isomer mixtures as, for example, photo-starting materials. Therefore, the present invention also relates to a mixture of configurational isomers of the photoinitiator (C-1) of the structure represented by the formula (C-I).

COR₁₆或NO₂，或R₁及R₂、R₂及R₃、R₃及R₄、R₅及R₆、R₆及R₇或R₇及R₈彼此独立地共同为

The preferred one is the photoinitiator (C-1) of the structure represented by the formula (CI) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ independently of each other are hydrogen, C ₁ -C ₂₀ alkyl,

COR ₁₆ or NO ₂ , or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ independently of each other and together

provided that at least one pair of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , or R ₇ and R ₈ is

X is CO or direct bond;

R ₁₃ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, OR ₁₇ , SR ₁₈ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ;

Or R ₁₃ is C ₂ -C ₂₀ alkyl, which is mixed with one or more O, S, NR ₂₆ or CO;

或COR₁₆取代；or R ₁₃ is phenyl or naphthyl, both unsubstituted or substituted by one or more

or COR ₁₆ superseded;

R ₁₄ is C ₁ -C ₂₀ alkyl, phenyl or C ₁ -C ₈ alkoxy;

R ₁₅ is phenyl, naphthyl, C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ or C ₂ -C ₂₀ alkyl, which is mixed with one or more O or S; or each substituted by one or more C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or Substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R _2o , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl , C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ;

or R ₁₅ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl , NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ;

R' ₁₄ is one of the meanings given for R ₁₄ ;

R' ₁₅ is one of the meanings given for R ₁₅ ;

R ₁₆ is phenyl, unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ , or a C ₂ -C ₂₀ alkane interspersed with one or more O, S or NR ₂₆ radical, or R ₁₆ is phenyl substituted with _one or _more C ₁ -C ₂₀ alkyl groups that are unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₄ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ;

or R ₁₆ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with: halogen, phenyl, OH, SH, CN, C ₃ -C ₆ alkenyloxy, OCH ₂ CH ₂ (CO) O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl) or (CO)O(C ₁ -C ₄ alkyl);

R ₁₇ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(C ₁ -C ₄ alkyl), (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O; or

R ₁₇ is C ₂ -C ₂₀ alkyl, which is mixed with one or more O;

R ₁₈ is methyl substituted with (CO)OR ₁₇ ;

R ₁₉ and R ₂₀ are independently of each other hydrogen, phenyl, C ₁ -C ₂₀ alkyl, C ₁ -C ₈ alkanoyl or C ₁ -C ₈ alkanoyloxy;

取代；or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or

replace;

provided that at least one group is present in the molecule

COR₁₆或NO₂，R₃及R₄一起为

Attention must be paid to the photoinitiator (C-1) of the structure represented by formula (CI) as defined above, wherein R ₁ , R ₂ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen,

COR ₁₆ or NO ₂ , R ₃ and R ₄ together are

R9, _R10 , _R11 and _R12 are hydrogen;

X is a direct key;

R ₁₃ is C ₁ -C ₂₀ alkyl;

R ₁₄ is C ₁ -C ₂₀ alkyl;

R ₁₅ is C ₁ -C ₂₀ alkyl or phenyl substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl;

R ₁₆ is phenyl substituted with one or more C ₁ -C ₂₀ alkyl or OR ₁₇ ; and

R ₁₇ is an unsubstituted or C ₁ -C ₂₀ alkyl group substituted with one or more halogens or a C ₂ -C ₂₀ alkyl group interspersed with one or more O;

provided that at least one group is present in the molecule

The subject matter of the present invention is further a photoinitiator (C-1) having a structure represented by formula (CI) as defined above, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ independently of each other are hydrogen, or R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ independently of each other and together are

provided that at least one pair of R ₁ and R ₂ , R ₃ and R ₄ or R ₅ and R ₆ is

COR₁₆、NO₂或

or _R2 is

COR ₁₆ , NO ₂ or

或COR₁₆；or _R7 is

or COR ₁₆ ;

R ₉ , R ₁₁ and R ₁₂ are hydrogen;

R ₁₀ is hydrogen, OR ₁₇ or COR ₁₆ ;

X is CO or direct bond;

R ₁₃ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H _2k+1 ) ₂ ;

Or R ₁₃ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O;

or R ₁₃ is phenyl;

k is the integer 2;

R ₁₄ is C ₁ -C ₂₀ alkyl or thienyl;

R ₁₅ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more OR ₁₇ or C ₁ -C ₂₀ alkyl; or R ₁₅ is thienyl, hydrogen, C ₁ -C ₂₀ alkyl, the C ₁ -C ₂₀ alkyl is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , C ₃ -C ₈ cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ;

or R ₁₅ is a C ₂ -C ₂₀ alkyl group with SO ₂ mixed therebetween;

R ₁₆ is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl;

or R ₁₆ is thienyl;

R ₁₇ is hydrogen, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, unsubstituted or through one or more of the following groups: halogen, O(CO)-(C ₁ -C ₄ alkyl ), O(CO)-(C ₂ -C ₄ ) alkenyl or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O;

Or R ₁₇ is a C ₂ -C ₂₀ alkyl group, which is mixed with one or more O;

R ₁₈ is C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more OH, O(CO)-(C ₂ -C ₄ )alkenyl or (CO) OR ₁₇ substituted;

or _R18 is phenyl, which is unsubstituted or substituted with one or more halogens;

R ₁₉ and R ₂₀ are independently of each other C ₁ -C _8alkanoyl or C ₁ -C _8alkanoyloxy ;

Or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a 5-membered or 6-membered saturated ring interspersed with O;

provided that at least one group is present in the molecule

Examples of compounds of the present invention are compounds of formulae (Ia)-(Ig) as defined above. Compounds of formula (Ia), (Ib), (Ic), especially formula (Ia) or (Ic) or formula (Ia), (Ic) or (Id), especially formula (Ia) are of interest.

或COR₁₆，或R₁及R₂、R₂及R₃、R₃及R4或R₅及R₆、R₆及R₇、R₇及R₈彼此独立地共同为

For example, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen,

or COR ₁₆ , or R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R 4 or R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ independently of each other and together

或R₃及R₄及R₅及R₆共同为

R₃及R₄尤其共同为

For example, R ₃ and R ₄ or R ₁ and R ₂ together are

Or R ₃ and R ₄ and R ₅ and R ₆ together are

R ₃ and R ₄ are especially jointly

For example, R ₁ , R ₅ , R ₆ and R ₈ are hydrogen.

或COR₁₆。或R₇是

或COR₁₆、尤其为

R ₇ is especially hydrogen,

or COR ₁₆ . or _R7 is

or COR ₁₆ , especially for

COR₁₆或

或R₂与R₁一起为

R₂尤其为COR₁₆。 _R2 is especially

COR ₁₆ or

or _{R2 together} with R1 is

R ₂ is in particular COR ₁₆ .

X is preferably a direct bond.

或COR₁₆。For example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ , wherein the substituents OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ forms a 5- or 6-membered ring with one carbon atom of the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other for

or COR ₁₆ .

或COR₁₆。Specifically, for example, R9, _R10 , _R11 , and _R12 are independently of each other hydrogen, _C1 - _C20 alkyl, unsubstituted phenyl, or benzene substituted with one or more of the following groups group: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other

or COR ₁₆ .

或COR₁₆。For example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or substituted with one or more C ₁ -C ₆ alkyl phenyl; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other

or COR ₁₆ .

In another embodiment, for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or via one or more of the following group-substituted phenyl: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ ; or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ , wherein the substituent OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ forms a 5- or 6-membered ring with one carbon atom of the naphthyl ring via the groups R ₁₇ , R ₁₈ , R ₁₉ and/or R ₂₀ .

Furthermore, for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups : C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of each other are halogen, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or COR ₁₆ .

Or for example, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, unsubstituted phenyl, or phenyl substituted with one or more of the following groups: C ₁ -C ₆ alkyl, halogen, OR ₁₇ or SR ₁₈ , or R ₉ , R ₁₀ , R ₁₁ and R ₁₂ independently of one another are halogen, OR ₁₇ , COR ₁₆ or NR ₁₉ R ₂₀ .

Preferably, R ₉ , R ₁₁ and R ₁₂ are hydrogen and R ₁₀ is hydrogen, OR ₁₇ or COR ₁₆ .

COR₁₆、NO₂、卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、C₂-C₂₀烷基，其间杂有一或多个O；或是C₁-C₂₀烷基，其未经取代或经一或多个以下基团取代：卤素、R₁₇、COOR₁₇、OR₁₇、SR₁₈、CONR₁₉R₂₀或PO(OC_kH_2k+1)₂；或是C₂-C₂₀烷基，其间杂有一或多个O。R ₁₃ is, for example, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, COOR ₁₇ or CONR ₁₉ R ₂₀ ; or R ₁₃ is C ₂ -C ₂₀ alkyl , which is mixed with one or more O, S, SO, SO ₂ , NR ₂₆ or CO, or C ₂ -C ₁₂ alkenyl, which is mixed with one or more O, CO or NR ₂₆ as the case may be, or R ₁₃ is C ₃ -C ₁₀ cycloalkyl, optionally interspersed with one or more O, S, CO, NR ₂₆ , or R ₁₃ is phenyl or naphthyl, both unsubstituted or through one or more of the following Group substitution: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

COR ₁₆ , NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, mixed with one or more O; or C ₁ -C ₂₀ alkyl, It is unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; or C ₂ - C ₂₀ alkyl, mixed with one or more O.

COR₁₆、NO₂、卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、C₂-C₂₀烷基，其间杂有一或多个O。In addition, R ₁₃ is, for example, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , COOR ₁₇ , OR ₁₇ , SR ₁₈ , CONR ₁₉ R ₂₀ or PO(OC _k H _2k+1 ) ₂ ; or C ₂ -C ₂₀ alkyl with one or more Os in between; or C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₀ cycloalkyl; or R ₁₃ is phenyl or naphthyl, both unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ ,

COR ₁₆ , NO ₂ , halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, mixed with one or more O.

In another embodiment, R ₁₃ is, for example, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ , or PO(OC _k H _2k+1 ) ₂ ; or C ₂ -C ₂₀ alkyl, which is mixed with one or more O; or C ₂ -C ₁₂ alkenyl, C ₃ -C ₁₀ cycloalkyl, phenyl or naphthyl .

or R ₁₃ is, for example, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, R ₁₇ , OR ₁₇ , SR ₁₈ or PO(OC _k H2 _k+1 ) ₂ ; or C ₂ -C ₂₀ alkyl, which is mixed with one or more O; or phenyl, C ₂ -C ₁₂ alkenyl or C ₃ -C ₁₀ cycloalkyl.

Or R ₁₃ is, for example, C ₁ -C ₂₀ alkyl, phenyl, C ₂ -C ₁₂ alkenyl or C ₃ -C ₁₀ cycloalkyl.

Or R ₁₃ is, for example, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₂ alkenyl or C ₃ -C ₁₀ cycloalkyl.

Preferably, R ₁₃ is C ₁ -C ₂₀ alkyl, especially C ₁ -C ₈ alkyl, such as 2-ethylhexyl.

R ₁₄ is, for example, hydrogen, C ₃ -C ₈ cycloalkyl, C ₂ -C ₅ alkenyl, C ₁ -C ₂₀ alkoxy, or C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted by a mono- or Multiple halogen or phenyl substitution; or R ₁₄ is phenyl or naphthyl, both unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl , halogen, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; or R ₁₄ is C ₃ -C ₅ heteroaryl, such as thienyl, or C ₁ -C ₈ alkoxy, benzyloxy or phenoxy base.

or R ₁₄ is, for example, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more halogen or phenyl; or R ₁₄ is C ₃ -C ₅ heteroaryl (eg, thienyl) or unsubstituted phenyl substituted or substituted with one or more of the following groups: C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, halogen, OR ₁₇ , SR ₁₈ and/or NR ₁₉ R ₂₀ ; or R ₁₄ is _C1 - _C8alkoxy , benzyloxy or phenoxy.

In another embodiment, R ₁₄ represents C ₁ -C ₂₀ alkyl, unsubstituted or substituted with phenyl; or R ₁₄ is phenyl, unsubstituted or substituted with one or more C ₁ -C ₆ Alkyl substitution.

Preferably, R ₁₄ is C ₁ -C ₂₀ alkyl, C ₃ -C ₅ heteroaryl (eg thienyl), or phenyl, especially C ₁ -C ₂₀ alkyl or thienyl, especially C ₁ - _C8 alkyl.

苯基或经以下基团取代的苯基：卤素、C₁-C₂₀烷基、C₁-C₄卤代烷基、OR₁₇或NR₁₉R₂₀；或R₁₅是C₂-C₂₀烷基，其间杂有一或多个O、S或SO₂，或R₁₅是C₂-C₂₀烷酰基、苯甲酰基、C₂-C₁₂烷氧基羰基、苯氧基羰基、CONR₁₉R₂₀、NO₂或C₁-C₄卤代烷基。R ₁₅ is, for example, C ₆ -C ₂₀ aryl or C ₅ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkane or _{R 15 is} hydrogen, C _{3 -C 8 cycloalkyl} , _{the C 3 -C 8 cycloalkyl} optionally interspersed with one or more O, CO, or NR ₂₆ ; or R ₁₅ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following: halogen, OR ₁₇ , C ₃ -C ₈ cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₈ -C ₂₀ phenoxycarbonyl, C ₅ -C ₂₀ heteroaryloxy-carbonyl, NR ₁₉ R ₂₀ , COOR ₁₇ , CONR ₁₉ R ₂₀ , PO (OC _k H _2k+1 ) ₂ ,

Phenyl or phenyl substituted with halogen, _C1 - _C20 alkyl, _C1 - _C4 haloalkyl, OR ₁₇ or NR ₁₉ R ₂₀ ; or R ₁₅ is C ₂ -C ₂₀ alkyl, It is mixed with one or more O, S or SO ₂ , or R ₁₅ is C ₂ -C ₂₀ alkanoyl, benzoyl, C ₂ -C ₁₂ alkoxycarbonyl, phenoxycarbonyl, CONR ₁₉ R ₂₀ , NO ₂ or C ₁ -C ₄ haloalkyl.

Furthermore, R ₁₅ is, for example, hydrogen, C ₆ -C ₂₀ aryl, especially phenyl or naphthyl, each of which is unsubstituted or substituted with C ₁ -C ₁₂ alkyl; or C ₃ -C ₅ hetero Aryl, such as thienyl; or C3- _C8cycloalkyl , _C1 - _C20alkyl , unsubstituted or substituted with one or more _{of the} following groups: _OR17 , _SR17 , C3- C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ is C ₂ -C ₂₀ alkyl, mixed with one or more O or SO ₂ .

The photoinitiator (C-1) having the structure of formula (CI) is interesting, wherein R ₁₅ is, for example, hydrogen, phenyl, naphthyl, each of which is unsubstituted or C ₁ -C ₈ Alkyl-substituted; or R ₁₅ is thienyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₇ , C ₃ -C ₈ -cycloalkyl, NR ₁₉ R ₂₀ or COOR ₁₇ ; or R ₁₅ is a C ₂ -C ₂₀ alkyl group mixed with one or more O or SO ₂ .

R ₁₅ is especially, for example, C ₃ -C ₈ cycloalkyl or C ₁ -C ₂₀ alkyl, especially C ₁ -C ₂₀ alkyl, especially C ₁ -C ₁₂ alkyl.

Preferred for _R'14 and _R'15 are as given above for _R14 and _R15 , respectively.

X ₁ is, for example, O, S or SO, for example O or S, especially O.

R ₁₆ is, for example, C ₆ -C ₂₀ aryl (especially phenyl or naphthyl, especially phenyl) or C ₅ -C ₂₀ heteroaryl (especially thienyl), each of which is unsubstituted or substituted by one or more Substituted with one of the following groups: phenyl, halogen, C ₁ -G ₄ haloalkyl, CN, NO ₂ , OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl interspersed with one or more O; or each substituted with _one or _more C ₁ -C ₂₀ alkyl groups which are unsubstituted or substituted with one or more of the following groups: halogen, COOR ₁₇ , CONR ₁₉ R ₂₀ , benzene radical, C ₃ -C ₈ cycloalkyl, C ₅ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₅ -C ₂₀ heteroaryloxycarbonyl, OR ₁₇ , SR ₁₈ or NR ₁₉ R ₂₀ ; or R ₁₆ is hydrogen, C ₁ -C ₂₀ alkyl, which is unsubstituted or substituted with _one or more of _the following groups: halogen, phenyl, OH, SH, C ₃ - C ₆ alkenyloxy, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-phenyl, (CO) OH or (CO)O(C ₁ -C ₄ alkyl); or R ₁₆ is C ₂ -C ₁₂ alkyl, mixed with one or more O; or (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl, and n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

Furthermore, R ₁₆ is, for example, phenyl or naphthyl, especially phenyl, thienyl or carbazole, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: Halogen, Phenyl, OH, SH, C3 _{- C6alkenyloxy} , _OCH2CH2 ( _CO )O( _{C1 -} C4Alkyl), O(CO)-( _{C1 -} C4Alkyl) , O(CO)-phenyl, (CO)OH, or (CO)O(C ₁ -C ₄ alkyl); or R ₁₆ is C ₂ -C ₁₂ alkyl, mixed with one or more O; or (CH ₂ CH ₂ O) _n+1 H, (CH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl), C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl , and n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

Furthermore, R ₁₆ is, for example, phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl; or R ₁₆ is C ₃ -C ₅ heteroaryl, especially thienyl.

R ₁₆ is especially, for example, phenyl, which is unsubstituted or substituted with one or more of the following groups: OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ or C ₁ -C ₂₀ alkyl, or R ₁₆ is thienyl .

Preferably, R ₁₆ is, for example, phenyl or naphthyl, each of which is unsubstituted or substituted with one or more C ₁ -C ₂₀ alkyl groups.

R ₁₆ is especially phenyl substituted with one or more C ₁ -C ₂₀ alkyl groups.

R ₁₇ is, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, OCH ₂ CH ₂ (CO)O(C ₁ -C ₄ alkyl), O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-benzene group, (CO)OH, (CO)O(C ₁ -C ₄ alkyl), C ₃ -C ₂₀ cycloalkyl or C ₃ -C ₂₀ cycloalkyl interspersed with one or more O; or R ₁₇ is C ₂ -C ₂₀ alkyl, interspersed with one or more O; are (CH ₂ CH ₂ O) _n+1 H, (GH ₂ CH ₂ O) _n (CO)-(C ₁ -C ₈ alkyl) , C ₁ -C ₈ alkanoyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenoyl or C ₃ -C ₂₀ cycloalkyl, optionally interspersed with one or more O; or R ₁₇ is benzyl Acyl, unsubstituted or substituted with one or more _C1 - _C6 alkyl, halogen, OH, or _{C1 -} C3 alkoxy; or _R17 is phenyl, naphthyl, or C5- _C20 heteroaryl radicals, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, _C1 - _C12alkyl , _{C1 - C12alkoxy} , CN, NO2, phenyl _- C1- C ₃ alkoxy, phenoxy, C ₁ -C ₁₂ alkylthio, phenylthio, N(C ₁ -C ₁₂ alkyl) ₂ , diphenyl-amino or

In another embodiment, R ₁₇ is, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: halogen , O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or C ₂ -C ₂₀ alkyl interspersed with one or more O; or C ₁ -C ₈ alkanoyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₆ alkenoyl, C ₂ -C ₂₀ alkyl interspersed with one or more O, C ₃ -C interspersed with one or more O as appropriate ₂₀ cycloalkyl; or benzoyl, unsubstituted or substituted with one or more of the following: C ₁ -C ₆ alkyl, halogen, OH or C ₁ -C ₃ alkoxy; or benzene or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy.

R ₁₇ is also, for example, hydrogen, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups : halogen, C ₃ -C ₂₀ cycloalkyl, O(CO)-(C ₁ -C ₄ alkyl), O(CO)-(C ₂ -C ₄ alkenyl) or C interspersed with one or more O ₂ - _C20 alkyl, or _R17 is C2 _{- C20} alkyl, with one or more Os interspersed.

R ₁₇ is especially hydrogen, C ₁ -C ₈ alkanoyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: O(CO)-(C ₁ -C ₄ alkyl ), O(CO)-(C ₂ -C ₄ alkenyl) or C ₂ -C ₂₀ alkyl with one or more O interspersed, or R ₁₇ is C ₂ -C ₂₀ alkyl with one or more interspersed O.

R ₁₈ is, for example, C ₃ -C ₂₀ cycloalkyl, uninterrupted or interspersed with one or more O; or R ₁₈ is C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following Group substitution: OH, O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ ; or R ₁₈ is C ₂ -C ₂₀ alkyl, which is mixed with one or more O, S, CO, NR ₂₆ or COOR ₁₇ ; or R ₁₈ is C ₂ -C ₈ alkanoyl or C ₃ -C ₆ alkenoyl, benzoyl; or R ₁₈ is Phenyl, naphthyl or C3 _{- C20} heteroaryl, each of which is unsubstituted or substituted with one or more _of the following groups: halogen, _C1 -C12 alkyl, _C1 - _C4 haloalkyl, C ₁ -C ₁₂ alkoxy or NO ₂ .

In another embodiment, R ₁₈ is, for example, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ alkyl, unsubstituted or substituted with one or more of the following groups: OH, O(CO )-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ -C ₄ alkyl) or (CO)OR ₁₇ ; or R ₁₈ is phenyl or naphthyl, each of which is unsubstituted or One or more halogen or C ₁ -C ₁₂ alkyl, especially halogen substitution.

R ₁₈ is, for example, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₂ alkenyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₂ -C ₈ alkanoyl, Benzoyl, phenyl or naphthyl.

For example, R ₁₈ is C ₁ -C ₂₀ alkyl substituted with one or more of the following groups: OH, O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-(C ₁ - _C4 alkyl) or (CO)OR ₁₇ , or R ₁₈ is phenyl substituted with one or more halogens.

Preferably, R ₁₈ is C ₁ -C ₈ alkyl, which is substituted as defined above.

For example, R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C _{4hydroxyalkyl, C 3 -C 20} cycloalkyl, phenyl-C ₁ -C ₃ alkane group, phenyl or naphthyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl or benzoyl; or the N atom to which R ₁₉ and R ₂₀ are attached together to form a 5- or 6-membered saturated or unsaturated ring optionally interspersed with O, S or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a heteroaromatic ring system, which is unsubstituted or substituted with one or more of the following groups: C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl or

Also, for example, R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₄ hydroxyalkyl, C ₃ -C ₂₀ cycloalkyl, phenyl-C ₁ -C ₃ alkyl, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl or benzoyl; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form as the case may be A 5- or 6-membered saturated ring interspersed with O or NR ₁₇ ; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a carbazole ring.

For example, R ₁₉ and R ₂₀ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C _{4hydroxyalkyl, C 3 -C 20} cycloalkyl, phenyl-C ₁ -C ₃ alkane group, C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy, C ₃ -C ₁₂ alkenoyl or benzoyl; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a mixed as the case may be A 5- or 6-membered saturated ring of O or NR ₁₇ .

Preferably, R ₁₉ and R ₂₀ independently of each other are C ₁ -C ₈ alkanoyl, C ₁ -C ₈ alkanoyloxy; or R ₁₉ and R ₂₀ together with the N atom to which they are attached form a morpholine ring.

For example, R ₂₁ and R ₂₂ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₁₀ cycloalkyl, or phenyl; or R ₂₁ and R ₂₂ are therewith The attached N atoms together form a morpholine ring. R ₂₁ and R ₂₂ are in particular independently of one another hydrogen or C ₁ -C ₂₀ -alkyl.

R ₂₃ is, for example, hydrogen, OH, phenyl or C ₁ -C ₂₀ alkyl. R ₂₃ is especially hydrogen, OH or C ₁ -C ₄ alkyl.

Preferred for R ₂₄ are as given for R ₁₉ and R ₂₀ . Preferred for R ₂₅ are as given for R ₁₇ .

R ₂₆ is, for example, hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₂₀ alkyl, mixed with one or more O or CO; or phenyl -C ₁ - C ₄ alkyl, C ₃ -C ₈ cycloalkyl, optionally interspersed with one or more O or CO; or (CO)R ₁₉ or phenyl, unsubstituted or substituted with one or more of the following groups Substituted: C ₁ -C ₂₀ alkyl, halogen, C ₁ -C ₄ haloalkyl, OR ₁₇ , SR ₁₈ , NR ₁₉ R ₂₀ .

or R ₂₆ represents (for example) hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ haloalkyl; is phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₈ cycloalkyl, (CO)R ₁₉ or phenyl, which is unsubstituted or substituted with one or more _C1 - _C20 alkyl groups. Furthermore, R ₂₆ is, for example, hydrogen or C ₁ -C ₂₀ alkyl, especially C ₁ -C ₄ alkyl.

Examples of the photoinitiator (C-1) having the structure represented by the formula (C-I) of the present invention are shown in the following formulae (I-1) to (I-86).

Use of the photoinitiator (C-1) having the structure represented by the formula (C-I) for photopolymerizing a composition comprising at least one ethylenically unsaturated photopolymerizable compound.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the first photoinitiator (C-1) is 0.3 to 30 parts by weight, preferably 0.4 to 20 parts by weight , more preferably 0.5 to 10 parts by weight.

When the amount of the photoinitiator (C-1) having the structure represented by the formula (C-I) is within the above range, the black pattern obtained from the black photosensitive resin composition has a high dielectric constant and high The linearity of the fineness pattern is better.

If the black photosensitive resin composition of the present invention does not contain the first photoinitiator (C-1), the black pattern obtained from the black photosensitive resin composition has a dielectric constant and a high-definition pattern. Defects of poor straightness.

The black photosensitive resin composition of the present invention may optionally add a second photoinitiator (C-2). The second photoinitiator (C-2) of the present invention has the structure shown in the following formula (C-II):

In formula (C-II), E ₂₇ is independently selected from a hydrogen atom, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen atom.

Preferably, the second photoinitiator (C-2) can be 1-chloro-4-propoxythioxanthone (1-chloro-4-proxythioxanthone, CPTX) or isopropylthioxanthone (Isopropylthioxanthone, ITX).

Isopropylthioxanthone is a relatively inexpensive photoinitiator. And other second photoinitiators (C-2) suitable for the black photosensitive resin composition of the present invention may include but are not limited to thioxanthone, 2,4-diethylthioxanthone (or 2,4 -diethyl-9H-thiazol-9-one), 2-tert-butyl thioxanthone, 2-chlorothioxanthone or 2-propoxythioxanthone, etc.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the second photoinitiator (C-2) is 0.2 to 2 parts by weight, preferably 0.25 to 1.5 parts by weight, And more preferably, it is 0.3 to 1 weight part.

When the black photosensitive resin composition of the present invention contains the second photoinitiator (C-2), the linearity of the high-definition pattern of the black pattern prepared from the black photosensitive resin composition is better .

Another photoinitiator (C-3) can be selectively added to the black photosensitive resin composition of the present invention.

Specific examples of the other photoinitiator (C-3) may include O-acyl oxime compounds, triazine compounds, acetophenone compounds, and diimidazole compounds other than the first photoinitiator (C-1). , benzophenone compounds, alpha-diketone compounds, ketol compounds, ketol ether compounds, acylphosphine oxides, quinone compounds, halogen-containing compounds, peroxides, or any combination of the above compounds.

Specific examples of O-acyl oxime compounds other than the above-mentioned first photoinitiator (C-1) may include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2- (O-benzoyl oxime), 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyl oxime), 1-[4-(benzene Acyl)phenyl]-heptane-1,2-dione-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-Substituent]-ethanone-1-(O-acetyloxime), 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazole-3-substituent] -Ethanone-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazole-3-substituent)-ethanone-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl benzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime ), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl benzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl benzoyl)-9H-carbazole-3-substituent]-1-(O- acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-( O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-substituent ]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazole-3- Substituent]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H- Carbazole-3-substituent]-1-(O-acetyloxime), ethanone-1-{9-ethyl-6-[2-methyl-4-(2,2-dimethyl- 1,3-dioxolane)benzoyl]-9H-carbazole-3-substituent}-1-(O-acetyloxime), ethanone-1-{9-ethyl-6- [2-methyl-4-(2,2-dimethyl-1,3-dioxolane)methoxybenzoyl]-9H-carbazole-3-substituent}-1-(O -acetyl oxime) and other compounds, or any combination of the above compounds.

Preferably, the O-acyl oxime compound other than the first photoinitiator (C-1) can be 1-[4-(phenylthio)phenyl]-octane-1,2-dione- 2-(O-Benzoyl oxime), which can be a commodity manufactured by Ciba Refinery Co., Ltd., and the model is OXE-01; 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazole-3-substituent]-ethanone-1-(O-acetyl oxime), which can be a commodity manufactured by Ciba Refinery Co., Ltd., and the model is OXE-02; Ethanone-1 -[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyloxime); ethanone- 1-{9-Ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolane)methoxybenzoyl]-9H-carbazole- 3-Substituent}-1-(O-acetyloxime) or any combination of the above. These O-acyl oxime compounds may be used alone or in combination.

Specific examples of the above triazabenzene compounds may include, but are not limited to, vinyl-halomethyl-s-triazabenzene compounds, 2-(naphtho-1-substituent)-4,6-bis-halo Compounds such as methyl-s-triazabenzene compounds, 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compounds, or any combination of the above compounds.

Specific examples of the aforementioned vinyl-halomethyl-s-triazabenzene compound may include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene , 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene or 2-trichloromethane compound, or any combination of the above compounds.

Specific examples of the aforementioned 2-(naphtho-1-substituent)-4,6-bis-halomethyl-s-triazabenzene compound may include 2-(naphtho-1-substituent)-4, 6-Bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triaza Benzene, 2-(4-ethoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-butoxy-naphtho- 1-Substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-methoxyethyl)-naphtho-1-substituent]-4, 6-Bis-trichloromethyl-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphtho-1-substituent]-4,6-bis-trichloromethyl -s-triazabenzene, 2-[4-(2-butoxyethyl)-naphtho-1-substituent]-4,6-bis-trichloromethyl-s-triazabenzene, 2-(2-Methoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-methoxy-5-methyl- naphtho-2-substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-methoxy-naphtho-2-substituent)-4,6-bis -Trichloromethyl-s-triazabenzene, 2-(5-methoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2 -(4,7-Dimethoxy-naphtho-1-substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-ethoxy-naphtho- 2-Substituent)-4,6-bis-trichloromethyl-s-triazabenzene or 2-(4,5-dimethoxy-naphtho-1-substituent)-4,6-bis -Trichloromethyl-s-triazabenzene and other compounds, or any combination of the above compounds.

Specific examples of the aforementioned 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound may include 4-[p-N,N-bis(ethoxycarbonyl) Methyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl) ) aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6 -Bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloro Methyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p- -N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(phenyl)amino Phenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-bis(trichloromethyl) )-s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene , 4-[m-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo -p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p- N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N -Bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis( Ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxy) Carbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl) ) aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl] -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di (Trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl) -s-triazabenzene, 4-[m-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triaza Benzene, 4-[m-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m -Fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)- s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4 -(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p- N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-ethoxycarbonylmethyl) aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2, 6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl) )-s-triazabenzene, 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4- (m-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethyl aminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6- Bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-tris Azabenzene, 4-(o-Fluoro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene or 2,4-bis(triazine) Chloromethyl)-6-{3-bromo-4-[N,N-bis(ethoxycarbonylmethyl)amino]phenyl}-1,3,5-triazabenzene and other compounds, or the above Any combination of compounds.

The above-mentioned triazabenzene compound can preferably be 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)- s-triazabenzene, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, or a combination of the foregoing. These triazabenzene compounds can be used alone or in combination.

Specific examples of the above-mentioned acetophenone compound may include p-dimethylamine acetophenone, α,α'-dimethoxyazo acetophenone, 2,2'-dimethyl-2-phenyl Acetophenone, p-methoxyacetophenone, 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone or 2-methyl base-1-[4-(methylthio)phenyl]-2-(4-morpholino)-1-propanone and other compounds, or any combination of the above-mentioned compounds. The acetophenone compound is preferably 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholino)-1-propanone, 2-benzyl-2- N,N-Dimethylamine-1-(4-morpholinophenyl)-1-butanone. The above-mentioned acetophenone compounds may be used alone or in combination.

Specific examples of the above-mentioned diimidazole compound may include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorobenzene) base)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4 ',5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'- Bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)- 4,4',5,5'-tetraphenyldiimidazole or 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole and other compounds , or any combination of the above compounds. The above-mentioned diimidazole compounds may be used alone or in combination. The diimidazole compound can preferably be 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

Specific examples of the above-mentioned benzophenone compounds may include compounds such as benzophenone, 4,4'-bis(dimethylamine)benzophenone or 4,4'-bis(diethylamine)benzophenone, Or any combination of the above compounds. These benzophenone compounds may be used alone or in combination. The benzophenone compound is preferably 4,4'-bis(diethylamine)benzophenone.

Specific examples of the above-mentioned α-diketone compound may contain benzil, acetyl, and the like.

Specific examples of the above-mentioned ketone alcohol compound may include benzophenone.

Specific examples of the above-mentioned ketone alcohol ether compounds may include compounds such as benzophenone methyl ether, benzophenone ethyl ether, or benzophenone isopropyl ether, or any combination of the above-mentioned compounds.

Specific examples of the above-mentioned acylphosphine oxide may include 2,4,6-trimethylbenzoyldiphenylphosphine oxide or bis-(2,6-dimethoxybenzoyl)-2,4,4-tris Compounds such as methylphenylphosphine oxide, or any combination of the above.

Specific examples of the above-mentioned quinone compounds may include compounds such as anthraquinone or 1,4-naphthoquinone, or any combination of the above-mentioned compounds.

Specific examples of the above halogen-containing compounds may include compounds such as benzoyl methyl chloride, tribromomethyl phenyl sulfone, tris(trichloromethyl)-s-triazabenzene, or any combination of the above compounds.

Specific examples of the above-mentioned peroxide can include compounds such as di-tert-butyl peroxide.

Preferably, other photoinitiators (C-3) can be 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone -1-(O-Acetyl oxime), which can be a commodity manufactured by Ciba Refinery Co., Ltd., and the model is OXE-02; 1-[4-(phenylthio)phenyl]-octane-1 , 2-diketone-2-(O-benzoyl oxime), which can be a commodity manufactured by Ciba Refinery Co., Ltd., and the model is OXE-01; 2-methyl-1-(4-methylthio Phenyl)-2-morpholino-1-propanone, which can be a commercial product manufactured by Ciba Refinery Co., Ltd. and has the model number IRGACURE 907 or any combination of the above compounds.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the photoinitiator (C) used is 0.4 to 40 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably 0.6 to 20 parts by weight.

The solvent (D) of the present invention can dissolve the above-mentioned alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), and optionally the silane compound (F) having an epoxy group. , but does not react with the black pigment (E) described later, and has appropriate volatility.

Specific examples of the solvent (D) include alkyl glycol monoalkyl ether compounds, alkyl glycol monoalkyl ether acetate compounds, diethylene glycol alkyl ethers, other ether compounds, ketone compounds, and alkyl lactate Compounds, other ester compounds, aromatic hydrocarbon compounds, carboxylic acid amine compounds, or any combination of the foregoing. The above-mentioned solvent (D) may be used alone or in combination.

Specific examples of the aforementioned alkyl glycol monoalkyl ether compounds may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, and diethylene glycol mono-n-butyl ether ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether , tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether compound, or any combination of the above compounds.

Specific examples of the aforementioned alkyl glycol monoalkyl ether acetate compounds may include compounds such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate, or any combination of the above compounds .

Specific examples of the aforementioned diethylene glycol alkyl ether may include compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, or diethylene glycol diethyl ether, or any combination of the aforementioned compounds.

Specific examples of the aforementioned other ether compounds may include compounds such as tetrahydrofuran.

Specific examples of the aforementioned ketone compounds may include compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, or diacetone alcohol, or any combination of the aforementioned compounds.

Specific examples of the aforementioned alkyl lactate compound may include compounds such as methyl lactate or ethyl lactate, or any combination of the above compounds.

Specific examples of the aforementioned other ester compounds may include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl propionate, methyl 3-ethoxy propionate, ethyl 3-ethoxy propionate, ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methyl butyrate , 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate , isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Compounds such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate or ethyl 2-oxybutyrate, or any combination of the above compounds.

Specific examples of the aforementioned aromatic hydrocarbon compounds may include compounds such as toluene or xylene, or any combination of the foregoing compounds.

Specific examples of the aforementioned carboxylic acid amine compounds may be compounds such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, or any combination of the above-mentioned compounds.

Preferably, the solvent (D) can be propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate.

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the solvent (D) used is 300 parts by weight to 3000 parts by weight, preferably 400 parts by weight to 2000 parts by weight, and more preferably 500 parts by weight to 1500 parts by weight.

The black pigment (E) according to the present invention comprises the first black pigment (E-1), and may optionally comprise the second black pigment component (E-2), which will be described below.

The first black pigment (E-1) is a compound represented by the following formula (E-I), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof.

In formula (EI), R ^1e and R ^6e are independently hydrogen atom, CH ₃ , CF ₃ , fluorine atom or chlorine atom; R ^2e , R ^3e , R ^4e , R ^5e , R ^7e , R ^8e , R ^9e and R ^10e and all others independently of each other are hydrogen atom, halogen atom, R ^11e , COOH, COOR ^11e , COO-, CONH ₂ , CONHR ^11e , CONR ^11e R ^12e , CN, OH, OR ^11e , COCR ^11e , OOCNH ₂ , OOCNHR ^11e , OOCNR ^11e R ^12e , NO ₂ , NH ₂ , NHR ^11e , NR ^11e R ^12e , NHCOR ^12e , NR ^11e COR ^12e , N=CH ₂ , N=CHR ^11e , N=CR ^11e R ^12e , SH, SR ^11e , SOR ^11e , SO ₂ R ^11e , SO ₃ R ^11e , SO ₃ H, 5O ₃ -, SO ₂ NH ₂ , SO ₂ ^{NHR 11e} or SO ₂ ^{NR 11e} R ^12e ; At least one combination of the group consisting of R ^3e and R ^4e , R ^4e and R ^5e , R ^7e and R ^8e , R ^8e and R ^9e , and R ^9e and R ^10e , are directly bonded to each other, or through Oxygen atom, sulfur atom, NH or NR ^11e are bridged and bonded to each other; R ^11e and R ^12e are independently each other an alkyl group having 1 to 12 carbons, a cycloalkyl group having 3 to 12 carbons, and an alkene having 2 to 12 carbons. group, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

The geometric isomers of the compounds represented by the above formula (E-I) have the following core structures (however, the substituents in the structural formulas are omitted), and the trans-trans isomers may be the most stable.

When the compound represented by the above formula (E-I) is anionic, it is preferably by any known appropriate cation, such as metal, organic, inorganic or metal-organic cations, specifically, alkali metals, alkaline earth metals, Transition metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkyl ammonium, quaternary ammonium such as tetraalkyl ammonium, or salts in which the charge is compensated by organic metal complexes. Moreover, when the geometric isomer of the compound represented by the said formula (E-I) is anionic, it is preferable that it is the same salt.

Among the substituents of the above-mentioned formula (EI) and these definitions, the following are preferable in that the shielding ratio tends to be high. The reason for this is that the following substituents are thought to have no absorption and not affect the hue of the pigment. R ^2e , R ^4e , R ^5e , R ^7e , R ^9e and R ^10e are independent of each other, preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom. R ^3e and R ^8e are independent of each other, preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ —, more preferably a hydrogen atom or SO ₃ H.

R ^1e and R ^6e are independent of each other, preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom. Preferably, at least one combination selected from the group consisting of R ^1e and R ^6e , R ^2e and R ^7e , R ^3e and R ^8e , R ^4e and R ^9e , and R ^5e and R ^10e is the same, more preferably R ^1e is the same as R ^6e , R ^2e is the same as R ^7e , R ^3e is the same as R ^8e , R ^4e is the same as R ^9e , and R ^5e is the same as R ^10e .

The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2- Ethylhexyl, nonyl, decyl, undecyl or dodecyl.

基、

基、降蒈基(norcaryl)、蒈基(caryl)、

基、降蒎基(norpinyl)、蒎基(pinyl)、1-金刚烷基或2-金刚烷基。The cycloalkyl group having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, normyl

base,

base, norcaryl, caryl,

group, norpinyl, pinyl, 1-adamantyl or 2-adamantyl.

基-1-丁烯-3-基、2-甲基-3-丁烯-2-基、3-甲基-2-丁烯-1-基、1，4-戊二烯-3-基、己烯基、辛烯基、壬烯基、癸烯基或十二烯基。The alkenyl group having 2 to 12 carbon atoms is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butanedi En-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-

Alkyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl , hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

烯-8-基、4(10)-侧柏烯-10-基、2-降

烯-1-基、2，5-降

二烯-1-基、7，7-二甲基-2，4-降蒈二烯-3-基或莰烯基(camphenyl)。The cycloalkenyl having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl base, 2,4-cyclohexadien-1-yl, 1-pair

Alken-8-yl, 4(10)-thujene-10-yl, 2-nor

Alken-1-yl, 2,5-nor

Dien-1-yl, 7,7-dimethyl-2,4-norcaren-3-yl or camphenyl.

The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl base, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn -1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyne -9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In a preferred embodiment of the present invention, R ^2e , R ^4e , R ^5e , R ^7e , R ^9e and R ^10e of formula (EI) are independently hydrogen atom, fluorine atom or chlorine atom, R ^3e and R ^8e independently hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ -, R ^1e is the same as R ^6e , R ^2e is the same as R ^7e , R ^3e is the same as R ^8e , R ^4e Same as R ^9e , R ^5e same as R ^10e .

The first black pigment (E-1) is preferably a compound represented by the following formula (E-I-1).

Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the first black pigment (E-1) used is 15 to 150 parts by weight, preferably 20 to 130 parts by weight, and more It is preferably 25 parts by weight to 100 parts by weight.

When the amount of the first black pigment (E-1) is within the above range, the black pattern obtained from the black photosensitive resin composition has a better dielectric constant.

When the black pigment (E) of the present invention does not contain the first black pigment (E-1), the black pattern obtained from the black photosensitive resin composition has the defect of poor dielectric constant.

The second black pigment (E-2) includes but is not limited to (1) black organic pigments: perylene black, cyanine black, aniline black, etc.; (2) composed of From red, blue, green, violet, yellow, cyanine, magenta and other pigments, two or more pigments are selected and mixed to form a near-black color mixing organic pigment; (3) Shading material: carbon black, chromium oxide, iron oxide, titanium black, graphite, etc.

Specific examples of the above carbon black include, but are not limited to, C.I. Pigment black 7, or a commodity manufactured by Mitsubishi Chemical Corporation, and its model is MA100, MA220, MA230, MA8, #970, #1000, #2350 or #2650. The black pigment (E) can be used alone or in combination.

Preferably, the second black pigment (E-2) can be carbon black, or the aforementioned commercial product with the model number MA100 or MA230.

The black pigment (E) is used in an amount of 15 to 150 parts by weight, preferably 20 to 130 parts by weight, and more preferably 25 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A) parts to 100 parts by weight.

According to the black photosensitive resin composition of the present invention, the epoxy group-containing silane compound (F) is further included. The epoxy group-containing group that the epoxy group-containing silane compound (F) has is, for example, a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, or a cyclohexyl group. Oxetanyl group.

Specifically, the epoxy-containing group may include at least one of a group represented by formula (F-I), a group represented by formula (F-II), and a group represented by formula (F-III);

In formula (F-I), L represents an oxygen atom or a single bond; f represents an integer from 1 to 3; i represents an integer from 0 to 6, wherein when i represents 0, L represents a single bond;

In formula (F-II), j represents an integer from 0 to 6;

In formula (F-III), B represents an alkylene group having 2 to 6 carbon atoms; D represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The epoxy group-containing group preferably includes at least one of a group represented by formula (1-1), a group represented by formula (2-1), and a group represented by formula (3-1).

Specific examples of the epoxy group-containing silane compound (F) include 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3-(N-allyl-N-glycidyl ) aminopropyl trimethoxysilane, 3-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether propyl triethoxy silane, 3-glycidyl ether propyl methyl dimethoxy silane Silane, 3-glycidyl propyl methyl diethoxy silane, 3-glycidyl propyl dimethyl methoxy silane, 3-glycidyl propyl dimethyl ethoxy silane , 2-glycidyl ether base ethyl trimethoxy silane, 2-glycidyl ether base ethyl triethoxy silane, 2-glycidyl ether base ethyl methyl dimethoxy silane, 2-glycidyl ether base Ethylmethyldiethoxysilane, 2-glycidylethyldimethylmethoxysilane, 2-glycidylethyldimethylethoxysilane, 4-glycidylbutylbutyl Trimethoxysilane, 4-glycidylbutyltriethoxysilane, 4-glycidylbutylmethyldimethoxysilane, 4-glycidylbutylmethyldiethoxysilane, 4-glycidyl Glyceryl ether-based butyldimethylmethoxysilane, 4-glycidyl ether-based butyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2- (3,4-Epoxycyclohexyl)ethyltriethoxysilane, 3-)3,4-Epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-Epoxycyclohexyl)propyl triethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy) Propyltriethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propylmethyldimethoxysilane, or ((3-ethyl-3-epoxypropanyl) Methoxy)propanedimethylmethoxysilane, or a combination of the foregoing.

Specific examples of the epoxy group-containing silane compound (F) preferably include 3-glycidyl propyltrimethoxysilane, 2-glycidyl ethyl trimethoxysilane, and 4-glycidyl ether Butyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl))ethyltriethoxysilane, ((3 -Ethyl-3-epoxypropanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-epoxypropanyl)methoxy)propyltriethoxysilane or the above compounds The combination.

The amount of the epoxy-based silane compound (F) used is 0.5 to 5 parts by weight, preferably 0.6 to 4 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A), and more It is preferably 0.7 parts by weight to 3 parts by weight.

When the alkali-soluble resin (A) of the present invention contains the epoxy-group silane compound (F), the black pattern obtained from the black photosensitive resin composition has a better dielectric constant.

On the premise of not affecting the efficacy of the present invention, the black photosensitive resin composition of the present invention may further selectively add an additive (G). Specific examples of the additive (G) may include surfactants, fillers, adhesion promoters, antioxidants, anti-aggregation agents, or polymers other than the aforementioned alkali-soluble resin (A) that can increase various properties (eg, mechanical properties) thing.

Specific examples of the aforementioned surfactants may include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorine surfactants or the above-mentioned surfactants any combination of agents.

Specific examples of the surfactant may include, but are not limited to, polyethoxyalkyl ethers such as polyethoxy lauryl ether, polyethoxy stearyl ether or polyethoxy oleyl ether; polyethoxylate Polyethoxyalkyl phenyl ethers such as octyl phenyl ether or polyethoxy nonyl phenyl ether; polyethylene glycols such as polyethylene glycol dilaurate or polyethylene glycol distearate Diesters; sorbitan fatty acid ester compounds; fatty acid-modified polyester compounds; tertiary amine-modified polyurethane compounds; or commercial products. Among them, the commercially available commodity can be a product manufactured by Shin-Etsu Chemical Industry Co., Ltd., and its model is KP; a product manufactured by Dow Corning Toray Co., Ltd., and its model is SF-8427; Products manufactured by Kyoeisha Oil Chemical Industry, and its model is Polyflow; products manufactured by TochemProducts Co., Ltd., and its model is F-Top; products, and the model number is Megafac; products manufactured by Sumitomo 3M, and the model number is Fluorade; or products manufactured by Asahi Glass, and the model number is Asahi Guard or Surflon. These surfactants may be used alone or in combination.

Specific examples of the aforementioned filler can include glass, aluminum, or the like.

Specific examples of the aforementioned adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ring Oxypropoxypropyltrimethoxysilane (product of Shin-Etsu Chemical Co., Ltd., and its model is KBM-403), EPPN501H (manufactured by Nippon Kayaku Co., Ltd.), EPIKOTE152 (manufactured by Shell Chemical Co., Ltd.), 3-glycidoxy Propylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane Silane, compounds such as 3-methylpropionyloxypropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane, or any combination of the above.

Specific examples of the aforementioned antioxidants may include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or any combination of the foregoing compounds.

Specific examples of the aforementioned anti-aggregation agent may include compounds such as sodium polyacrylate.

Based on 100 parts by weight of the alkali-soluble resin (A), fillers, adhesion promoters, antioxidants, anti-aggregation agents, or polymers other than the alkali-soluble resin (A) in the additive (G) are not used in amounts More than 10 parts by weight, and preferably not more than 6 parts by weight.

Preparation of black photosensitive resin composition

The black photosensitive resin composition is prepared by placing the aforementioned alkali-soluble resin (A), compound (B) having an ethylenically unsaturated group, photoinitiator (C), solvent (D) and black pigment (E) on Stir in a stirrer to make it uniformly mixed into a solution state. If necessary, epoxy silane compounds (F) and/or additives (G) can also be added, and after uniform mixing, black photosensitivity in solution state can be obtained. resin composition.

Next, the preparation method of the black photosensitive resin composition is not particularly limited. The black pigment (E) can be directly added to the mixture consisting of the alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C) and the solvent (D), and is dispersible The photosensitive resin composition of the said solution state is formed. Alternatively, part of the black pigment (E) is first added to a mixture consisting of part of the alkali-soluble resin (A) and part of the solvent (D) to form a pigment dispersion. Then, the remaining alkali-soluble resin (A), the compound having an ethylenically unsaturated group (B), the photoinitiator (C), the remaining solvent (D) and the remaining black pigment (E) are added to the aforementioned In the pigment dispersion liquid, a photosensitive resin composition in a solution state is obtained.

The dispersing step of the above-mentioned black pigment (E) can be performed by a mixer such as a bead mill or a roll mill.

Preparation of black matrix/black spacer

The black matrix is prepared by coating the above-mentioned black photosensitive resin composition on a thin film transistor (TFT) substrate or a transparent substrate, and performing pre-baking treatment, exposure treatment, development treatment and post-baking treatment in sequence. Therefore, the method can be (1) an integrated color filter method, in which a color filter including a black matrix and a pixel layer is disposed on the substrate side of the TFT device; or (2) an integrated black matrix method, in which only the The black matrix is arranged on the substrate side of the TFT element, and the above method is not particularly limited. When the film thickness of the obtained black matrix is 2 μm, the optical density may be in the range of 3.0 or more, preferably 3.2 to 5.5, and more preferably 3.5 to 5.5.

In addition, the black matrix of the present invention is formed on the TFT substrate, and the method may be (1) an integrated color filter method, in which the color filter including the black matrix and the pixel layer is disposed on the substrate side of the TFT component; or (2) An integrated black matrix method, in which the black matrix is only provided on the substrate side of the TFT element, and the above method is not particularly limited.

When the above-mentioned black photosensitive resin composition was used to manufacture a black spacer, it was formed by the same method as above, and the thickness of the black spacer was 3 μm. The preparation method of the black matrix/black spacer of the present invention will be described in detail below.

First, a black photosensitive resin composition in a solution state is uniformly coated on a substrate by a coating method such as spin coating or cast coating to form a coating film. Specific examples of the above-mentioned substrates may include thin film transistor (TFT) substrates or transparent substrates used in liquid crystal display devices: alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz glass and the aforementioned A transparent conductive film is attached to the glass; or it is used for a photoelectric conversion device substrate (for example, a silicon substrate) such as a solid-state imaging device.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure. Then, the remaining solvent is removed in a pre-bake manner to form a pre-bake coating film. The above-mentioned conditions for drying under reduced pressure and pre-baking vary according to the types and ratios of the components. The drying under reduced pressure is generally carried out at a pressure of less than 200 mmHg for 1 to 20 seconds, and the pre-baking is a heat treatment of the coating film at 70°C to 110°C for 1 minute to 15 minutes.

Next, the above-mentioned pre-baked coating film is exposed to light with a photomask having a specific pattern. The light used in the exposure treatment can be ultraviolet light such as g-line, h-line or i-line, and the irradiation device of the ultraviolet light can be (ultra) high pressure mercury lamp or metal halide lamp.

After exposure treatment, the pre-bake coating film after exposure is immersed in a developing solution at 21° C. to 25° C. to remove the pre-bake coating film of the unexposed part, and the pre-bake coating film can be formed on the substrate. specific pattern.

The aforementioned developer can be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, diethylamine, dimethyl Basic compounds such as ethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene. The concentration of the developer is generally 0.001 to 10 percent by weight, preferably 0.005 to 5 percent by weight, and more preferably 0.01 to 1 percent by weight.

After developing treatment, the substrate having the specific pattern is washed with water, and the substrate is air-dried with compressed air or compressed nitrogen. Then, the black matrix can be formed on the substrate by post-baking treatment with a heating device such as a hot plate or an oven. The temperature of the post-baking treatment is generally 150°C to 250°C. When the heating device uses a hot plate, its heating time is 5 minutes to 60 minutes; when the heating device uses an oven, its heating time is 15 minutes to 150 minutes.

Preparation method of color filter

The preparation of the color filter of the present invention is to firstly coat the photosensitive resin composition for the color filter in the solution state uniformly on the coating method such as spin coating, casting coating or roll coating. A coating film is formed on the substrate having the black matrix and/or the black spacer.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and the remaining solvent is removed by pre-baking to form a pre-baking coating film. However, the conditions for drying under reduced pressure and pre-baking vary according to the type or ratio of each component. The drying under reduced pressure is generally performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the prebaking is a heat treatment of the coating film at 70° C. to 110° C. for 1 minute to 15 minutes.

Then, the aforementioned pre-baked coating film is exposed to light with a photomask having a specific pattern. The light used in the exposure treatment can be ultraviolet light such as g-line, h-line or i-line, and the irradiation device of the ultraviolet light can be (ultra) high pressure mercury lamp or metal halide lamp.

After exposure treatment, the pre-bake coating film after exposure is immersed in a developing solution at 21° C. to 25° C. to remove the pre-bake coating film of the unexposed part, and the pre-bake coating film can be formed on the substrate. specific pattern.

After developing treatment, the substrate having the specific pattern is washed with water, and the substrate is air-dried with compressed air or compressed nitrogen. Then, post-baking treatment is performed with a heating device such as a hot plate or an oven. The conditions of the post-baking treatment are as described above and will not be repeated here. The above steps are repeated to form red, green, blue and other pixel coloring layers on the substrate.

Next, in a vacuum environment of 220° C. to 250° C., an ITO protective film (vapor deposition film) is formed on the surface of the aforementioned pixel coloring layer by sputtering. When necessary, the ITO protective film is etched and wired, and a liquid crystal alignment film (polyimide for liquid crystal alignment film) is coated on the surface of the ITO protective film to form a color filter with a pixel layer.

Preparation method of liquid crystal display

The color filter prepared above and the substrate provided with the thin film transistor (TFT) are arranged to face each other, and a gap (cell gap) is set between the two. Then, the color filter and the peripheral portion of the above-mentioned substrate are bonded together with an adhesive and an injection hole is left. Next, the liquid crystal is injected through the injection hole on the surface of the substrate and the gap separated by the adhesive, and the injection hole is sealed to form a liquid crystal layer. Afterwards, the polarizing plate is arranged on the other side of the color filter contacting the liquid crystal layer and the other side of the substrate contacting the liquid crystal layer, so as to manufacture a liquid crystal display.

The above-mentioned liquid crystal can be a liquid crystal compound or a liquid crystal composition, which is not particularly limited here, but any liquid crystal compound and liquid crystal composition can be used.

In addition, the liquid crystal alignment film used in the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and either inorganic or organic materials can be used, and the present invention is not limited thereto.

In addition to the above-mentioned methods, the liquid crystal display device having the resin black matrix of the present invention can also be used, for example, as disclosed in Japanese Patent Laid-Open No. Hei 4-253028, Japanese Patent Laid-Open No. 7-159772, and Japanese Patent Laid-Open No. 9-311348. manufactured by well-known methods. In addition, the resin black matrix of the present invention is particularly preferably a liquid crystal display device such as a BOA method or a Japanese Patent In the liquid crystal display device of the COA method according to Japanese Patent Laid-Open No. 10-206888, Japanese Patent Laid-Open No. 2002-277899, and the like.

The following examples illustrate the present invention in detail, but the present invention is not limited to the contents involved in these examples.

Preparation of Resin (A-1) Having Unsaturation

Preparation of A-1-1

100 parts by weight of a fluorene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol, and the propylene glycol monomethyl ether acetate of 130 parts by weight are added in the four-necked flask of 500 mL by continuous addition, and the feeding speed is controlled at 25 parts by weight/min , the temperature of the reaction process is maintained at 100° C. to 110° C., and the reaction is performed for 15 hours to obtain a pale yellow transparent mixed solution with a solid content concentration of 50 wt %.

Next, 100 parts by weight of the light yellow transparent mixed solution obtained above was dissolved in 25 parts by weight of ethylene glycol ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of diphenyl ether were added simultaneously. ketone tetracarboxylic dianhydride, heated to 110°C to 115°C, and reacted for 2 hours to obtain an unsaturated resin with an acid value of 98.0 mgKOH/g (hereinafter referred to as A-1-1).

Preparation A-1-2

100 parts by weight of a fluorene epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-tert-butyl-p-cresol, and the propylene glycol monomethyl ether acetate of 130 parts by weight are added in the four-necked flask of 500 mL by continuous addition, and the feeding speed is controlled at 25 parts by weight/min , the temperature of the reaction process is maintained at 100° C. to 110° C., and the reaction is performed for 15 hours to obtain a light yellow transparent mixed solution with a solid content concentration of 50 wt %.

Next, 100 parts by weight of the light yellow transparent mixed solution obtained above was dissolved in 25 parts by weight of ethylene glycol diethyl ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride was added, and the mixture was heated at 90°C to 95°C. Then, add 6 parts by weight of tetrahydrophthalic anhydride, and react at 90°C to 95°C for 4 hours to obtain a resin with an unsaturated group with an acid value of 99.0 mgKOH/g (hereinafter referred to as A-1-2).

Preparation of A-1-3

400 parts by weight of epoxy compound [Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 288], 102 parts by weight of acrylic acid, 0.3 parts by weight of p-methoxyphenol, and 5 parts by weight of triphenyl base phosphine, and 264 parts by weight of propylene glycol monomethyl ether acetate were placed in a reaction flask, the temperature of the reaction process was maintained at 95 ° C, and the reaction was performed for 9 hours to obtain an intermediate product with an acid value of 2.2 mgKOH/g. Next, 151 parts by weight of tetrahydrophthalic anhydride was added, and the reaction was carried out at 95° C. for 4 hours to obtain a resin with an unsaturated group having an acid value of 102 mgKOH/g and a weight average molecular weight of 3,200 (hereinafter referred to as the as A-1-3).

Preparation of other alkali-soluble resins (A-2)

Preparation of A-2-1

1 part by weight of 2,2'-azobisisobutyronitrile, 240 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, 15 parts by weight of styrene, 35 parts by weight of methyl Benzyl acrylate, 10 parts by weight of glycerol monomethacrylate and 20 parts by weight of nitrogen-phenylmaleimide were placed in a round-bottomed flask equipped with a stirrer and a condenser, and the inside of the flask was After being filled with nitrogen, the temperature was raised to 80° C. with slow stirring, the reactants were uniformly mixed, and a polymerization reaction was carried out for 4 hours. After that, the temperature was raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added for 1 hour of polymerization to obtain another alkali-soluble resin (hereinafter referred to as A-2-1 ).

Preparation of A-2-2

2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl ether, 15 parts by weight of methacrylic acid, 15 parts by weight of 2-hydroxyethyl acrylate and 70 parts by weight of Benzyl methacrylate was placed in a round-bottomed flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen, and then slowly stirred and heated to 80°C, so that the reactants were uniformly mixed and polymerized The reaction was carried out for 3 hours. After that, the temperature was raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added for 1 hour of polymerization to obtain another alkali-soluble resin (hereinafter referred to as A-2-2 ).

Example

Preparation of black photosensitive resin composition

Example 1

100 parts by weight of the aforementioned alkali-soluble resin A-1-1, 30 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as B-2-1), 0.1 part by weight of the first photoinitiator (C-1- 1; Compounds such as formula (I-1)), 0.2 parts by weight of 1-chloro-4-propoxythioxanthone (C-2-1), 0.1 parts by weight of 1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone-1-(O-acetyloxime) (hereinafter referred to as C-3-1), 10 parts by weight of The first black pigment (E-1-1), 5 parts by weight of the second black pigment (trade name MA220; hereinafter referred to as E-2-1) and 0.5 parts by weight of 3-glycidyl propyl trimethoxy Silane (F-1) was added to 300 parts by weight of propylene glycol monomethyl ether acetate (hereinafter abbreviated as D-1), and after stirring with a shaking type stirrer, the examples were prepared 1 of the black photosensitive resin composition. The obtained photosensitive resin composition was evaluated by the following evaluation methods for the dielectric constant and the linearity of the high-definition pattern, and Table 1 shows the obtained results.

Examples 2 to 13 and Comparative Examples 1 to 5

Examples 2 to 13 and Comparative Examples 1 to 5 use the same preparation method as that of the black photosensitive resin composition of Example 1, except that Examples 2 to 13 and Comparative Examples 1 to 5 change the black color. The types and usage amounts of the raw materials in the photosensitive resin composition, and their formulations and evaluation results are shown in Table 1 and Table 2, respectively, and will not be repeated here.

Table 2

In Table 1 and Table 2:

Evaluation method

Linearity of high-definition patterns

The black photosensitive resin composition of each said Example and the comparative example was apply|coated on the glass substrate of 100 mm x 100 mm by spin coating. Then, drying under reduced pressure was performed under a pressure of about 100 millimeters of mercury (mmHg) for about 30 seconds. Next, the above-mentioned glass substrate was pre-baked at 80° C. for 3 minutes to form a pre-baked coating film with a film thickness of 2.5 μm. After that, using an exposure machine (manufactured by Canon, model PLA-501F) at 300 millijoules/square centimeter (mJ/cm ² ) through a mask having a stripe pattern of 25 μm [pitch 50 μm] The above pre-baked coating film is irradiated with UV light. After irradiation with ultraviolet light, the pre-baked coating film was immersed in a developing solution at 23° C. for 2 minutes. After that, the pre-baking coating film was washed with pure water, and the pre-baking coating film was post-baked at 200° C. for 80 minutes to form a black pattern with a film thickness of 2.0 μm on the glass substrate.

The stripe pattern formed by the above method was observed with an optical microscope, and the linearity of the high-definition pattern was evaluated according to the following criteria:

⊚: 90% or more of high-definition patterns have good linearity;

○: 80% or more and less than 90% of high-definition patterns have good linearity;

△: 70% or more and less than 80% of the high-definition patterns have good linearity;

×: The linearity of the high-definition pattern of less than 70% is good.

Dielectric constant

On the glass substrate on which the ITO film with a thickness of 150 nm was formed by the sputtering method, a black pattern was formed on the entire surface under the same conditions as described above, and an ITO substrate was produced. The ITO substrate of this sample was used as the main electrode, and the counter electrode of gold was formed on the resin black matrix by the vapor deposition method. The dielectric constant was obtained by measuring an equivalent parallel capacitance with a frequency of 1 KHz and an amplitude of 1 V of the reference signal using an LCR meter 4284A manufactured by HP (now Agilent). The dielectric constant is evaluated according to the following criteria:

◎: The dielectric constant is less than 3.5;

○: The dielectric constant is 3.5 or more and less than 4;

△: The dielectric constant is 4 or more and less than 5;

×: The dielectric constant is 5 or more.

The above-mentioned embodiments are only to illustrate the principle and effect of the present invention, but not to limit the present invention. Modifications and changes made by those skilled in the art to the above embodiments are still within the scope of the present invention. The protection scope of the present invention is described in the claims.

Claims (13)

1. A black photosensitive resin composition comprising:

an alkali-soluble resin (A);

a compound (B) having an ethylenically unsaturated group;

a photoinitiator (C);

a solvent (D); and

a black pigment (E) which is a pigment,

wherein: the photoinitiator (C) comprises a first photoinitiator (C-1) having a structure represented by formula (C-I):

in the formula (C-I), R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another are hydrogen, C₁-C₂₀Alkyl, aryl, heteroaryl, and heteroaryl,

COR₁₆；

Or R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another together are

With the proviso that R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈At least one pair of

R₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, said C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl;

or R₉、R₁₀、R₁₁And R₁₂Independently of one another, unsubstituted phenyl or phenyl substituted by one or more of the following groups: c₁-C₆Alkyl, halogen;

x is CO or a direct bond;

R₁₃is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R₁₇、COOR₁₇、OR₁₇；

Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O or CO, interrupted by C₂-C₂₀Alkyl is unsubstituted or substituted with one or more halogen;

or R₁₃Is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₄A haloalkyl group;

R₁₄is hydrogen, C₁-C₂₀Alkoxy or C₁-C₂₀An alkyl group;

R₁₅is C₆-C₂₀Aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₄Haloalkyl, OR₁₇C interrupted by one or more O₂-C₂₀An alkyl group; or each channel thereof C₁-C₂₀Alkyl substitution, said C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇Phenyl, OR₁₇；

Or R₁₅Is hydrogen, C₃-C₈A cycloalkyl group;

or R₁₅Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen;

R₁₆is C₆-C₂₀Aryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₄Haloalkyl, OR₁₇(ii) a Or each of which is passed through one or more C₁-C₂₀Alkyl substitution, said C₁-C₂₀Alkyl is not takenSubstituted or substituted with one or more of the following groups: halogen, OR₁₇；

R₁₇Is hydrogen, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen or C interrupted by one or more O₃-C₂₀A cycloalkyl group;

or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O;

or R₁₇Is phenyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₁₂Alkyl radical, C₁-C₁₂An alkoxy group;

with the proviso that at least one group is present in the first photoinitiator (C-1)

The black pigment (E) comprises a first black pigment (E-1), wherein the first black pigment (E-1) comprises a compound having the formula (E-I):

in the formula (E-I), R^1eAnd R^6eIndependently of one another are hydrogen atom, CH₃、CF₃Fluorine atom or chlorine atom; r^2e、R^3e、R^4e、R^5e、R^7e、R^8e、R^9eAnd R^10eAnd all others, independently of one another, are hydrogen, halogen, R^11e、COOH、COOR^11e、COO-、CONH₂、CONHR^11e、CONR^11eR^12e、CN、OH、OR^11e、COCR^11e、OOCNH₂、OOCNHR^11e、OOCNR^11eR^12e、NO₂、NH₂、NHR^11e、NR^11eR^12e、NHCOR^12e、NR^11eCOR^12e、N＝CH₂、N＝CHR^11e、N＝CR^11eR^12e、SH、SR^11e、SOR^11e、SO₂R^11e、SO₃R^11e、SO₃H、SO₃-、SO₂NH₂、SO₂NHR^11eOr SO₂NR^11eR^12e(ii) a And is selected from the group consisting of R^2eAnd R^3e、R^3eAnd R^4e、R^4eAnd R^5e、R^7eAnd R^8e、R^8eAnd R^9eAnd R^9eAnd R^10eAt least 1 combination of the group consisting of^11eBridging to bond to each other; r^11eAnd R^12eIndependently of one another, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms;

the compound (B) having an ethylenically unsaturated group contains a first compound (B-1) having an ethylenically unsaturated group, and the first compound (B-1) having an ethylenically unsaturated group is used in an amount of 30 to 300 parts by weight based on 100 parts by weight of the alkali-soluble resin (A);

the first compound (B-1) having an ethylenically unsaturated group comprises a compound having a structure represented by the formula (B-I):

in the formula (B-I), R^1bIs a hydrogen atom or a methyl group; r^2bIs a hydrogen atom, an acryloyl group or a methacryloyl group; and b is an integer from 2 to 3;

the photoinitiator (C) further comprises a second photoinitiator (C-2) having a structure represented by formula (C-II), and the second photoinitiator (C-2) is used in an amount of 0.2 to 2 parts by weight based on 100 parts by weight of the alkali-soluble resin (A);

in the formula (C-II), the E₂₇Independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a halogen atom.

2. The black photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises an unsaturated group-containing resin (A-1), wherein the unsaturated group-containing resin (A-1) is obtained by polymerizing a mixture comprising an epoxy compound (a-1-1) having at least two epoxy groups and a compound (a-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.

3. The black photosensitive resin composition according to claim 2, wherein the epoxy compound a-1-1 having at least two epoxy groups comprises a compound having a structure represented by formula (I), a compound having a structure represented by formula (II), or a combination thereof:

in the formula (I), R^1aTo the R^4aEach independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms; and

in the formula (II), R^5aTo R^18aEach independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms; and a represents an integer of 0 to 10.

4. The black photosensitive resin composition according to claim 2, wherein the resin (A-1) having an unsaturated group is used in an amount of 30 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

5. The black photosensitive resin composition according to claim 1, wherein the first photoinitiator (C-1) is used in an amount of 0.3 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

6. The black photosensitive resin composition according to claim 1, wherein in the formula (E-I), R is^2e、R^4e、R^5e、R^7e、R^9eAnd R^10eIndependently of one another, is a hydrogen atom, a fluorine atom or a chlorine atom, R^3eAnd R^8eIndependently of each other hydrogen atom, NO₂、OCH₃、OC₂H₅Bromine atom, chlorine atom, CH₃、C₂H₅、N(CH₃)₂、N(CH₃)(C₂H₅)、N(C₂H₅)₂Alpha-naphthyl, beta-naphthyl, SO₃H or SO₃-，R^1eAnd R^6eSame as R^2eAnd R^7eSame as R^3eAnd R^8eSame as R^4eAnd R^9eSame as R^5eAnd R^10eThe same is true.

7. The black photosensitive resin composition according to claim 1, wherein the black pigment (E-1) is used in an amount of 15 to 150 parts by weight based on 100 parts by weight of the alkali-soluble resin (A).

8. The black photosensitive resin composition according to claim 1, wherein the compound (B) having an ethylenically unsaturated group is used in an amount of 30 to 300 parts by weight based on 100 parts by weight of the alkali-soluble resin (a); the photoinitiator (C) is used in an amount of 0.4 to 40 parts by weight; the solvent (D) is used in an amount of 300 to 3000 parts by weight; and the black pigment (E) is used in an amount of 15 to 150 parts by weight.

9. The black photosensitive resin composition according to claim 1, further comprising an epoxy group-containing silane compound (F).

10. A black matrix formed by subjecting the black photosensitive resin composition according to any one of claims 1 to 9 to a pre-baking treatment, an exposure treatment, a development treatment and a post-baking treatment.

11. A black spacer formed by subjecting the black photosensitive resin composition according to any one of claims 1 to 9 to a pre-baking treatment, an exposure treatment, a development treatment and a post-baking treatment.

12. A liquid crystal display comprising the black matrix as claimed in claim 10.

13. A liquid crystal display comprising the black spacer of claim 11.