CN105974738A

CN105974738A - Blue photosensitive resin composition, color filter and liquid crystal display device having the same

Info

Publication number: CN105974738A
Application number: CN201610130152.2A
Authority: CN
Inventors: 裵辰哲; 权凤壹; 金佑泰
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2015-03-11
Filing date: 2016-03-08
Publication date: 2016-09-28
Also published as: TWI647285B; TW201632591A

Abstract

The invention relates to a blue photosensitive resin composition, a color filter and a liquid crystal display device having the same, the blue photosensitive resin composition adopts an oxime ester derivative compound as a photopolymerization initiator which is used in a blue pigment, so that the close adaptation is good in a hot and humid environment, the stripping does not occur, and the liquid crystal bubble phenomenon can be improved. In addition, the color filter and liquid crystal display device are made by using the blue photosensitive resin composition, the pattern does not fall off, so that the reliability can be improved.

Description

Blue-sensitive resin combination, color filter and comprise its liquid crystal indicator

Technical field

The present invention relates to blue-sensitive resin combination, color filter and the liquid crystal indicator comprising it.

Background technology

Color filter is widely used at capturing element, liquid crystal indicator etc., thus its range of application expands the most rapidly.With Color filter in color liquid crystal display arrangement or capturing element etc. is generally as follows manufacture: by spin coating, be formed with black matrix On the substrate of pattern, even spread contains the coloring phototonus resin combination being equivalent to the assorted coloring agent of redness, green and blueness Thing, then heat drying (following, otherwise referred to as pre-fired), by the film exposure formed, development, and as required by face Color repeats to be heating and curing further the operation of (following, otherwise referred to as then burn till), thus forms the pixel of colors.

As such photosensitive composition, use containing alkali-soluble binder resin, optical polymerism chemical combination Thing, Photoepolymerizationinitiater initiater, pigment solvent, and the photosensitive polymer combination containing the black pigment for forming black matrix.

Especially, in photosensitive polymer combination, blue pigment is different from the pigment of other colors only, has at shortwave Long (about, the later half band of 400nm) region, the problem that adaptation reduces under hot and humid environment.

In recent years, in order to realize low exposure, high sensitivity, disclose and oxime ester derivative compound is used as photopolymerization initiation The example of agent, but this example makes the quality of liquid crystal indicator drop typically without solving to occur color filter to peel off in blue pigment Low problem etc..

Additionally, KR published patent the 10-2013-0115272nd (2013.10.21 is open) has been directed to use with oxime ester and has spread out The oxime ester derivative of the benzo carbazole compound of biologic artifact is made as in Photoepolymerizationinitiater initiater and optical polymerism composition Purposes for light trigger.

Additionally, KR published patent the 10-2013-0124215th (2013.1.13 is open) relates to novel oxime ester fluorenes chemical combination Thing, the Photoepolymerizationinitiater initiater comprising it and photo-corrosion-resisting agent composition.Above-mentioned conventional art uses oxime ester fluorene derivative chemical combination Thing is as Photoepolymerizationinitiater initiater such that it is able to reduce their usage amount also have highly sensitive sensitiveer than original even if providing The photo-corrosion-resisting agent composition of degree.

Additionally, Ebrean Registered Patent the 10-1435652nd (2014.8.22 registration) relate to novel β-oxime ester fluorene compound, Comprise its Photoepolymerizationinitiater initiater and photo-corrosion-resisting agent composition.Above-mentioned conventional art uses β-oxime ester fluorene derivative compound As Photoepolymerizationinitiater initiater, even if thus providing reduction usage amount also to have the original highly sensitive sensitivity of ratio, and pattern The photo-corrosion-resisting agent composition that stability, chemical resistance and ductility etc. are excellent.

In above-mentioned conventional art, use oxime ester derivative compound is as Photoepolymerizationinitiater initiater, but only has low exposure and height Sensitivity effect, due to not by its technical market used along with specific blue pigment, does not the most solve height The quality of liquid crystal indicator is caused to reduce because the closing force of color filter reduces by liquid crystal bubbles phenomenon under temperature high humidity environment Problem.

Prior art literature

Patent documentation

Patent documentation 1: KR published patent the 10-2013-0115272nd

Patent documentation 2: KR published patent the 10-2013-0124215th

Patent documentation 3: Ebrean Registered Patent the 10-1435652nd

Summary of the invention

Problem to be solved

The present invention is used for solving problem described above, it is intended that by the Photoepolymerizationinitiater initiater of ad hoc structure is answered For blue pigment, it is provided that though a kind of the most peeling-off under hot and humid environment, and there is no that pattern comes off reliable Blue-sensitive resin combination that property is high, color filter and comprise its liquid crystal indicator.

The method solving problem

Blue-sensitive resin combination according to the embodiments of the invention for realizing above-mentioned purpose comprises photopolymerization Initiator and coloring agent,

Above-mentioned Photoepolymerizationinitiater initiater is characterised by, comprises in following [chemical formula 1] oxime ester derivative compound At least one.

[chemical formula 1]

(in chemical formula 1,

Z is CR ' R " or NR ',

R ' and R " it is each independently hydrogen, halogen, substituted or non-substituted C1-C20 alkyl, substituted or non-substituted C6- C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base, C3-C20 cycloalkyl, replacement or non-take The C2-C12 thiazolinyl in generation, C4-C8 cycloalkenyl group or C2-C12 alkynyl,

R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈It is each independently hydrogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alcoxyl Base, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base, C3-C20 cycloalkyl, amino, nitro, cyano group, hydroxyl,Or COR₁₆,

Or, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇, or R₇And R₈It is the most together

R₉、R₁₀、R₁₁And R₁₂It is each independently hydrogen, substituted or non-substituted C1-C20 alkyl,

Or R₉、R₁₀、R₁₁And R₁₂It is substituted or non-substituted phenyl independently of one another,

X be CO or directly in conjunction with,

R₁₄For hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C2-C5 thiazolinyl, C1-C20 alkoxyl, C1-C20 hydroxyl alkane Base, C1-C20 hydroxy alkoxy base or C3-C20 cycloalkyl,

R₁₅For hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 Hydroxy alkoxy base, C3-C20 cycloalkyl or C3-C20 heteroaryl, each of which be non-substituted or by more than 1 phenyl, halogen, C1-C4 haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂, SO-C1-C10 alkyl, SO₂-C1-C10 alkyl, It is situated between and is having more than 1 O, S or NR₂₆C2-C20 alkyl replace, or, each of which is non-substituted or is replaced by following radicals, Described group is by more than 1 halogen, COOR₁₇、CONR₁₉R₂₀, phenyl, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6-C20 virtue Base epoxide carbonyl, C3-C20 heteroaryloxycarbonyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted C1-C20 alkyl,

R₁₆For C6-C20 aryl that is non-substituted or that replaced by more than 1 C1-C20 alkoxyl or C1-C20 alkyl,

K is integer 1-10,

R₁₇For C1-C4 haloalkyl,

R₁₈For hydrogen, C2-C12 thiazolinyl, C3-C20 cycloalkyl or phenyl-C1-C3 alkyl, wherein, C2-C12 thiazolinyl, C3-C20 Cycloalkyl or phenyl-C1-C3 alkyl be non-Jie or be situated between and having more than 1 O, S, CO, NR₂₆Or COOR₁₇,

Or, R₁₈For non-substituted or by more than 1 OH, SH, CN, C3-C6 alkenyloxy group, OCH₂CH₂CN、OCH₂CH₂(CO)O (C1-C4 alkyl), O (CO)-(C2-C4) thiazolinyl, O (CO)-(C1-C4 alkyl), O (CO)-phenyl or (CO) OR₁₇Substituted C1- C20 alkyl,

Or, R₁₈More than 1 O, S, CO, NR is being had for being situated between₂₆Or COOR₁₇C2-C20 alkyl,

Or, R₁₈For (CH₂CH₂O)_nH、(CH₂CH₂O)_n(CO)-(C1-C8 alkyl), C2-C8 alkanoyl or C3-C6 alkene acyl Base,

Or, R₁₈For non-substituted or by more than 1 C1-C6 alkyl, halogen, OH, C1-C4 alkoxyl or C1-C4 alkyl sulphur The substituted benzoyl of acyl group,

Or, R₁₈For phenyl, naphthyl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 halogen, C1- C12 alkyl, C1-C4 haloalkyl, C1-C12 alkoxyl, CN, NO₂, phenyl-C1-C3 alkyl oxy, phenoxy group, C1-C12 alkane Base sulfonyl, phenyl sulfonyl, N (C1-C12 alkyl)₂, diphenyl amino, (CO) O (C1-C8 alkyl), (CO)-C1-C8 alkane Base, (CO) N (C1-C8 alkyl)₂OrReplace,

X₂For O, CO, S or directly in conjunction with,

R₁₉And R₂₀It is hydrogen, C1-C20 alkyl, C2-C4 hydroxy alkyl, C2-C10 alkoxyalkyl, C2-C5 independently of one another Thiazolinyl, C3-C20 cycloalkyl, phenyl-C1-C3 alkyl, C1-C8 alkanoyl, C1-C8 alkanoyl epoxide, C3-C12 enoyl-, SO₂-(C1-C4 haloalkyl) or benzoyl,

Or, R₁₉And R₂₀For phenyl, naphthyl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 halogen Element, C1-C4 haloalkyl, C1-C20 alkoxyl, C1-C12 alkyl, benzoyl or C1-C12 alkoxyl replace,

Or, R₁₉And R₂₀With they with atom N together formed non-Jie or be situated between having O, S or NR₁₇Five yuan or Hexa-atomic saturated or unsaturated ring, above-mentioned five yuan or hexa-atomic saturated or unsaturated ring be non-substituted or by more than 1 C1-C20 alkyl, C1-C20 alkoxyl ,=O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、NO₂, halogen, C1-C4-haloalkyl, CN, phenyl,Replace or by non-Jie or be situated between having more than 1 O, S, CO or NR₁₇C3-C20 cycloalkyl substituted,

Or, R₁₉And R₂₀With they with atom N together form heteroaromatic ring system, described heteroaromatic ring system is non- Replace or by more than 1 C1-C20 alkyl, C1-C4 haloalkyl, C1-C20 alkoxyl ,=O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO) R₂₃、Halogen, NO₂, CN, phenyl replace or by non-Jie or be situated between having more than 1 O, S, CO or NR₁₇ C3-C20 cycloalkyl substituted,

R₂₁And R₂₂It is hydrogen, C1-C20 alkyl, C1-C4 haloalkyl, C3-C10 cycloalkyl or phenyl independently of one another,

Or, R₂₁And R₂₂With they with atom N together formed non-Jie or be situated between having O, S or NR₂₆Five yuan or Hexa-atomic saturated or unsaturated ring, above-mentioned five yuan or hexa-atomic saturated or unsaturated ring be not condensed or above-mentioned five yuan or hexa-atomic saturated or Unsaturated cyclic condensation has phenyl ring,

R₂₃For hydrogen, OH, C1-C20 alkyl, C1-C4 haloalkyl, non-Jie or be situated between having more than 1 O, CO or NR₂₆'s C2-C20 alkyl, non-Jie or be situated between having O, S, CO or NR₂₆C3-C20 cycloalkyl, or, R₂₃For phenyl, naphthyl, phenyl- C1-C4 alkyl, OR₁₇、SR₁₈Or NR₂₁R₂₂,

R₂₄For (CO) OR₁₇、CONR₁₉R₂₀、(CO)R₁₇, or, R₂₄Have and R₁₉And R₂₀Identical implication,

R₂₅For COOR₁₇、CONR₁₉R₂₀、(CO)R₁₇, or, R₂₅Have and R₁₇Identical implication,

R₂₆For hydrogen, C1-C20 alkyl, C1-C4 haloalkyl, being situated between is having the C2-C20 alkyl of more than 1 O or CO, or it is benzene Base-C1-C4 alkyl, non-Jie or be situated between and having the C3-C8 cycloalkyl of more than 1 O or CO, or be (CO) R₁₉, or be non-substituted or By more than 1 C1-C20 alkyl, halogen, C1-C4 haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀OrSubstituted Phenyl,

Wherein, molecular memory is at least 1 group

When Z is CR ' R " time, R₆For

When Z is NR ', R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇, or R₇And R₈Middle least one set is)

Invention effect

As it has been described above, use oxime ester derivative compound to gather as light according to the blue-sensitive resin combination of the present invention Close initiator, even if thus also be able in the environment of hot and humid improve adaptation, it is thus possible to improve liquid crystal bubbles phenomenon.

Additionally, utilize the color filter of the blue-sensitive resin combination manufacture of the present invention and liquid crystal indicator not to scheme Case comes off, therefore, it is possible to improve reliability.

Detailed description of the invention

Blue-sensitive resin combination according to the present invention comprises Photoepolymerizationinitiater initiater and coloring agent, and can be further Comprise alkali-soluble binder resin, photopolymerizable compound and solvent.

The Photoepolymerizationinitiater initiater contained by blue-sensitive resin combination of the present invention is characterised by, comprises and is selected from down State at least one in the oxime ester derivative compound of [chemical formula 1].

[chemical formula 1]

(in chemical formula 1,

Z is CR ' R " or NR ',

R ' and R " it is each independently hydrogen, halogen, substituted or non-substituted C1-C20 alkyl, substituted or non-substituted C6- C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base, C3-C20 cycloalkyl, replacement or non-take The C2-C12 thiazolinyl in generation, C4-C8 cycloalkenyl group, C2-C12 alkynyl,COR₁₆、OR₁₇, halogen, NO₂Or

Or, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇, or R₇And R₈It is quilt independently of one anotherSubstituted C2-C10 thiazolinyl,

Or, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇, or R₇And R₈It is-(CH the most together₂)_p-Y- (CH₂)_q-,

R₉、R₁₀、R₁₁And R₁₂It is each independently hydrogen, non-substituted or by more than 1 halogen, phenyl, CN, OH, SH, C1- C4-alkoxyl replaces or any group substituted C1-C20 alkyl,

Specifically, R₉、R₁₀、R₁₁And R₁₂Be independently of one another hydrogen, non-substituted or by more than 1 halogen, phenyl, CN, OH, SH, C1-C4-alkoxyl, (CO) OH or (CO) O (C1-C4 alkyl) substituted C1-C20 alkyl,

Or, R₉、R₁₀、R₁₁And R₁₂Be independently of one another non-substituted phenyl or by more than 1 C1-C6 alkyl, halogen, CN、OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted phenyl,

Or, R₉、R₁₀、R₁₁And R₁₂It is halogen, CN, OR independently of one another₁₇、SR₁₈、SOR₁₈、SO₂R₁₈Or NR₁₉R₂₀, its In, substituent group OR₁₇、SR₁₈Or NR₁₉R₂₀At random with 1 in the carbon atom of naphthalene nucleus together by free radical R₁₇、R₁₈、R₁₉With/ Or R₂₀Form five yuan or hexatomic ring,

Or, R₉、R₁₀、R₁₁And R₁₂It is independently of one anotherCOR₁₆Or NO₂,

Or, R₉、R₁₀、R₁₁And R₁₂It is substituted or non-substituted phenyl independently of one another,

X be CO or directly in conjunction with,

Y is O, S, NR₂₆Or directly in conjunction with,

P is integer 0,1,2 or 3,

Q is integer 1,2 or 3,

Specifically, R₁₄For hydrogen, C3-C8 cycloalkyl, C2-C5 thiazolinyl, C1-C20 alkoxyl or non-substituted or by more than 1 Halogen, phenyl, C1-C20 alkyl phenyl or CN substituted C1-C20 alkyl,

Or, R₁₄For phenyl or naphthyl, each of which is non-substituted or by more than 1 C1-C6 alkyl, C1-C4 alkyl halide Base, halogen, CN, OR₁₇、SR₁₈And/or NR₁₉R₂₀Replace,

Or, R₁₄For C3-C20 heteroaryl, C1-C8 alkoxyl, benzyl epoxide or phenoxy group, above-mentioned benzyl epoxide and benzene oxygen Base is non-substituted or by more than 1 C1-C6 alkyl, C1-C4 haloalkyl and/or halogen substiuted,

R₁₅For hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 Hydroxy alkoxy base, C3-C20 cycloalkyl or C3-C20 heteroaryl, each of which be non-substituted or by more than 1 phenyl, halogen, C1-C4 haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂, SO-C1-C10 alkyl, SO₂-C1-C10 alkyl, It is situated between and is having more than 1 O, S or NR₂₆C2-C20 alkyl replace, or, each of which is that unsubstituted or substituted has more than 1 Halogen, COOR₁₇、CONR₁₉R₂₀, phenyl, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6-C20 aryloxycarbonyl, C3-C20 miscellaneous Aryloxycarbonyl, OR₁₇、SR₁₈Or NR₁₉R₂₀C1-C20 alkyl replace,

Or, R₁₅For hydrogen, C2-C12 thiazolinyl, non-Jie or be situated between having more than 1 O, CO or NR₂₆C3-C8 cycloalkyl,

Or, R₁₅For non-substituted or by more than 1 halogen, OR₁₇、SR₁₈, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6- C20 aryloxycarbonyl, C3-C20 heteroaryloxycarbonyl, NR₁₉R₂₀、COOR₁₇、CONR₁₉R₂₀、PO(OC_kH_2k+1)₂、Phenyl substituted C1-C20 alkyl, above-mentioned C1-C20 alkyl be replaced halogen, C1-C20 alkyl, C1-C4 haloalkyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Phenyl replace,

Or, R₁₅More than 1 O, SO or SO is being had for being situated between₂C2-C20 alkyl, above-mentioned by be situated between C2-C20 alkyl be Non-substituted or by more than 1 halogen, OR₁₇、COOR₁₇、CONR₁₉R₂₀, phenyl replace or be replaced OR₁₇、SR₁₈Or NR₁₉R₂₀'s Phenyl replaces,

Or, R₁₅For C2-C20 alkanoyl, or it is non-substituted or by more than 1 C1-C6 alkyl, halogen, phenyl, OR₁₇、 SR₁₈Or NR₁₉R₂₀Substituted benzoyl,

Or, R₁₅For non-substituted or by more than 1 OR₁₇Substituted naphthoyl, or be C3-C14 Heteroarylcarbonyl,

Or, R₁₅For non-Jie or be situated between having the C2-C12 alkoxy carbonyl of more than 1 O, above-mentioned non-Jie or by be situated between exist C2-C12 alkoxy carbonyl be non-substituted or replaced by more than 1 hydroxyl,

Or, R₁₅For non-substituted or by more than 1 C1-C6 alkyl, halogen, C1-C4 haloalkyl, phenyl, OR₁₇、SR₁₈ Or NR₁₉R₂₀Substituted phenyloxycarbonyl,

Or, R₁₅For CN, CONR₁₉R₂₀、NO₂, C1-C4 haloalkyl, S (O)_m-C1-C6 alkyl, for non-substituted or by C1- C12 alkyl or SO₂-C1-C6 alkyl substituted S (O) m-phenyl,

Or, R₁₅For SO that is non-substituted or that replaced by C1-C12 alkyl₂O-phenyl, or be diphenylphosphino or two- (C1-C4 alkoxyl)-phosphono,

M is 1 or 2,

R'₁₄Have and R₁₄Identical implication,

R'₁₅Have and R₁₅Identical implication,

X₁For O, S, SO or SO₂,

X₂For O, CO, S or directly in conjunction with,

R₁₆For C6-C20 aryl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 phenyl, halogen, C1- C4 haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀Replace or had more than 1 O, S or NR by being situated between₂₆C1-C20 alkyl take Generation, or, each of which is had more than 1 halogen, COOR by non-substituted or replacement₁₇、CONR₁₉R₂₀, phenyl, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6-C20 aryloxycarbonyl, C3-C20 heteroaryloxycarbonyl, OR₁₇、SR₁₈Or NR₁₉R₂₀More than 1 C1-C20 alkyl replaces,

Or, R₁₆For hydrogen, non-substituted or by more than 1 halogen, phenyl, OH, SH, CN, C3-C6 alkenyloxy group, OCH₂CH₂CN、OCH₂CH₂(CO) O (C1-C4 alkyl), O (CO)-(C1-C4 alkyl), O (CO)-phenyl, (CO) OH or (CO) O (C1-C4 alkyl) substituted C1-C20 alkyl,

Or, R₁₆More than 1 O, S or NR is being had for being situated between₂₆C2-C12 alkyl,

Or, R₁₆For (CH₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C1-C8 alkyl), C2-C12 thiazolinyl or C3-C8 cycloalkanes Base,

Or, R₁₆For by SR₁₈Substituted phenyl, wherein, free radical R₁₈Represent with COR₁₆The benzene of the carbazole moiety of group Base or with naphthalene nucleus directly in conjunction with,

N is 1-20,

K is integer 1-10,

R₁₇For hydrogen, phenyl-C1-C3 alkyl, non-substituted or by more than 1 halogen, OH, SH, CN, C3-C6 alkenyloxy group, OCH₂CH₂CN、OCH₂CH₂(CO) O (C1-C4 alkyl), O (CO)-(C1-C4 alkyl), O (CO)-(C2-C4) thiazolinyl, O (CO)-benzene Base, (CO) OH, (CO) O (C1-C4 alkyl), C3-C20 cycloalkyl, SO2-(C1-C4 haloalkyl), O (C1-C4 haloalkyl), It is situated between at the C1-C20 alkyl of the C3-C20 cycloalkyl substituted having more than 1 O,

Or, R₁₇More than 1 O, S or NR is being had for being situated between₂₆C2-C20 alkyl,

Or, R₁₇For C1-C4 haloalkyl,

Or, R₁₇For (CH₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C1-C8 alkyl), C1-C8 alkanoyl, C2-C12 alkene Base, C3-C6 enoyl-or non-Jie or be situated between having more than 1 O, S, CO or NR₂₆C3-C20 cycloalkyl,

Or, R₁₇For non-Jie or be situated between having the C1-C8 alkyl-C3-C10 cycloalkyl of more than 1 O,

Or, R₁₇For benzoyl that is non-substituted or that replaced by more than 1 C1-C6 alkyl, halogen, OH or C1-C3 alkoxyl Base,

Or, R₁₇For phenyl, naphthyl or C3-C20 heteroaryl, each of which be non-substituted or by more than 1 halogen, OH, C1-C12 alkyl, C1-C12 alkoxyl, CN, NO₂, phenyl-C1-C3 alkyl oxy, phenoxy group, C1-C12 alkyl sulphonyl, benzene Base sulfonyl, N (C1-C12 alkyl)₂, diphenyl amino orReplace,

Or, R₁₇With groupIn residing phenyl ring or the carbon atom of naphthalene nucleus 1 formation directly in conjunction with,

X₂For O, CO, S or directly in conjunction with,

Or, R₁₉And R₂₀With they with atom N together formed non-Jie or be situated between having O, S or NR₁₇Five yuan or Hexa-atomic saturated or unsaturated ring, above-mentioned five yuan or hexa-atomic saturated or unsaturated ring be non-substituted or by more than 1 C1-C20 alkyl, C1-C20 alkoxyl ,=O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、NO₂, halogen, C1-C4-haloalkyl, CN, phenyl,Non-Jie or be situated between and having more than 1 O, S, CO or NR₁₇C3-C20 cycloalkyl substituted,

Or, R₁₉And R₂₀With they with atom N together form heteroaromatic ring system, described heteroaromatic ring system is non- Replace or by more than 1 C1-C20 alkyl, C1-C4 haloalkyl, C1-C20 alkoxyl ,=O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO) R₂₃、Halogen, NO₂, CN, phenyl or be situated between or be situated between having more than 1 O, S, CO or NR₁₇C3- C20 cycloalkyl substituted,

R₂₄For (CO) OR₁₇、CONR₁₉R₂₀、(CO)R₁₇, or R₂₄Have and R₁₉And R₂₀Identical implication,

R₂₆For hydrogen, C1-C20 alkyl, C1-C4 haloalkyl, be situated between have the C2-C20 alkyl of more than 1 O or CO, phenyl- C1-C4 alkyl, non-Jie or be situated between having the C3-C8 cycloalkyl of more than 1 O or CO, (CO) R₁₉, or non-substituted or by more than 1 C1-C20 alkyl, halogen, C1-C4 haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀OrSubstituted phenyl,

Wherein, molecular memory is at least 1 group

When Z is CR ' R " time, R₆For

When Z is NR ', R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Middle least one set is)

Alkyl disclosed in the present invention, alkoxyl and the substituent comprising moieties in addition comprise straight chain or prop up Chain form, cycloalkyl not only includes monocycle system hydrocarbon, also includes polycyclic system hydrocarbon.Aryl disclosed in the present invention be remove a hydrogen and From the organic free radical of aromatic hydrocarbon induction, comprise 4 to 7 annular atomses suitably including each ring, to preferably comprise 5 or 6 rings former The monocycle of son or condensed ring system, also include that multiple aryl is with singly linked form.The meaning of hydroxy alkyl is, hydroxyl is fixed with above-mentioned The OH-alkyl that the alkyl of justice is combined into, the meaning of hydroxy alkoxy alkyl is, alkoxyl is combined into above-mentioned hydroxy alkyl Hydroxy alkyl-O-alkyl.

Alkyl disclosed in the present invention refers to, is only made up of carbon atom and hydrogen atom, does not has degree of unsaturation and pass through singly-bound The straight chain being combined with molecule remainder or side chain type hydrocarbon chain radical.

C1-C20 alkyl is straight chain type or branched chain type, can be such as C1-C18-, C1-C14-, C1-C12-, C1-C8-, C1-C6-or C1-C4 alkyl or C4-C12-or C4-C8 alkyl, specifically, alkyl preferred C1-C20 straight chain type or side chain Type alkyl, more preferably C1-C10 straight chain type or branch chain type alkyl, most preferably C1-C6 straight chain type or branch chain type alkyl.As so Non-substituted alkyl, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, penta Base, isopentyl, hexyl, heptyl, 2,4,4-tri-methyl-amyl, 2-ethylhexyl, octyl group, nonyl, decyl, dodecyl, 14 Alkyl, pentadecyl, cetyl, octadecyl, eicosyl etc..More than one hydrogen atom that abovementioned alkyl is comprised is permissible By halogen atom, hydroxyl, mercapto (-SH), nitro, cyano group, substituted or non-substituted amino, amidino groups, diazanyl, hydrazone group, carboxyl, Sulfonic group, phosphate, C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 thiazolinyl, C1-C20 alkynyl, the miscellaneous alkyl of C1-C20, C6-C20 aryl, C6-C20 aryl alkyl, C6-C20 heteroaryl or C6-C20 heteroaryl alkyl replace.

The thiazolinyl of the description below is referred to containing the non-substituted of more than 1 C-C multiple bond or substituted C1-C20 alkyl.

Alkoxyl is preferably oxygen-containing straight chain type or the branched chain type alkoxyl of the moieties each with C1-C20.More preferably For having the alkoxyl of 1 to 10 carbon atom, most preferably there is the alkoxyl of 1 to 4 carbon atom.As such alkoxyl Example, methoxyl group, ethyoxyl, propoxyl group, butoxy and tert-butoxy can be enumerated.Above-mentioned alkoxyl can be by fluorine, chlorine or bromine etc. More than one halogen atom is further substituted with and becomes halogenated alkoxy.As such example, fluorine methoxyl group, chloromethane oxygen can be enumerated Base, trifluoromethoxy, trifluoro ethoxy, fluorine ethyoxyl and fluorine propoxyl group etc..More than one hydrogen atom in above-mentioned alkoxyl can To be replaced by the substituent group identical with the situation of abovementioned alkyl.

Cycloalkyl not only includes monocycle system hydrocarbon, also includes polycyclic system hydrocarbon, and at least more than one hydrogen in above-mentioned cycloalkyl is former Son can be replaced by the substituent group identical with the situation of abovementioned alkyl.The carbon atom of above-mentioned cycloalkyl is preferably 3 to 20, more excellent Elect the cycloalkyl with 3 to 10 carbon atoms as, most preferably there is the cycloalkyl of 3 to 8 carbon atoms.

In the present invention, C3-C10 cycloalkyl and C3-C8 cycloalkyl are interpreted as comprising the alkyl of more than 1 ring.Such as, ring Propyl group, Cvclopropvlmethvl, cyclobutyl, cyclopenta, cyclohexyl, ring octyl group adamantyl and replacement and non-substituted bornyl, Norborny and norbornene, especially cyclopenta and cyclohexyl.In the context of invention, C3-C10 cycloalkyl also includes double Ring, i.e. cross-links ring, such asAnd corresponding ring.The example added isMore specifically, above-mentioned term not only includes Etc. structure, also include cross-linking ring or condensed ring system, such asDeng.

C1-C8 alkyl-C3-C10 cycloalkyl be the alkyl that be there are less than 8 carbon atoms by more than 1 replace as above fixed The C3-C10 cycloalkyl of justice.It is situated between and is having the C1-C8 alkyl-C3-C10 cycloalkyl of more than 1 O for be there are less than 8 by more than 1 The substituted O-as defined above of alkyl of carbon atom be situated between C3-C10 cycloalkyl.

C1-C12 alkoxyl is the C1-C12 alkyl replaced by 1 O atom.C1-C12 alkyl have with C atom corresponding to The identical implication of above-mentioned C1-C20 alkyl.C1-C4 alkoxyl is line style or branched chain type, for example, methoxyl group, ethyoxyl, the third oxygen Base, isopropoxy, normal-butyl epoxide, sec-butyl epoxide, isobutyl group epoxide, tert-butyl group epoxide, n-pentyloxy.C1-C8 alkoxyl With the above-mentioned C1-C4-alkoxyl corresponding to C atomic number, there is identical implication.

C2-C10 alkoxyalkyl is to be situated between having the C2-C10 alkyl of 1 O atom.C2-C10 alkyl has and C atomic number The implication that corresponding above-mentioned C1-C20 alkyl is identical.For example, methoxy, methoxy ethyl, methoxy-propyl, ethoxy Ylmethyl, ethoxyethyl group, ethoxycarbonyl propyl, propoxy methyl, Among, propoxypropyl.

C1-C12 alkyl sulphonyl is the C1-C12 alkyl replaced by 1 S atom.C1-C12 alkyl has and C atomic number The implication that corresponding above-mentioned C1-C20 alkyl is identical.C1-C4 alkyl sulphonyl is line style or branched chain type, for example, sulfonyloxy methyl Base, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl, normal-butyl sulfonyl, sec-butylsulfonyl, iso-butylsulfonyl, Tert. butylsulfonyl.

Phenyl-C1-C3 alkyl for example, benzyl, phenylethyl, α-methylbenzyl or alpha, alpha-dimethylbenzyl, be especially benzyl Base.

Phenyl-C1-C3 alkoxyl for example, benzyl epoxide, phenylethyl epoxide, α-methylbenzyl epoxide or α, alpha, alpha-dimethyl Base benzyl epoxide, is especially benzyl epoxide.

C2-C12 alkenyl radical is single unsaturated or the most unsaturated, for example, C2-C10-thiazolinyl, C2-C8-thiazolinyl, C2- C5-thiazolinyl, for example, vinyl, pi-allyl, methylallyl, 1,1-dimethyl-allyl, 1-butylene base, 3-cyclobutenyl, 2- Cyclobutenyl, 1,3-pentadiene base, 5-hexenyl, 7-octenyl or laurylene base, be especially pi-allyl.C2-C5 alkenyl radical There is the implication identical with the above-mentioned C2-C12 alkenyl radical corresponding to C atomic number.

C4-C8 cycloalkenyl group has more than 1 double bond, for example, C4-C6-cycloalkenyl group or C6-C8-cycloalkenyl group.For example, ring Cyclobutenyl, cyclopentenyl, cyclohexenyl group or cyclo-octene base, be especially cyclopentenyl or cyclohexenyl group, preferably cyclohexenyl group.

C3-C6 alkenyloxy group is single the most unsaturated or the most unsaturated, and it has to possess to be connected with above-mentioned corresponding to C atomic number and has The implication that the thiazolinyl of epoxide is identical.For example, pi-allyl epoxide, methylallyl epoxide, cyclobutenyl epoxide, pentenyl epoxide, 1, 3-pentadienyl epoxide, 5-hexenyl epoxide.

C2-C12 alkynyl is single unsaturated or the most unsaturated, and is line style or branched chain type, for example, C2-C8-alkynyl, C2-C6-alkynyl or C2-C4 alkynyl.For example, acetenyl, propinyl, butynyl, ethyl acetylene base, 3-butynyl, 2-butyne base, Pentynyl, hexin base, 2-hexin base, 5-hexin base, octynyl etc..

C2-C20 alkanoyl is line style or branched chain type, for example, C2-C18-alkanoyl, C2-C14-alkanoyl, C2-C12- Alkanoyl, C2-C8-alkanoyl, C2-C6-alkanoyl, C2-C4 alkanoyl, C4-C12-alkanoyl or C4-C8 alkanoyl.Such as For acetyl group, propiono, bytyry, isobutyryl, valeryl, caproyl, heptanoyl group, caprylyl, pelargonyl group, capryl, ten Dialkanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, octadecanoyl, eicosane acyl group, preferably acetyl group. C1-C8 alkanoyl has the implication identical with the above-mentioned C2-C20 alkanoyl corresponding to C atomic number.

C2-C12 alkoxy carbonyl is line style or branched chain type, for example, methoxycarbonyl, ethoxy carbonyl, propoxyl group carbonyl Base, normal-butyl epoxide carbonyl, isobutyl group epoxide carbonyl, 1,1-dimethyl propoxycarbonyl, amyl group epoxide carbonyl, hexyl epoxide carbonyl Base, heptyl epoxide carbonyl, octyl group epoxide carbonyl, nonyl epoxide carbonyl, decyloxycarbonyl or dodecyl epoxide carbonyl, especially For methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, normal-butyl epoxide carbonyl or isobutyl group epoxide carbonyl, preferably methoxy Base carbonyl.

The meaning of aryl is the aromatic monocyclic or multicyclic hydrocarbon ring system being only made up of hydrogen and carbon, and now, member ring systems is permissible The most saturated.At least more than one hydrogen atom in aryl can be taken by the substituent group identical with the situation of abovementioned alkyl Generation.Above-mentioned aryl is the organic free radical induced from aromatic hydrocarbon by removing a hydrogen, and it includes wrapping suitably in each ring The monocycle containing 4 to 7 annular atomses, preferably comprising 5 or 6 annular atomses or condensed ring system, also include that multiple aryl is with singly linked Form.Above-mentioned aryl preferably has 6 to 20 carbon atoms, more preferably has 6 to 18 carbon atoms.

C6-C20 aryl for example, phenyl, xenyl, terphenyl, stilbene radicals, naphthyl, anthryl (anthryl), anthryl (anthracenyl), phenanthryl, pyrenyl, pyrene,Aphthacene, benzophenanthrene etc., be especially phenyl or naphthyl, preferably phenyl.

The meaning of hydroxy alkyl is, the OH-alkyl that hydroxyl and alkyl defined above are combined into, hydroxy alkoxy alkyl The meaning be, the hydroxy alkyl-O-alkyl that above-mentioned hydroxy alkyl is formed by connecting by oxygen and alkyl.The carbon of above-mentioned hydroxy alkyl is former Subnumber is preferably 1-20, more preferably 1-10, most preferably 1-6.The carbon number of above-mentioned hydroxy alkoxy alkyl is excellent Electing 2 to 40 as, more preferably carbon number is 2 to 20, and most preferably carbon number is 2 to 9.

The meaning of C2-C4 hydroxy alkyl is, the C2-C4 alkyl replaced by 1 or 2 O atom.Alkyl diradical is line style Or branched chain type.Example is 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl Butyl, 4-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 2,3-dihydroxypropyl or 2,4-dihydroxy butyl.

The meaning of aryl alkyl is, more than one hydrogen atom of abovementioned alkyl is replaced by above-mentioned aryl.Aryl alkyl is preferred Carbon number is 7 to 40, and more preferably carbon number is 7 to 28, most preferably 7 to 24.

C1-C4 haloalkyl is by the C1-C4 alkyl as defined above of the halogen substiuted of following definitions.Alkyl diradical Such as can be by single or multiple halogenation (until all H atom be replaced by halogen).Its for example, C_nH_xHal_y(wherein, x+y= 2n+1, Hal are halogen, preferably F).Object lesson is chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, is especially three Methyl fluoride or trichloromethyl.

In the context of the present invention, C3-C20 heteroaryl is 1 ring or polycyclic system, and such as, its meaning includes condensed ring system. Such as there are thienyl, benzo [b] thienyl, naphtho-[2,3-b] thienyl, thianthrene group, furyl, dibenzofuran group, benzo Pyranose (chromenyl), ton base, thiopheneAlkyl, fenPiperazine base, pyrrole radicals, imidazole radicals, pyrazolyl, pyrazinyl, pyrimidine Base, pyridazinyl, indolizinyl, isoindolyl, indyl, indazolyl, purine radicals, quinolizinyl, isoquinolyl, quinolyl, phthalazines Base, naphthyridinyl, quinoxalinyl, quinazolyl, cinnolines base, pteridyl, carbazyl, B-carboline base, phenanthridinyl, acridinyl,Pyridine Base (perimidiny), luxuriant and rich with fragrance quinoline base, phenazinyl, isothiazolyl, phenothiazinyl, differentOxazolyl, furan a word used for translation base, fenPiperazine base, 7-phenanthryl, anthraquinone-2-base (=9,10-dioxo-9,10-dihydroanthracene-2-base), 3-benzo [b] thienyl, 5-benzo [b] thiophene Fen base, 2-benzo [b] thienyl, 4-dibenzofuran group, 4,7-dibenzofuran group, 4-methyl-7-dibenzofuran group, 2- Ton base, 8-methyl-2-ton base, 3-ton base, 2-fen thiopheneBase (phenoxathiinyl), 2,7-fen thiopheneBase, 2- Pyrrole radicals, 3-pyrrole radicals, 5-methyl-3-pyrrole radicals, 2-imidazole radicals, 4-imidazole radicals, 5-imidazole radicals, 2-methyl-4-imidazole radicals, 2- Ethyl-4-imidazole radicals, 2-ethyl-5-imidazole radicals, 1H-triazole-5-base, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl group-4- Pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl isophthalic acid-different Indyl, 1-methyl-2-indyl, 1-methyl-3-indyl, 1,5-dimethyl-2-indyl, 1-methyl-3-indazolyl, 2, 7-dimethyl-8-purine radicals, 2-methoxyl group-7-methyl-8-purine radicals, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7- Isoquinolyl, 3-methoxyl group-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxyl group-3-quinolyl, 2- Methoxyl group-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxyl group-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1, 8-naphthyridines-2-base, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxaline Base, 2-quinazolyl, 7-quinazolyl, 2-dimethylamino-6-quinazolyl, 3-cinnolines base, 6-cinnolines base, 7-cinnolines base, 3-methoxyl group-7-cinnolines base, 2-pteridyl, 6-pteridyl, 7-pteridyl, 6,7-dimethoxy-2-pteridyl, 2-carbazyl, 3-carbazyl, 9-methyl-2-carbazyl, 9-methyl-3-carbazyl, B-carboline-3-base, 1-methyl-ss-carboline-3-base, 1-first Base-B-carboline-6-base, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-Piperidinyl, 1-methyl-5-Piperidinyl, 5-phenanthrene quinoline Base, 6-phenanthrene quinoline base, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-are differentOxazolyl, 4-are differentOxazolyl, 5-are differentOxazolyl, 4-methyl-3-furan A word used for translation base, 2-fenPiperazine base, 10-methyl-2-fenPiperazine base etc..

C3-C20 heteroaryl is especially thienyl, benzo [b] thienyl, thianthrene group, thiopheneAlkyl, 1-methyl-2-indole Base or 1-methyl-3-indyl, be especially thienyl.

C4-C20 Heteroarylcarbonyl is the C3-C20 heteroaryl defined above being connected with molecule remainder by CO base.

Substituted aryl radical i.e. phenyl, naphthyl, C6-C20 aryl or C5-C20 heteroaryl each substituted 11 to 7 times, 1 to 6 time or 1 to 4 time, be especially 1,2 or 3 times.Obviously, defined aryl radical will not have than the freedom in aryl rings More substituent group is compared in position.

C1-C20 alkyl phenyl refers to the phenyl replaced by more than 1 alkyl, wherein, C atom add up to less than 20.

Substituent group on phenyl ring is preferably placed at 4 or 3,4-, 3,4,5-, 2,6-, 2,4-or 2,4,6-position on phenyl ring.

The free radical more than 1 time of being situated between such as is situated between 1-19,1-15,1-12,1-9,1-7,1-5,1-4,1-3 or 1 or 2 time (obviously, be situated between atomic number be intended to be situated between the difference of C atomic number and different).

Replace more than 1 time, substituted free radical such as there is 1-7,1-5,1-4,1-3 or 1 or 2 identical or different Substituent group.

The free radical replaced by 1 substituent group defined above has the 1 of identical or different definition as provided above Individual substituent group, or there is more substituent group.

Halogen is fluorine, chlorine, bromine and iodine, is especially fluorine, chlorine and bromine, preferably fluorine and chlorine.

The oxime ester derivative compound of above-mentioned [chemical formula 1] is represented by following [chemical formula 1-1].

[chemical formula 1-1]

In above-mentioned chemical formula 1-1,

R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Be independently of one another hydrogen, C1-C20 alkyl,COR₁₆、OR₁₇、 Halogen, NO₂Or

Or, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈It is quilt independently of one anotherSubstituted C2-C10 thiazolinyl,

Or, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈It is-(CH the most together₂)_p-Y- (CH₂)_q-,

Or, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈It is the most together

Wherein, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Middle least one set for for

R₉、R₁₀、R₁₁And R₁₂It is hydrogen, non-substituted or by more than 1 halogen, phenyl, CN, OH, SH, C1-independently of one another C4-alkoxyl, (CO) OH or (CO) O (C1-C4 alkyl) substituted C1-C20 alkyl,

Or, R₉、R₁₀、R₁₁And R₁₂Be independently of one another non-substituted phenyl or by more than 1 C1-C6 alkyl, halogen, CN, OR17, SR18 or NR₁₉R₂₀Substituted phenyl,

Y is O, S, NR₂₆Or directly in conjunction with,

P is integer 0,1,2 or 3,

Q is integer 1,2 or 3,

X be CO or directly in conjunction with,

R ' is non-substituted or by more than 1 halogen, R₁₇、COOR₁₇、OR₁₇、SR₁₈、CONR₁₉R₂₀、NR₁₉R₂₀、PO (OC_kH_2k+1) 2 orSubstituted C1-C20 alkyl,

Or, R ' is having more than 1 O, S, SO, SO for being situated between₂、NR₂₆Or the C2-C20 alkyl of CO, be non-Jie or be situated between and exist There are more than 1 O, CO or NR₂₆C2-C12 thiazolinyl,

Wherein, by be situated between C2-C20 alkyl and non-Jie or by be situated between C2-C12 thiazolinyl be non-substituted or by 1 with Upper halogen substiuted,

Or, R ' be C4-C8 cycloalkenyl group, C2-C12 alkynyl or non-Jie or be situated between and having more than 1 O, S, CO or NR₂₆'s C3-C10 cycloalkyl,

Or, R ' is phenyl or naphthyl, and each of which is non-substituted or by more than 1 OR₁₇、SR₁₈、NR₁₉R₂₀、COR₁₆、CN、NO₂, halogen, C1-C20 alkyl, C1-C4 haloalkyl, It is situated between and is having more than 1 O, S, CO or NR₂₆C2-C20 alkyl replace, or, each of which by C3-C10 cycloalkyl or be situated between having 1 Individual above O, S, CO or NR₂₆C3-C10 cycloalkyl substituted,

K is integer 1-10,

R₁₄For hydrogen, C3-C8 cycloalkyl, C2-C5 thiazolinyl, C1-C20 alkoxyl, or be non-substituted or by more than 1 halogen, Phenyl, C1-C20 alkyl phenyl or CN substituted C1-C20 alkyl,

Or, R₁₄For phenyl or naphthyl, each of which be non-substituted by more than 1 C1-C6 alkyl, C1-C4 haloalkyl, Halogen, CN, OR₁₇、SR₁₈And/or NR₁₉R₂₀Replace,

Or, R₁₄For C3-C20 heteroaryl, C1-C8 alkoxyl, benzyl epoxide or phenoxy group, above-mentioned benzyl epoxide and benzene oxygen Base is non-substituted, or, by more than 1 C1-C6 alkyl, C1-C4 haloalkyl and/or halogen substiuted,

R₁₅For C6-C20 aryl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 phenyl, halogen, C1- C4 haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂, SO-C1-C10 alkyl, SO₂-C1-C10 alkyl, Jie There are being more than 1 O, S or NR₂₆C2-C20 alkyl replace, or, each of which is non-substituted or is replaced by following radicals, institute State group by more than 1 halogen, COOR₁₇、CONR₁₉R₂₀, phenyl, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6-C20 aryl Epoxide carbonyl, C3-C20 heteroaryloxycarbonyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted C1-C20 alkyl,

Or, R₁₅For non-substituted or by more than 1 halogen, OR₁₇、SR₁₈, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6- C20 aryloxycarbonyl, C3-C20 heteroaryloxycarbonyl, NR₁₉R₂₀、COOR₁₇、CONR₁₉R₂₀、PO(OC_kH_2k+1)₂、Phenyl substituted C1-C20 alkyl, above-mentioned C1-C20 alkyl is replaced by following radicals, Described group is by halogen, C1-C20 alkyl, C1-C4 haloalkyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted phenyl,

Or, R₁₅More than 1 O, SO or SO is being had for being situated between₂C2-C20 alkyl, above-mentioned by be situated between C2-C20 alkyl be Non-substituted or by more than 1 halogen, OR₁₇、COOR₁₇、CONR₁₉R₂₀, phenyl or following radicals replace, described group is by OR₁₇、 SR₁₈Or NR₁₉R₂₀Substituted phenyl,

Or, R₁₅For non-substituted or by more than 1 OR₁₇Substituted naphthoyl or C3-C14 Heteroarylcarbonyl,

Or, R₁₅For CN, CONR₁₉R₂₀、NO₂, C1-C4 haloalkyl, S (O)_m-C1-C6 alkyl, or be non-substituted or quilt C1-C12 alkyl or SO₂-C1-C6 alkyl substituted S (O) m-phenyl,

M is 1 or 2,

R'₁₄Have and R₁₄Identical implication,

R'₁₅Have and R₁₅Identical implication,

X₁For O, S, SO or SO₂,

X₂For O, CO, S or directly in conjunction with,

R₁₆For C6-C20 aryl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 phenyl, halogen, C1- C4 haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀Or Jie is having more than 1 O, S or NR₂₆C1-C20 alkyl replace, or Each of which is non-substituted or is replaced by more than 1 following radicals, and described group is by more than 1 halogen, COOR₁₇、 CONR₁₉R₂₀, phenyl, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6-C20 aryloxycarbonyl, C3-C20 heteroaryl epoxide carbonyl Base, OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted C1-C20 alkyl,

N is 1-20,

R₁₇For hydrogen, phenyl-C1-C3 alkyl, non-substituted or by more than 1 halogen, OH, SH, CN, C3-C6 alkenyloxy group, OCH₂CH₂CN、OCH₂CH₂(CO) O (C1-C4 alkyl), O (CO)-(C1-C4 alkyl), O (CO)-(C2-C4) thiazolinyl, O (CO)-benzene Base, (CO) OH, (CO) O (C1-C4 alkyl), C3-C20 cycloalkyl, SO2-(C1-C4 haloalkyl), O (C1-C4 haloalkyl) Or it is situated between at the C1-C20 alkyl of the C3-C20 cycloalkyl substituted having more than 1 O,

Or, R₁₇For C1-C4 haloalkyl,

Or, R₁₇For (CH₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C1-C8 alkyl), C1-C8 alkanoyl, C2-C12 alkene Base, C3-C6 enoyl-, or for non-Jie or be situated between having more than 1 O, S, CO or NR₂₆C3-C20 cycloalkyl,

Or, R₁₉And R₂₀With they with atom N together form heteroaromatic ring system, described heteroaromatic ring system is non- Replace or by more than 1 C1-C20 alkyl, C1-C4 haloalkyl, C1-C20 alkoxyl ,=O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO) R₂₃、Halogen, NO₂, CN, phenyl or be situated between or be situated between having more than 1 O, S, CO or NR₁₇C3-C20 Cycloalkyl substituted,

Wherein, molecular memory is at least 1 group

The compound of chemical formula 1-1 is characterised by, it is (many that they comprise more than one thick and unsaturated ring at carbazole moiety Individual unsaturated ring).That is, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Middle least one set is

It is situated between and is having more than 1 O, S, NR₂₆Or the C2-C20 alkyl of CO be such as situated between 1-9,1-5,1-3 or 1 or 2 O, S, NR₂₆Or CO.Being situated between in the case of free radical more than 1 in existence, they are identical type or variety classes.2 O atom are by 1 Individual above methylene, preferably by more than 2 i.e. ethylidene of ofmcthylene-based separately.Alkyl is line style or branched chain type.Such as there will be Following construction unit-CH₂-CH₂-O-CH₂CH₃、-[CH₂CH₂O]_y-CH₃(wherein, y=1-9) ,-(CH₂-CH₂O)₇-CH₂CH₃、- CH₂-CH(CH₃)-O-CH₂-CH₂CH₃、-CH₂-CH(CH₃)-O-CH₂-CH₃、-CH₂-CH₂-S-CH₂CH₃、-CH₂-CH(CH₃)- NR₂₆-CH₂-CH₃、-CH₂-CH₂-COO-CH₂CH₃Or-CH₂-CH(CH₃)-OCO-CH₂-CH₂CH₃。

O, S, CO, NR is being had being situated between₂₆C3-C20 cycloalkyl in, more than 1 CH of alkyl₂-base is by O, S, CO or NR26 Replace, there is the implication of above-mentioned imparting.

It is situated between and is having more than 1 O, CO or NR₂₆C2-C12 thiazolinyl be such as situated between at 1-9,1-5,1-3 or 1 or 2 O, S, NR₂₆ Or CO.Being situated between in the case of free radical more than 1 in existence, they are identical type or variety classes.2 O atom by 1 with Upper methylene, preferably by more than 2 i.e. ethylidene of methylene separately.Thiazolinyl is line style or branched chain type, as defined above.Example As, following construction unit-CH=CH-O-CH can be formed₂CH₃,-CH=CH-OCH=CH₂Deng.

Being situated between at the C2-C12 alkoxy carbonyl having more than 1 O is line style or branched chain type.2 O atom are by more than 2 methylenes Base i.e. ethylidene is separately.Above-mentioned by be situated between alkoxy carbonyl be non-substituted or replaced by more than 1 hydroxyl.

C6-C20 aryloxycarbonyl for example, phenyloxycarbonyl [=phenyl-O-(CO)-], naphthyl epoxide carbonyl, anthracene Base epoxide carbonyl etc..

C5-C20 heteroaryloxycarbonyl is C5-C20 heteroaryl-O-CO-.

C3-C10 naphthene base carbonyl is C3-C10 cycloalkyl-CO-, and wherein, it is upper that cycloalkyl has with corresponding to C atomic number State the implication that cycloalkyl is identical.

It is situated between and is having more than 1 O, S, CO, NR₂₆C3-C10 naphthene base carbonyl refer to by be situated between cycloalkyl-CO-, wherein, By be situated between cycloalkyl as defined above.

C3-C10 cycloalkyloxycarbonyl be C3-C10 cycloalkyl-O-(CO)-, wherein, cycloalkyl has and C atomic number institute The implication that corresponding above-mentioned cycloalkyl is identical.

It is situated between and is having more than 1 O, S, CO, NR₂₆C3-C10 cycloalkyloxycarbonyl refer to by be situated between cycloalkyl-O- (CO)-, wherein, by be situated between cycloalkyl as defined above.

Naphthyl is 1-naphthyl or 2-naphthyl.

Work as R₁And R₂、R₂And R₃、R₃And R₄Or R₅And R₆、R₆And R₇、R₇And R₈Time the most together, such as, formed following Structure I a-Ii:

Or be preferably Such structure.

The compound of chemical formula 1-1 is carried out characterization and refers to that more than 1 phenyl ring and carbazole moiety condensation form " naphthalene " Ring.It i.e. provides with chemical formula 1-1 for the one in said structure.

Work as R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇, or R₇And R₈It is-(CH the most together₂)_p-Y- (CH₂)_q-time, such as, formed such asSuch structure etc..

Substituent group OR on phenyl ring or naphthalene nucleus₁₇、SR₁₈、SOR₁₈、SO₂R₁₈Or NR₁₉R₂₀By having the carbon atom of naphthalene nucleus In the free radical R of 1₁₇、R₁₈、R₁₉And/or R₂₀Form five yuan or during hexatomic ring, it is thus achieved that comprise more than 3 rings (comprising naphthalene nucleus) Structure.

Work as R₁₇WithIn residing phenyl ring or the carbon atom of naphthalene nucleus 1 Individual formation directly in conjunction with time, such as formed such asEtc. structure.

Work as R₁₆For by SR₁₈(wherein, free radical R₁₈Represent and COR₁₆Phenyl ring or the naphthalene nucleus of the carbazole moiety that base is connected directly are tied Close) substituted phenyl time, such as formed such as Etc. structure.That is, R is worked as₁₆For by SR₁₈(wherein, free radical R₁₈Represent and COR₁₆The phenyl ring of the carbazole moiety that base is connected or naphthalene nucleus Directly in conjunction with) substituted phenyl time, together form thiophene with in the phenyl ring of carbazole moiety or naphthalene nucleusMoieties.

Work as R₁₉And R₂₀With they with atom N together formed at random to be situated between and having O, S or NR₁₇Five yuan or hexa-atomic During saturated or unsaturated ring, form saturated or unsaturated ring, such as ethylene imine, pyrroles, thiazole, pyridine,Azoles, pyrimidine, 1,3- Diazine, 1,2-diazine, piperidines or morpholine.

Preferably, R is worked as₁₉And R₂₀With they with atom N together formed at random to be situated between and having O, S or NR₁₇Five yuan Or during hexa-atomic saturated or unsaturated ring, being formed is not situated between or is situated between O or NR₁₇, five yuan of especially O or hexa-atomic saturated rings.

Work as R₂₁And R₂₂With they with atom N together formed at random to be situated between and having O, S or NR₂₆And phenyl ring is at random With five yuan of saturated or unsaturated cyclic condensation or hexa-atomic saturated or during unsaturated ring, form saturated or unsaturated ring, such as a word used for translation third Pyridine, pyrroles, thiazole, pyridine,Azoles, pyrimidine, 1,3-diazines, 1,2-diazine, piperidines or morpholine, or the ring of the thickest sum, example AsDeng.

Work as R₁₉And R₂₀With they with atom N together form heteroaromatic ring system time, above-mentioned ring system is more than 1 Ring, such as 2 or 3 rings, and for comprising 1 or more than 1 identical type or different types of heteroatomic ring.Suitably Hetero atom for example, N, S, O or P, be especially N, S or O.

For example, carbazole, indole, iso-indoles, indazole, purine, isoquinolin, quinoline, carboline or phenothiazine etc..

The oxime ester derivative compound of above-mentioned [chemical formula 1] can be represented by following [chemical formula 1-2].

[chemical formula 1-2]

(in chemical formula 1-2,

R’、R”、R₁₄And R₁₅Be each independently hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base or C3-C20 cycloalkyl,

R₁To R₅、R₇And R₈For hydrogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base, C3-C20 cycloalkyl, amino, nitro, cyano group or hydroxyl,

R is 0 or 1.)

Now, about Photoepolymerizationinitiater initiater, r can be 1 or 2, when r is 0, can be represented by following chemical formula 2, work as r When being 1, can be represented by following chemical formula 3, described further below.

[chemical formula 2]

(in above-mentioned chemical formula 2,

R’、R”、R₂₇And R₂₈Be each independently hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base or C3-C20 cycloalkyl,

A is hydrogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxyl alkane Epoxide, C1-C20 alkyl or C3-C20 cycloalkyl, amino, nitro, cyano group or hydroxyl.)

Additionally, the C1-C20 alkyl disclosed in the present invention is preferably C1-C10 alkyl, more preferably C1-C6 alkyl.C6- C20 aryl is preferably C6-C18 aryl.C1-C20 alkoxyl is preferably C1-C10 alkoxyl, more preferably C1-C4 alkoxyl. C6-C20 aryl and C1-C20 alkyl are preferably C6-C18 aryl and C1-C10 alkyl, more preferably C6-C18 aryl and C1-C6 Alkyl.C1-C20 hydroxy alkyl is preferably C1-C10 hydroxy alkyl, more preferably C1-C6 hydroxy alkyl.C1-C20 hydroxy alkoxy Base and C1-C20 alkyl are preferably C1-C10 hydroxy alkoxy base and C1-C10 alkyl, more preferably C1-C4 hydroxy alkoxy base and C1- C6 alkyl.C3-C20 cycloalkyl is preferably C3-C10 cycloalkyl.

Specifically, above-mentioned R ', R ", R₁₄And R₂₇It is each independently hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-pro-pyl, different Propyl group, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, phenyl, naphthyl, xenyl, terphenyl Base, anthryl, indenyl, phenanthryl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, Hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl N-hexyl, hydroxyl isohesyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl group, hydroxymethoxy fourth Base, hydroxyethoxymethyl, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl Or hydroxyl-oxethyl hexyl,

A can be hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, phenyl, naphthyl, biphenyl Base, terphenyl, anthryl, indenyl, phenanthryl, methoxyl group, ethyoxyl, propoxyl group, butoxy, hydroxymethyl, hydroxyethyl, hydroxyl Propyl group, hydroxybutyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl group, hydroxymethoxy butyl, hydroxyl Base oxethyl methyl, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, amino, nitro, cyano group or hydroxyl Base, but it is not limited to this.

More specifically, above-mentioned R ' and R " can be hydrogen or normal-butyl, R₂₇Can be methyl, R₁₄Can be methyl, positive fourth Base or phenyl.

Following reaction equation 1 can be passed through according to the oxime ester fluorene derivative compound represented by the above-mentioned chemical formula 2 of the present invention Manufacture.

[reaction equation 1]

(in above-mentioned reaction equation 1, R ', R ", R₁₄And R₂₇Identical with the definition in chemical formula 2, X is halogen.)

[chemical formula 3]

(in above-mentioned chemical formula 3,

R’、R”、R₂₉To R₃₇Be each independently hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C7-C40 aryl alkyl, C1-C20 hydroxy alkyl, C2-C40 hydroxy alkoxy alkyl or C3-C20 cycloalkyl.)

Specifically, above-mentioned R ', R ", R₂₉And R₃₇It is each independently hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-pro-pyl, different Propyl group, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, phenyl, naphthyl, xenyl, terphenyl Base, anthryl, indenyl, phenanthryl, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, Hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxyl n-pentyl, hydroxyl isopentyl, hydroxyl N-hexyl, hydroxyl isohesyl, hydroxymethoxy methyl, hydroxymethoxy ethyl, hydroxymethoxy propyl group, hydroxymethoxy fourth Base, hydroxyethoxymethyl, hydroxyl ethoxy ethyl, hydroxyethoxypropyl, hydroxyl-oxethyl butyl, hydroxyethoxypentyl Or hydroxyl-oxethyl hexyl.

More specifically, above-mentioned R ' and R " can be hydrogen, methyl, ethyl, propyl group or butyl, R₃₇Can be methyl, ethyl Or propyl group, R₃₆Can be methyl, ethyl, propyl group or butyl, R₂₉To R₃₅Can be hydrogen.

Following reaction equation 2 can be passed through according to the oxime ester fluorene derivative compound represented by the above-mentioned chemical formula 3 of the present invention Manufacture.

[reaction equation 2]

(in above-mentioned reaction equation 2, R ', R ", R₂₉To R₃₇And A is each independently hydrogen, halogen, C1-C20 alkyl, C6- C20 aryl, C1-C20 alkoxyl, C7-C40 aryl alkyl, C1-C20 hydroxy alkyl, C2-C40 hydroxy alkoxy alkyl or C3- C20 cycloalkyl, X is halogen.)

About above-mentioned Photoepolymerizationinitiater initiater, relative to the solid constituent in the blue-sensitive resin combination of the present invention Gross weight, comprises 0.1 to 10 weight portion with mass ratio range.If Photoepolymerizationinitiater initiater is in above-mentioned scope, then exist because of indigo plant The intensity in the pixel portion that color sensation photosensitive resin composition high-sensitivity and use said composition are formed or the table in this pixel portion The tendency that the flatness in face is good, the most preferably.

The coloring agent contained by blue-sensitive resin combination of the present invention can use at Colour Index (Color (The Society of Dyers and Colourists publication) Index) is classified as the chemical combination of pigment (pigment) Thing i.e. organic pigment, or use metal-oxide, metallic complex salt, the inorganic salt i.e. inorganic pigment of barium sulfate, from thermostability and The aspect of excellent color reproducing performance is set out, and more preferably uses organic pigment.

Object lesson as coloring agent, it may include select free C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment Blue 15:4, C.I. pigment blue 15: 6, more than a kind in the group of the blue pigment composition such as C.I. pigment blue 60.

Additionally, coloring agent can further include choosing free C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. a kind in the group of the violet pigment such as pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38 composition Above.

About coloring agent, relative to the solid constituent in blue-sensitive resin combination, 5 to 40 weight can be comprised Part, if above-mentioned coloring agent is in above-mentioned scope, even if then forming thin film, the colour saturation of pixel is also abundant, and when developing The defect in non-pixel portion will not reduce, and does not the most produce residue.

Now, coloring agent processes because implementing dispersion containing pigment dispersing agent such that it is able to obtain dividing equably in solution Dissipate the dispersible pigment dispersion having blue pigment state.As above-mentioned pigment dispersing agent, such as cation system, anion system, non-can be enumerated The surfactants etc. such as ionization series, both sexes, Polyester, polyamine system and polyacrylic, they can be alone or in combination of two kinds or more Use.

About the alkali-soluble binder resin contained by the blue-sensitive resin combination of the present invention, in order to make it relative The alkaline developer used in development treatment operation in time forming pattern has solubility, will have the ethylene insatiable hunger of carboxyl As neccessary composition with monomer and carry out copolymerization and manufacture.Additionally, in order to ensure the compatibility and blue-sensitive tree with dyestuff The storage stability of oil/fat composition, the acid number of alkali-soluble binder resin is preferably 30 to 150mgKOH/g.Bond at alkali solubility The acid number of agent resin is less than in the case of 30mgKOH/g, it is difficult to guarantee the sufficient developing powder of blue-sensitive resin combination, In the case of more than 150mgKOH/g, reduce with the adaptation of substrate and be prone to occur the short circuit of pattern, and with dyestuff The compatibility comes into question, thus dyestuff in blue-sensitive resin combination separates out or the depositing of blue-sensitive resin combination Storage stability reduces, thus viscosity easily rises.

In order to ensure the additional developability of above-mentioned alkali-soluble binder resin, hydroxyl can be given.If imparting hydroxyl, then There is the effect improving developing powder, but the hydroxyl value sum of alkali-soluble binder resin and photopolymerizable compound is defined as More than 50mgKOH/g and below 250mgKOH/g.In the case of hydroxyl value sum is less than 50mgKOH/g, it is impossible to guarantee sufficiently Developing powder, in the case of more than 250mgKOH/g, the dimensional stability of the pattern formed reduces and easily makes pattern Grazing becomes bad, and reduces with the compatibility of dyestuff, thus the problem easily producing storage stability.

As the object lesson of the above-mentioned ethylene unsaturated monomer with carboxyl, can enumerate acrylic acid, methacrylic acid, The monocarboxylic acid classes such as .beta.-methylacrylic acid, omega-dicarboxylic acids and the anhydride of these dicarboxylic acids such as fumaric acid, mesaconic acid, itaconic acid, ω-carboxyl gathers Two ends such as caprolactone list (methyl) acrylate have list (methyl) esters of acrylic acid etc. of the polymer of carboxyl and hydroxyl, excellent Elect acrylic acid, methacrylic acid as.

In order to give hydroxyl to alkali-soluble binder resin, by having the ethylene unsaturated monomer of carboxyl and can have The ethylene unsaturated monomer copolymerization of hydroxyl manufactures, and can make to have the compound of glycidyl and have the ethylene of carboxyl The copolymer of property unsaturated monomer reacts further and manufactures.Additionally, the compound with glycidyl can be made and there is carboxylic The copolymer of the ethylene unsaturated monomer of base and the ethylene unsaturated monomer with hydroxyl reacts further and manufactures.

As the above-mentioned ethylene unsaturated monomer object lesson with hydroxyl, there is 2-hydroxyethyl (methyl) acrylic acid Ester, 2-hydroxypropyl (methyl) acrylate, 4-hydroxybutyl (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (first Base) acrylate, N-hydroxyethyl acrylamide etc., preferably 2-hydroxyethyl (methyl) acrylate, can combine 2 kinds with Upper use.

As the object lesson of the above-mentioned compound with glycidyl, there are butyl glycidyl ether, (+)-2,3-Epoxy-1-propanol third Ether, glycidyl phenyl ether, 2-hexyl glycidyl ether, Glycidyl Butyrate, (+)-2,3-Epoxy-1-propanol methyl ether, ethyl glycidyl Ether, (+)-2,3-Epoxy-1-propanol diisopropyl ether, tertiary butyl glycidyl ether, benzyl glycidyl ether, (+)-2,3-Epoxy-1-propanol 4-p t butylbenzoic acid ester, contracting Water glyceryl stearate, arylolycidyl ethers, glycidyl methacrylate etc., preferably butyl glycidyl ether, virtue Base glycidyl ether, glycidyl methacrylate, can combine two or more and use.

Hereinafter, can illustrate when manufacturing above-mentioned alkali-soluble binder resin can the unsaturated monomer of copolymerization, but be not limited to this.

As have can copolymerization unsaturated bond polymerization monomer object lesson, have styrene, vinyltoluene, α- Methyl styrene, to chlorostyrene, o-methoxystyrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl Base methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinylbenzyl glycidyl ether, a vinyl benzyl Glycidyl ether, to the aromatic ethenyl compounds such as vinylbenzyl glycidyl ether, N-N-cyclohexylmaleimide, N-benzyl Hydroxyphenyl-maleimides between base maleimide, N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, N-, Between N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, N-, methylphenylmaleimide, N-are to methyl Phenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-are to methoxybenzene The N-substituted maleimide amine compounds such as base maleimide, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (first Base) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (first Base) (methyl) alkyl-acrylates such as sec-butyl acrylate, (methyl) tert-butyl acrylate, cyclopenta (methyl) acrylic acid Ester, cyclohexyl (methyl) acrylate, 2-methylcyclohexyl (methyl) acrylate, three rings [5.2.1.02,6] decane-8-base The fat such as (methyl) acrylate, 2-dicyclopentenyl epoxide ethyl (methyl) acrylate, isobornyl (methyl) acrylate Ring race (methyl) esters of acrylic acid, (methyl) the benzyl acrylate class such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, 3-(methylacryloyl epoxide methyl) oxetanes, 3-(methylacryloyl epoxide methyl)-3-Ethyloxetane, 3-(methylacryloyl epoxide methyl)-2-trifluoromethyl oxetanes, 3-(methylacryloyl epoxide methyl)-2-phenyl Oxetanes, 2-(methylacryloyl epoxide methyl) oxetanes, 2-(methylacryloyl epoxide methyl)-4-trifluoro The unsaturated oxetane compound such as methy oxetane etc..

Above-mentioned unsaturated monomer can each be used alone or in combination of two kinds or more.

Hydroxyl value about the content of above-mentioned alkali-soluble binder resin, alkali-soluble binder resin and photopolymerizable compound Sum should meet the condition of 50mgKOH/g to 250mgKOH/g, relative to the solid constituent in blue-sensitive resin combination, Preferably comprise 1 to 40 weight portion in parts by weight, more preferably comprise 10 to 30 weight portions.If the content of above-mentioned alkali soluble resins Be in above-mentioned scope, then the dissolubility in developer solution fully and easily forms pattern, and exposure portion when preventing from developing The film of pixel portion reduces and makes the defect of non-pixel portion become good, the most preferably.

The photopolymerizable compound contained by blue-sensitive resin combination of the present invention is by light and light described later The effect of polymerization initiator and the compound that can be polymerized, can enumerate monofunctional monomer, bifunctional monomer and polyfunctional monomer Deng.

As the object lesson of above-mentioned monofunctional monomer, there are nonyl phenyl carbitol acrylate, 2-hydroxyl-3-phenoxy group Propyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethylmethacry,ate, NVP etc., But it is not limited to this.

As the object lesson of above-mentioned bifunctional monomer, have 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (first Base) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, double (propylene of bisphenol-A Acyloxy ethyl) ether, 3-methyl pentanediol two (methyl) acrylate etc., but it is not limited to this.

As the object lesson of polyfunctional monomer, there are trimethylolpropane tris (methyl) acrylate, ethoxylation three hydroxyl Methylpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (first Base) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, ethoxylation two season Penta tetrol six (methyl) acrylate, propoxylated dipentaerythritol six (methyl) acrylate or dipentaerythritol six (methyl) Acrylate etc., but it is not limited to this.

In foregoing illustrative photopolymerizable compound, it may be preferred to ground uses the polyfunctional monomer of more than difunctionality.Above-mentioned The photopolymerizable compound illustrated can each be used alone or in combination of two kinds or more.

About above-mentioned photopolymerizable compound, relative to the solid constituent in blue-sensitive resin combination, can wrap Containing 1 to 20 weight portion, if above-mentioned photopolymerizable compound is in above-mentioned scope, then intensity or the flatness in pixel portion can become Obtain well, the most preferably.

The solvent contained by blue-sensitive resin combination of the present invention is not particularly limited, it is possible to use in this area The various solvents used.

As the object lesson of solvent, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, second two can be enumerated The ethylene glycol monoalkyl ether classes such as alcohol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethyl The diethylene glycol dialkyl ether classes such as dibutyl ether, the ethylene glycol alkyl such as methylcellosolve acetate, ethyl cellosolve acetate Ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetas, methoxyl group fourth The aklylene glycol alkylether acetates classes such as yl acetate and methoxypentyl acetas, benzene,toluene,xylene, sym-trimethylbenzene. Etc. aromatic hydrocarbon, the ketone such as butanone, acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, ethanol, propanol, butanol, The alcohols such as hexanol, Hexalin, ethylene glycol, glycerol, the esters such as 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate, γ-Ding Nei The ring-type esters such as ester etc..

In above-mentioned solvent, when considering coating and during drying property aspect, it is 100 to 200 DEG C molten that boiling point is preferably used Agent, more preferably uses aklylene glycol alkylether acetates class, ketone, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate Deng esters, further preferably use selected from propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, Ketohexamethylene, 3-ethoxy Solvent in base ethyl propionate, 3-methoxy methyl propionate etc..Above-mentioned solvent can each individually or mix two or more and use.

About the content of above-mentioned solvent, relative to blue-sensitive resin combination total amount, preferably comprise 20 to 85 weight Part, more preferably comprise 50 to 80 weight portions.If the content of solvent is in above-mentioned scope, then when with roll coater, rotation When the apparatus for coating such as coating machine, slit spin coater, slit coater, ink-jet are coated, coating can become good.

The blue-sensitive resin combination of the present invention can further include additive.

Additive is the material that selectivity adds as required, as object lesson, can enumerate filler, other macromolecules Compound, pigment dispersing agent, closely sealed accelerator, antioxidant, UV absorbent, anticoagulant etc..

As the object lesson of above-mentioned filler, glass, silicon dioxide, aluminium oxide etc. can be enumerated.

As the object lesson of other macromolecular compounds above-mentioned, epoxy resin, maleimide resin etc. can be enumerated solid The property changed resin, the heat such as polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-fluoroalkyl, polyester, polyurethane Plastic resin etc..

As above-mentioned pigment dispersing agent, it is possible to use commercially available surfactant, can enumerate such as silicon-type, fluorine system, ester The surfactants such as system, cation system, anion system, nonionic system, both sexes system.They can the most alone or in combination 2 kinds with Upper use.As the object lesson of above-mentioned surfactant, polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether can be enumerated Class, polyethylene glycol di class, sorbitan fatty acid ester class, fatty acid modified polyesters, tertiary-amine modified polyurethanes, poly-second Alkene imines etc., in addition, can enumerate KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), POLYFLOW (common prosperity society with trade name Chemistry (strain) manufactures), (big Japanese ink chemical industry (strain) is made for EFTOP (Tohkem Products company manufacture), MEGAFAC Make), Flourad (Sumitomo 3M (strain) manufacture), Asahi guard, Surflon (more than, Asahi Glass glass (strain) manufacture), SOLSPERSE (Zeneca (strain) manufacture), EFKA (EFKA Chemicals company manufacture), PB 821 (aginomoto (strain) manufacture) Deng.

As above-mentioned closely sealed accelerator, can enumerate such as vinyltrimethoxy silane, VTES, ethylene Base three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino Ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyl group trimethoxy Silane, 3-glycidoxypropyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chlorine Hydroxypropyl methyl dimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3- Mercaptopropyi trimethoxy silane etc..

As above-mentioned antioxidant, 2 specifically can be enumerated, 2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-bis--uncle Butyl-4-methylphenol etc..

As above-mentioned UV absorbent, 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzene specifically can be enumerated And triazole, alkoxy benzene ketone etc..As anticoagulant, sodium polyacrylate etc. specifically can be enumerated.

As the object lesson of above-mentioned anticoagulant, sodium polyacrylate etc. can be enumerated.

Additionally, the present invention provides the color filter manufactured by above-mentioned blue-sensitive resin combination.

In the case of the color filter of the present invention is applied to image display device, sent out by the light of display device light source Light, therefore, it is possible to show more excellent light efficiency.Additionally, due to release carries coloured light, therefore colorrendering quality is more Add excellence, and owing to utilizing luminescence generated by light to discharge light to all directions, therefore can improve visual angle and make light characteristic excellent.

Color filter includes substrate and the patterned layer on the top being formed at aforesaid substrate.

About substrate, color filter itself can be substrate, or can also be the middle portions residing for color filter such as display device Position, is not particularly limited.Aforesaid substrate can be glass substrate, silicon (Si) substrate, Si oxide (SiO_x) substrate or macromolecule Substrate, above-mentioned polymeric substrate can be polyether sulfone (polyethersulfone, PES) or Merlon (polycarbonate, PC) etc..

Patterned layer is the layer of the photosensitive polymer combination comprising the present invention, can be to be coated with above-mentioned photosensitive resin composition After thing, expose in a predetermined pattern, develop and heat cure and the layer that formed.

The patterned layer formed by above-mentioned photosensitive composition can possess the redness containing red quantum dot particles Patterned layer, the green pattern layer containing green quantum dot particles and the blue color patterns layer containing blue quantum dot particles.When light irradiates, red Chromatic graph pattern layer release red light, green pattern layer release green light, blue color patterns layer release blue light.

When being applied to image display device with such situation, the release light of light source is not particularly limited, from more excellent Different brightness and colorrendering quality aspect are set out, and preferably use the light source of release blue light.

According to another embodiment of the present invention, above-mentioned patterned layer be further equipped with red pattern layer, green pattern layer and Do not contain the transparent pattern layer of quantum dot particles.In the case of the patterned layer only possessing 2 kinds of colors, it is possible to use release performance Go out the light source of the light of the wavelength of the residue color not comprised.Such as, in the case of comprising red pattern layer and green pattern layer, The light source of release blue light can be used.In this case, red quantum dot particles release red light, the release of green quantum dot particles is green Coloured light, transparent pattern layer is directed through blueness and shows blueness.

The color filter comprising aforesaid substrate and patterned layer can be further contained in the dividing plate formed between each pattern, it is possible to To comprise black matrix further.Further, it is also possible to comprise the protecting film on the patterned layer top being formed at color filter further.

Above-mentioned color filter is by comprising blue pigment, it is possible to when preventing hot and humid environment, and substrate may be sent out with patterned layer The raw problem peeled off.

Additionally, the present invention provides the liquid crystal display dress comprising the color filter manufactured by above-mentioned blue-sensitive resin combination Put.Therefore, by improving the closing force of color filter, it is possible to prevent the quality of liquid crystal indicator from reducing problem.

Hereinafter, in order to contribute to the understanding of the present invention, it is provided that preferred embodiment, but these embodiments are only used for illustrating this Invention, is not intended to appended claims scope, and those skilled in the art is it will be appreciated that think in scope of the invention and technology In the range of thinking, it is possible to carry out the numerous variations for embodiment and amendment, such change and amendment also ought to belong to encloses Right.

Synthesis example 1. Photoepolymerizationinitiater initiater (C-1) synthesizes: (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzene first Acyl)-13H-dibenzo [a, i] carbazole-8-base]-[4-(2,2,3,3-tetrafluoro propoxyl group)-phenyl]-ketoxime-O-acetas Synthesis

As intermediate 13-(2-ethylhexyl)-13H-dibenzo [a, i] carbazole, 1-naphthylhydrazine hydrochlorate is used to replace Phenyl hydrazine, and synthesize Photoepolymerizationinitiater initiater C-1 according to the order disclosed in following step 1 to 4.

Step 1:13-(2-ethylhexyl)-13H-dibenzo [a, i] carbazole

13H-dibenzo [a, i] carbazole can be public in such as document [SYNLETT, 2006,7,1021] according to particular order The order manufacture opened.

Sodium hydride is added at 0 DEG C of 13H-dibenzo [a, i] carbazole (0.70g, 3.22mol) in DMF (3ml) (0.19g, 4.67mmol).After 0 DEG C of stirring 1 hour, add 1-naphthylhydrazine hydrochlorate (1.24g, 6.44mmol) at 0 DEG C, will be mixed Compound is stirred at room temperature overnight.Reactant mixture is put into frozen water, crude product ethyl acetate is extracted 2 times.By having of merging Machine layer H₂O and saline clean, magnesium sulfate mutually in be dried and concentrate, be dried under vacuum, it is thus achieved that yellow liquid produces as thick Thing (1.08g).Product is the most further refined, and for subsequent reactions.

Step 2:(13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo [a, i] carbazole-8- Base] synthesis of-[4-(2,2,3,3-tetrafluoro propoxyl group)-phenyl]-ketone

0 DEG C of 13-(2-ethylhexyl)-13H-dibenzo [a, i] carbazole in METHYLENE CHLORIDE (400mL) (47.16g, 143.0mmol) add 2,4,6-tri-methyl chlorides (27.45g, 150.0mol) and aluminum chloride (20.00g, 150.0mol). After being stirred at room temperature 2 hours, add aluminum chloride (22.93g, 172.0mol) at 0 DEG C, and drip 2,4,6-tri-methyl chlorides (23.78g, 150.0mol), then stirs the mixture for 3 hours in room temperature.Reactant mixture is put into frozen water, crude product is used METHYLENE CHLORIDE is extracted 2 times.By merge organic layer water and saline clean, magnesium sulfate mutually in be dried.It is added thereto to just own After alkane 230ml, by concentrating, METHYLENE CHLORIDE is removed, it is thus achieved that beige solid.Reclaimed by filtering, cleaned with normal hexane, Then it is dried, it is thus achieved that beige solid (81.81g, 95.7%).

Step 3:(13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo [a, i] carbazole-8- Base] synthesis of-[4-(2,2,3,3-tetrafluoro propoxyl group)-phenyl]-ketoxime

At the room temperature (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-two in pyrimidine (10mL) Benzo [a, i] carbazole-8-base]-[4-(2,2,3,3-tetrafluoro propoxyl group)-phenyl]-ketone (5.98g, 10.0mol) interpolation 2-first Ethoxy-ethanol (2.28g, 30.00mol) and potassium t-butoxide (1.68g, 15.00mol).Heat the mixture to 80 DEG C, and will Its stirring 3.5 hours.After reactant mixture adds hydroxylammonium chloride (2.08g, 30.00mol), at 100 DEG C, mixture is stirred Mix overnight.After being cooled to room temperature, reactant mixture is put in 200ml water.By filtering, the solid of precipitation is reclaimed, so After it is cleaned with methanol.Obtain the white solid i.e. target compound of yield 71% (4.73g).

Step 4:(13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-dibenzo [a, i] carbazole-8- Base] synthesis of-[4-(2,2,3,3-tetrafluoro propoxyl group)-phenyl]-ketoxime-O-acetas

At 0 DEG C of (13-(2-ethylhexyl)-5-(2,4,6-trimethylbenzoyl)-13H-hexichol in acetone (20ml) And [a, i] carbazole-8-base]-[4-(2,2,3,3-tetrafluoro propoxyl group)-phenyl]-ketone (2.59g, 3.87mol) interpolation triethylamine (0.78g, 7.74mol) and chloroacetic chloride (0.61g, 7.74mol).Stir the mixture for 2 hours.After reaction terminates, reaction is mixed Compound puts in water.Then, crude product is extracted by t-butyl methyl ether.Organic layer water and saline are cleaned, magnesium sulfate mutually in It is dried and concentrates, it is thus achieved that residue.By this residue t-butyl methyl ether recrystallization, it is thus achieved that white solid (2.00g, 73%). Product is made up of admixture of isomeric compound.

Synthesis example 2. Photoepolymerizationinitiater initiater (C-2) synthesizes: 1-(9,9-H-7-nitrofluorene-2-base)-acetophenone oxime-O-acetas Synthesis

Step 1:1-(9,9-H-7-nitrofluorene-2-base)-ethyl ketone synthesizes

2-nitrofluorene (1) 5.0g (23.7mmol) is dissolved in anhydrous Nitrobenzol 100ml, adds anhydrous Aluminum chloride 6.31g (47.4mmol) after, reactant is warming up to 45 DEG C, was slowly added to dissolve chloroacetic chloride 2.79g (35.5mmol) via 30 minutes In the solution of anhydrous Nitrobenzol 30ml, reactant is warming up to 65 DEG C and stirs 1 hour.Afterwards, reactant is cooled to Room temperature, after adding distilled water 70ml and stirring about 30 minutes, filtration product.The solid product obtained is scattered in the ether of 50ml In, filter after being stirred at room temperature 30 minutes and be dried, obtaining lurid 1-(9,9-H-7-nitrofluorene-2-base)-ethyl ketone (2) 5.08g (84.7%).

Step 2:1-(9,9-H-7-nitrofluorene-2-base)-acetophenone oxime synthesizes

1-(9,9-H-7-nitrofluorene-2-base)-ethyl ketone (2) 1.5g (5.92mmol) is scattered in ethanol 30ml, adds salt Acid azanol 0.49g (7.1mmol) and sodium acetate 0.58g (7.1mmol), then slowly heat up reaction solution, carries out 2 hours returning Stream reaction.Reactant is cooled to room temperature, after adding distilled water 20ml, stirs about 30 minutes, the solid product mistake that will obtain Filter, is dried after being cleaned multiple times with distilled water, obtains grayish 1-(9,9-H-7-nitrofluorene-2-base)-acetophenone oxime (3) 1.38g (86.8%).

Step 3:1-(9,9-H-7-nitrofluorene-2-base)-acetophenone oxime-O-acetas synthesizes

1-(9,9-H-7-nitrofluorene-2-base)-acetophenone oxime (3) 1.20g (4.47mmol) is scattered in ethyl acetate 50ml, After adding anhydrous acetic acid 0.69g (6.76mmol), reaction solution is slowly heated up, carries out 3 hours back flow reaction.Reactant is cold But to room temperature, after cleaning successively with saturated sodium bicarbonate aqueous solution 20ml and distilled water 20ml, by the organic layer of recovery with anhydrous Magnesium sulfate is dried, and is distilled by solvent under reduced pressure, and by obtained product with methylalcohol 20ml recrystallization, obtain lurid 1-(9, 9-H-7-nitrofluorene-2-base)-acetophenone oxime-O-acetas (4) 1.22g (87.9%).

Synthesis example 3. Photoepolymerizationinitiater initiater (C-3) synthesizes: 1-(9,9-diethyl-9H-fluorenes-2-base)-1,2-propanedione-2- The synthesis of oxime-O-acetas

Step 1:9,9-diethyl-9H-fluorenes (2) synthesizes

In a nitrogen atmosphere by fluorenes (1) 200.0g (1.20mol), potassium hydroxide 268.8g (4.80mol) and potassium iodide 19.9g (0.12mol) is dissolved in anhydrous dimethyl sulfoxide 1L, reactant maintains 15 DEG C, was then slowly added to bromine via 2 hours Ethane 283.3g (2.60mol), stirs reactant 1 hour at 15 DEG C.Afterwards, add distilled water 2L to reactant, stir 30 After minute, extract product with dichloromethane 2L, the organic layer distilled water 2L extracted is cleaned 2 times, then organic by reclaim Layer anhydrous magnesium sulfate is dried, and is distilled by solvent under reduced pressure, and by the under reduced pressure fractional distillation of obtained product, obtains the liquid that viscosity is high Body the most lurid 9,9-diethyl-9H-fluorenes (2) 248.6g (93.3%).

The synthesis of step 2:1-(9,9-diethyl-9H-fluorenes-2-base)-1-acetone (3)

By 9,9-diethyl-9H-fluorenes (2) 100.5g (0.45mol) is dissolved in dichloromethane 1L, and reactant is cooled to-5 After DEG C, it is slowly added to aluminum chloride 72.3g (0.54mol), then while noting not making reactant heat up, delayed via 2 hours Slowly add the propionyl chloride 50.1g (0.54mol) being diluted in dichloromethane 50ml, at-5 DEG C, reactant is stirred 1 hour.It After, reactant slowly put into frozen water 1L and stirs 30 minutes, after organic layer is separated, cleaning with distilled water 500ml, will reclaim Organic layer decompression distillation, and by obtained product silica gel column chromatography (developing solvent: acetoacetic ester: normal hexane=1:4) essence System, obtains lurid solid 1-(9,9-diethyl-9H-fluorenes-2-base)-1-acetone (3) 75.8g (60.6%).

The synthesis of step 3:1-(9,9-diethyl-9H-fluorenes-2-base)-1,2-propanedione-2-oxime (4)

1-(9,9-diethyl-9H-fluorenes-2-base)-1-acetone (3) 44.5g (0.16mol) is dissolved in oxolane (THF) 900ml, is sequentially added into and is dissolved in Isosorbide-5-Nitrae-twoThe 4N HCl 150ml of alkane and isobutyl nitrite 24.7g (0.24mol), at 25 DEG C, reactant is stirred 6 hours.Afterwards, add ethyl acetate 500ml to reaction solution and stir 30 points Clock, after separating organic layer, cleans with distilled water 600ml, is then dried by the organic layer anhydrous magnesium sulfate of recovery, is subtracted by solvent Pressure distillation, and use ethyl acetate: the mixed solvent 300ml of hexane (1:6) will be dried after obtained solid product recrystallization, Obtain grayish solid 1-(9,9-diethyl-9H-fluorenes-2-base)-1,2-propanedione-2-oxime (4) 27.5g (56.0%).

The synthesis of step 4:1-(9,9-diethyl-9H-fluorenes-2-base)-1,2-propanedione-2-oxime-O-acetas (5)

In a nitrogen atmosphere by 1-(9,9-diethyl-9H-fluorenes-2-base)-1,2-propanedione-2-oxime (4) 89.0g (0.29mol) it is dissolved in METHYLPYRROLIDONE (NMP) 1L and reactant is maintained-5 DEG C, being subsequently adding triethylamine 35.4g (0.35mol), after being stirred 30 minutes by reaction solution, was slowly added to chloroacetic chloride 27.5g via 30 minutes (0.35mol) solution of METHYLPYRROLIDONE 75ml it is dissolved in, stirring while noting not making reactant heat up 30 minutes.Afterwards, it is slowly added to distilled water 1L to reactant and stirs 30 minutes, after separating organic layer, the organic layer that will reclaim Be dried with anhydrous magnesium sulfate and reduce pressure solvent distillation.Use ethanol 1L by being dried after obtained solid product recrystallization, obtain Grayish solid 1-(9,9-diethyl-9H-fluorenes-2-base)-1,2-propanedione-2-oxime-O-acetas (5) 93.7g (92.6%).

Embodiment 1 to 6 and comparative example 1 to 3

In embodiment 1 to 6 and comparative example 1 to 3, after mixer adds solvent, it is added to alkali-soluble binder Resin, photopolymerizable compound, Photoepolymerizationinitiater initiater and coloring agent, uniformly mixed by stirring, thus manufactures blue sense Photosensitive resin composition.Now, compositions has the composition of table 1 below.

[table 1]

(1) manufacture of color filter

After utilizing spin-coating method that the blue-sensitive resin combination of manufacture is coated glass substrate top, it is placed in heating plate On, keep 3 minutes at a temperature of 100 DEG C and form color layers thin film.Then, placement has the line/space pattern of 1 to 50 μm Test photomask, by and test photomask interval be set to 100 μm irradiation ultraviolet radiation.Now, ultraviolet light source uses and contains There is the high voltage mercury lamp of the whole 1kW of g, h, i line, with 50mJ/cm²Illumination be irradiated, do not use special optical filter. Thin film dipped for color layers after the irradiation ultraviolet radiation KOH aqueous solution in pH 10.5 i.e. developing solution is developed for 2 minutes.Make Will be formed with the cleaning glass substrate of the color layers thin film after development with distilled water after, it is dried in a nitrogen atmosphere, 200 DEG C heated oven in heating within 1 hour, carry out heat cure, thus manufacture color filter.

(1) PCT evaluates

Utilize the blue-sensitive resin combination of embodiment 1 to 6 and comparative example 1 to 3, by above-mentioned color filter manufacturer Method obtains and forms figuratum film.Afterwards, (pressure cooker steams the blue substrate crosscutting (Cross-cut) manufactured to be implemented PCT afterwards Boil test (Pressure-cookertest)), now, PCT process conditions be 3 atmospheric pressure, humidity 100%, temperature 130 DEG C, 12hr/1 circulation.Afterwards, 1～3 adhesive tape test (Tape test) is implemented, it is judged that whether coated face is peeled off, and the results are shown in Table 2 below.

[table 2]

From above-mentioned table 2 it has been confirmed that using the embodiment 1 to 6 according to the blue-sensitive resin combination of the present invention In the case of, closing force is excellent such that it is able to obtain the color filter of the high reliability not having pattern to come off during PCT test.

On the other hand, in the case of comparative example 1 to 3, liquid crystal bubbles phenomenon occur after PCT test, pattern comes off seriously, Whereby it was confirmed that quality reduces.

(2) developing powder, sensitivity, pattern breakaway and pattern grazing are evaluated

With the color filter by the blue-sensitive resin combination manufacture of embodiment 1 to 6 and comparative example 1 to 3 as object, comment Valency developing powder, sensitivity and pattern grazing, the results are shown in Table 3 below.

About developing powder, when measuring development, non-exposed portion is dissolved completely in the time needed for developer solution, about sensitivity, In order to form the minimum light exposure not having needed for the thin film of pattern breakaway, mensuration after developing.

Additionally, about pattern breakaway, when the pattern produced by optical microscope evaluation, with breakaway phenomenon journey on pattern Degree represents, it is expressed as follows: do not have breakaway, Δ=pattern breakaway 1～3, X=pattern breakaway more than 4 and XX on O=pattern =breakaway is multiple.

Evaluate about pattern grazing, when evaluating generated pattern by optical microscope, recessed to occur on pattern Degree convex, bending represents, it is expressed as follows: O=pattern does not has defect, Δ=pattern defect 1～3, X=pattern defect 4 More than individual, XX=does not develops, cannot measure.

[table 3]

With reference to above-mentioned table 3, it is believed that the developing powder of embodiment 1 to 6 constructed in accordance is fast, and sensitivity is the most excellent Different, occur without pattern breakaway, pattern defect.Therefore, embodiment 1 to 6 can manufacture the pattern of color filter of excellent quality.

On the other hand, it is known that for oxime ester derivative compound not being used as the comparative example 1 to 3 of Photoepolymerizationinitiater initiater, base Occurring pattern breakaway, pattern defect on plate, sensitivity is the most excellent.

Claims

1. a blue-sensitive resin combination, it is characterised in that comprise Photoepolymerizationinitiater initiater and coloring agent,

Described Photoepolymerizationinitiater initiater comprises at least one in the oxime ester derivative compound of following chemical formula 1:

[chemical formula 1]

In chemical formula 1,

Z is CR ' R " or NR ',

R ' and R " it is each independently hydrogen, halogen, substituted or non-substituted C1-C20 alkyl, substituted or non-substituted C6-C20 virtue Base, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base, C3-C20 cycloalkyl, substituted or non-substituted C2-C12 thiazolinyl, C4-C8 cycloalkenyl group or C2-C12 alkynyl,

R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Be each independently hydrogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base, C3-C20 cycloalkyl, amino, nitro, cyano group, hydroxyl, Or COR₁₆,

X be CO or directly in conjunction with,

R₁₄For hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C2-C5 thiazolinyl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxy alkoxy base or C3-C20 cycloalkyl,

R₁₅For hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 hydroxy alkyl, C1-C20 hydroxyl Alkoxyl, C3-C20 cycloalkyl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 phenyl, halogen, C1-C4 Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂, SO-C1-C10 alkyl, SO₂-C1-C10 alkyl, Jie exist There are more than 1 O, S or NR₂₆C2-C20 alkyl replace, or, each of which is non-substituted or is replaced by following radicals, described Group is by more than 1 halogen, COOR₁₇、CONR₁₉R₂₀, phenyl, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6-C20 aryl oxide Base carbonyl, C3-C20 heteroaryloxycarbonyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted C1-C20 alkyl,

K is integer 1-10,

R₁₇For C1-C4 haloalkyl,

R₁₈For hydrogen, C2-C12 thiazolinyl, C3-C20 cycloalkyl or phenyl-C1-C3 alkyl, wherein, C2-C12 thiazolinyl, C3-C20 cycloalkanes Base or phenyl-C1-C3 alkyl be non-Jie or be situated between and having more than 1 O, S, CO, NR₂₆Or COOR₁₇,

Or, R₁₈For non-substituted or by more than 1 OH, SH, CN, C3-C6 alkenyloxy group, OCH₂CH₂CN、OCH₂CH₂(CO)O(C1- C4 alkyl), O (CO)-(C2-C4) thiazolinyl, O (CO)-(C1-C4 alkyl), O (CO)-phenyl or (CO) OR₁₇Substituted C1-C20 alkane Base,

Or, R₁₈For (CH₂CH₂O)_nH、(CH₂CH₂O)_n(CO)-(C1-C8 alkyl), C2-C8 alkanoyl or C3-C6 enoyl-,

Or, R₁₈For non-substituted or by more than 1 C1-C6 alkyl, halogen, OH, C1-C4 alkoxyl or C1-C4 alkyl sulphonyl Substituted benzoyl,

Or, R₁₈For phenyl, naphthyl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 halogen, C1-C12 alkane Base, C1-C4 haloalkyl, C1-C12 alkoxyl, CN, NO₂, phenyl-C1-C3 alkyl oxy, phenoxy group, C1-C12 alkyl sulfonyl Base, phenyl sulfonyl, N (C1-C12 alkyl)₂, diphenyl amino, (CO) O (C1-C8 alkyl), (CO)-C1-C8 alkyl, (CO) N (C1-C8 alkyl)₂OrReplace,

X₂For O, CO, S or directly in conjunction with,

R₁₉And R₂₀Be independently of one another hydrogen, C1-C20 alkyl, C2-C4 hydroxy alkyl, C2-C10 alkoxyalkyl, C2-C5 thiazolinyl, C3-C20 cycloalkyl, phenyl-C1-C3 alkyl, C1-C8 alkanoyl, C1-C8 alkanoyl epoxide, C3-C12 enoyl-, SO₂-(C1- C4 haloalkyl) or benzoyl,

Or, R₁₉And R₂₀For phenyl, naphthyl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 halogen, C1- C4 haloalkyl, C1-C20 alkoxyl, C1-C12 alkyl, benzoyl or C1-C12 alkoxyl replace,

Or, R₁₉And R₂₀With they with atom N together formed non-Jie or be situated between having O, S or NR₁₇Five yuan or hexa-atomic Saturated or unsaturated ring, described five yuan or hexa-atomic saturated or unsaturated ring are non-substituted or by more than 1 C1-C20 alkyl, C1- C20 alkoxyl ,=O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、NO₂, halogen, C1-C4-haloalkyl, CN, phenyl,Replace or by non-Jie or be situated between at O, S, CO or the NR having more than 1₁₇C3-C20 cycloalkyl take Generation,

Or, R₁₉And R₂₀With they with atom N together form heteroaromatic ring system, described heteroaromatic ring system be non-substituted or By more than 1 C1-C20 alkyl, C1-C4 haloalkyl, C1-C20 alkoxyl ,=O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、Halogen, NO₂, CN, phenyl or non-Jie or be situated between and having more than 1 O, S, CO or NR₁₇C3-C20 Cycloalkyl substituted,

R₂₁Or R₂₂It is hydrogen, C1-C20 alkyl, C1-C4 haloalkyl, C3-C10 cycloalkyl or phenyl independently of one another,

Or, R₂₁And R₂₂With they with atom N together formed non-Jie or be situated between having O, S or NR₂₆Five yuan or hexa-atomic Saturated or unsaturated ring, described five yuan or hexa-atomic saturated or unsaturated ring are not condensed or described five yuan or hexa-atomic saturated or not Saturated rings condensation has phenyl ring,

R₂₃For hydrogen, OH, C1-C20 alkyl, C1-C4 haloalkyl, non-Jie or be situated between having more than 1 O, CO or NR₂₆C2-C20 Alkyl, non-Jie or be situated between having O, S, CO or NR₂₆C3-C20 cycloalkyl, or, R₂₃For phenyl, naphthyl, phenyl-C1-C4 alkane Base, OR₁₇、SR₁₈Or NR₂₁R₂₂,

R₂₆For hydrogen, C1-C20 alkyl, C1-C4 haloalkyl, be situated between having the C2-C20 alkyl of more than 1 O or CO, or be phenyl- C1-C4 alkyl, non-Jie or be situated between and having the C3-C8 cycloalkyl of more than 1 O or CO, or be (CO) R₁₉, or be non-substituted or by 1 Individual above C1-C20 alkyl, halogen, C1-C4 haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀OrSubstituted benzene Base,

Wherein, molecular memory is at least 1 groupOr

When Z is CR ' R " time, R₆For

When Z is NR ', R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Middle least one set is

Blue-sensitive resin combination the most according to claim 1, it is characterised in that the oxime ester of described chemical formula 1 spreads out Biologic artifact is represented by following chemical formula 1-1:

[chemical formula 1-1]

In chemical formula 1-1,

R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Be each independently hydrogen, C1-C20 alkyl,COR₁₆Or NO₂,

Wherein, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Middle least one set is

X be CO or for directly in conjunction with,

R ' be any substituted C1-C20 alkyl, C3-C10 cycloalkyl, C2-C12 thiazolinyl, C4-C8 cycloalkenyl group, C2-C12 alkynyl, Phenyl or naphthyl, wherein, phenyl or naphthyl is all optionally substituted,

R₁₄For hydrogen, C1-C20 alkyl, C3-C8 cycloalkyl, C2-C5 thiazolinyl, C1-C20 alkoxyl, phenyl or naphthyl,

R₁₅For C6-C20 aryl or C3-C20 heteroaryl, each of which is non-substituted or by more than 1 phenyl, halogen, C1-C4 halogen Substituted alkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂, SO-C1-C10 alkyl, SO₂-C1-C10 alkyl, Jie are having 1 Individual above O, S or NR₂₆C2-C20 alkyl replace, or, each of which is non-substituted or is replaced by following radicals, described group By more than 1 halogen, COOR₁₇、CONR₁₉R₂₀, phenyl, C3-C8 cycloalkyl, C3-C20 heteroaryl, C6-C20 aryloxy carbonyl Base, C3-C20 heteroaryloxycarbonyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted C1-C20 alkyl,

R₁₆To R₂₆And X₂Identical with the implication in claim 1.

Blue-sensitive resin combination the most according to claim 1, it is characterised in that the oxime ester of described chemical formula 1 spreads out Biologic artifact is represented by following chemical formula 1-2:

[chemical formula 1-2]

In chemical formula 1-2,

R’、R”、R₁₄And R₁₅It is each independently hydrogen, halogen, C1-C20 alkyl, C6-C20 aryl, C1-C20 alkoxyl, C1-C20 Hydroxy alkyl, C1-C20 hydroxy alkoxy base or C3-C20 cycloalkyl,

R is 0 or 1.

Blue-sensitive resin combination the most according to claim 1, it is characterised in that described blue-sensitive resin group Compound comprises alkali-soluble binder resin, photopolymerizable compound and solvent further.

Blue-sensitive resin combination the most according to any one of claim 1 to 4, it is characterised in that relative to indigo plant Color sensation photosensitive resin composition 100 weight portion, comprises the described alkali-soluble binder resin of 1 to 40 weight portion, 1 to 20 weight portion Photopolymerizable compound, the Photoepolymerizationinitiater initiater of 0.1 to 10 weight portion, the coloring agent of 5 to 40 weight portions and 20 to 85 weight The solvent of part.

Blue-sensitive resin combination the most according to claim 1, it is characterised in that described coloring agent comprise a kind with Blue pigment.

Blue-sensitive resin combination the most according to claim 6, it is characterised in that described coloring agent comprises choosing freely C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60 blueness face In the group of material composition more than a kind.

Blue-sensitive resin combination the most according to claim 7, it is characterised in that described coloring agent comprises further Select free C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. face In the group that material purple 36, C.I. pigment violet 38 violet pigment form more than a kind.

9. a color filter, it is characterised in that by the blue-sensitive resin combination according to any one of claim 1 to 8 Manufacture.

10. a liquid crystal indicator, it possesses the color filter described in claim 9.