阅读说明：本技术 蓝色感光性树脂组合物、利用其制造的滤色器及图像显示装置 (Blue-sensitive resin combination, the colour filter and image display device manufactured using it ) 是由 金亨柱 金胄皓 王贤正 于 2018-02-28 设计创作，主要内容包括：本发明的蓝色感光性树脂组合物的特征在于,包含碱溶性树脂、蓝色着色剂、及含有平均粒径30～500nm的金属氧化物的散射粒子,上述碱溶性树脂包含含有化学式1～化学式3中的至少一种重复单元的Cardo系粘合剂树脂。本发明的蓝色感光性树脂组合物具有以下优点：能够赋予优异的颜色再现特性和高光效率,热流动性优异而不产生图案直进性和倒锥面,工序性优异,面板工作时不产生残影,因优异的防反射效率而实现高品质的画质,能够实现优异的耐热性、耐化学性、耐久性和可靠性。(Blue-sensitive resin combination of the invention is characterized in that, scattering particles comprising alkali soluble resins, blue colorant and the metal oxide containing 30~500nm of average grain diameter, above-mentioned alkali soluble resins include the Cardo system adhesive resin containing at least one of 1~chemical formula of chemical formula 3 repetitive unit.Blue-sensitive resin combination of the invention, which has the advantage that, assigns excellent color reproduction characteristics and bloom efficiency, thermal fluidity is excellent without generating pattern rectilinear propagation and inverted cone surface, process is excellent, panel does not generate ghost when working, the image quality that high-quality is realized because of excellent antireflection efficiency, can be realized excellent heat resistance, chemical resistance, durability and reliability.)

1. a kind of blue-sensitive resin combination it includes alkali soluble resins, blue colorant and contains average grain diameter 30 The scattering particles of the metal oxide of~500nm,

The alkali soluble resins includes the Cardo containing at least one of 1~following chemical formula of following chemical formula 3 repetitive unit It is adhesive resin,

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

In the chemical formula 1 and 2,

X and X ' is each independently singly-bound ,-CO- ,-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、

Y is anhydride residue,

Z is acid dianhydride residue,

R ' is hydrogen atom, ethyl, phenyl ,-C₂H₄Cl、-C₂H₄OH or-CH₂CH=CH₂,

R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ', R6 and R6 ' are each independently hydrogen atom or methyl,

R7, R7 ', R8 and R8 ' are each independently the alkylidene of the linear chain or branched chain of carbon atom number 1~6, and the alkylidene can be with At least one of arlydene by ester bond, the cycloalkylidene of carbon atom number 6~14 and carbon atom number 6~14 interrupts,

R9, R9 ', R10, R10 ', R11, R11 ', R12 and R12 ' are each independently hydrogen atom, halogen atom or carbon atom number 1 The alkyl of~5 linear chain or branched chain,

M and n is each independently 0~30 integer,

Wherein, m and n is not 0 simultaneously,

In the chemical formula 3,

R13 is identical as the definition of X and X ' in the chemical formula 1 and 2,

R14 be methacrylate, vinyl or acrylate-based,

R15 is the reaction residue of the monomer represented by the following chemical formula 4,

The integer that r is 1~20,

[chemical formula 4]

In the chemical formula 4,

R16 and R17 are same or different to each other, and are each independently

2. blue-sensitive resin combination according to claim 1, repetitive unit represented by the chemical formula 3 is under The expression of at least one of chemical formula 5~9 is stated,

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

In the chemical formula 5~9,

R13, R14 and r are identical as the definition in chemical formula 3.

3. blue-sensitive resin combination according to claim 1, the alkali soluble resins also include containing selected from by The Cardo system adhesive resin of one or more of the group that following chemical formula 10 and following chemical formula 11 form repetitive unit,

[chemical formula 10]

[chemical formula 11]

In the chemical formula 10 and 11,

P is each independently

R19 and R20 is each independently hydrogen, hydroxyl, mercapto, amino, nitro or halogen atom,

Ar1 is each independently C6~C15 aryl,

Y ' is anhydride residue,

Z ' is acid dianhydride residue,

A be O, S, N, Si or Se,

A and b is each independently 1~6 integer,

P and q is each independently 0~30 integer,

Wherein, p and q is not 0 simultaneously.

4. blue-sensitive resin combination according to claim 1, the metal oxide include selected from by Li, Be, B、Na、Mg、Al、Si、K、Ca、Sc、V、Cr、Mn、Fe、Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Mo、Cs、Ba、La、Hf、W、Tl、 Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, DY, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and their combination The oxide of one or more of the group of composition.

5. blue-sensitive resin combination according to claim 4, the metal oxide includes selected from by Al₂O₃、 SiO₂、ZnO、ZrO₂、BaTiO₃、TiO₂、Ta₂O₅、Ti₃O₅、ITO、IZO、ATO、ZnO-Al、Nb₂O₃, SnO, MgO and their group One or more of group being combined into.

6. blue-sensitive resin combination according to claim 1, the alkali soluble resins is also viscous comprising acrylic acid series Mixture resin.

7. blue-sensitive resin combination according to claim 1, relative to the blue-sensitive resin combination Whole 100 parts by weight, the content of the scattering particles are 0.1~50 parts by weight.

8. blue-sensitive resin combination according to claim 1, relative to the blue-sensitive resin combination Whole 100 parts by weight, the content of Cardo system adhesive resin are 1~50 parts by weight.

9. blue-sensitive resin combination according to claim 1, the blue colorant includes selected from by C.I. face One or more of the group of material basket 15:3,15:4,15:6,16,21,28,60,64,76 and their combination composition blue pigment.

10. blue-sensitive resin combination according to claim 9, the blue colorant also includes selected from by dyestuff With one or more of the group of violet pigment composition.

11. blue-sensitive resin combination according to claim 1, relative to the blue-sensitive resin combination Whole 100 parts by weight, the content of the blue colorant are 0.1~50 parts by weight.

12. blue-sensitive resin combination according to claim 1, also include selected from by photopolymerizable compound, One or more of Photoepolymerizationinitiater initiater, solvent and group of additive composition.

13. a kind of colour filter containing spontaneous light pixel, it includes feel containing blue described in any one of claim 1~12 The blue color patterns layer of the solidfied material of photosensitive resin composition.

14. a kind of image display device, it includes the light sources of colour filter and sending blue light described in claim 13.

Technical field

The present invention relates to the blue-sensitive resin groups comprising specific scattering particles, alkali soluble resins and blue colorant The colour filter and image display device for closing object, being manufactured using the blue-sensitive resin combination.

Background technique

Colour filter is to extract red, these three colors of green and blue from white light and be capable of forming small pixel list The film-type optical component of member, the size of a pixel are tens of to hundreds of microns degree.For such colour filter, it can adopt Structure made of being stacked gradually with black matrix layer and pixel portion, wherein black matrix layer shape in a predetermined pattern on the transparent substrate At to carry out shading to the boundary part each pixel, pixel portion is by multiple color (usually red R, green G and blue B) Three primary colors arranged in a predefined order to form each pixel.

In recent years, as one of the method for forming colour filter, using the pigment of the photoresist using pigment-dispersing type Dispersion method, but from the light that light source irradiates during through colour filter, a part of light can be colored device and absorb and light efficiency Rate reduces, furthermore, it may occur that the problem of reducing color reproduction because of the characteristic for the pigment that colour filter is included.

In particular, as colour filter uses in the diversified field using various image display devices as representative, no Excellent pattern properties are required nothing more than, and require the performances such as high color reproduction rate and excellent high brightness, high contrast, in order to Such problems is solved, the manufacturer of the colour filter using the self-luminous photosensitive polymer combination comprising quantum dot is proposed Method.

Korean Patent Publication No. 2013-0000506 is related to a kind of display device, open the following contents: above-mentioned display Device includes color converter section, which includes to make multiple wavelength convert particles of the wavelength convert of light and in above-mentioned light Multiple color filter particles of the middle light for absorbing scheduled wave band.

But in the case where the colour filter containing quantum dot, with the efficiency of quantum dot, the efficiency of especially blue quantum dot Decline, the performance of colour filter may reduce, and in the case where blue quantum dot, there are the manufacturing expenses whole because of price height The problem of with being promoted, occurs showing bad such problems additionally, there are inverted cone surface is generated.

Therefore, status is, it is desirable that exploitation can prevent the efficiency of blue pixel from declining and reduce the photonasty of manufacturing cost Resin combination.

Summary of the invention

Problems to be solved by the invention

The object of the present invention is to provide can prevent the efficiency of blue pixel from declining, reduce the blue sense of manufacturing cost Photosensitive resin composition.

It is further an object that providing that thermal fluidity is excellent and the generation of pattern rectilinear propagation and inverted cone surface obtains Inhibit and be able to suppress the blue-sensitive resin combination of the generation of outgassing.

In addition, the present invention wants to provide the blue pixel layer comprising using blue-sensitive resin combination above-mentioned manufacture Colour filter and image display device.Specifically, the desired offer image quality of the present invention, visual angle, durability, reliability etc. are excellent Colour filter and image display device.

The method to solve the problem

Blue-sensitive resin combination of the invention for achieving the above object is characterized in that, includes alkali solubility tree The scattering particles of rouge, blue colorant and the metal oxide containing 30~500nm of average grain diameter, above-mentioned alkali soluble resins Include the Cardo system adhesive resin containing at least one of 1~following chemical formula of following chemical formula 3 repetitive unit.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

In above-mentioned chemical formula 1 and 2,

X and X ' is each independently singly-bound ,-CO- ,-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、

Y is anhydride residue,

Z is acid dianhydride residue,

R ' is hydrogen atom, ethyl, phenyl ,-C₂H₄Cl、-C₂H₄OH or-CH₂CH=CH₂,

R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ', R6 and R6 ' are each independently hydrogen atom or methyl,

R7, R7 ', R8 and R8 ' are each independently the alkylidene of the linear chain or branched chain of carbon atom number 1~6, above-mentioned alkylidene It can be interrupted by least one of arlydene of ester bond, the cycloalkylidene of carbon atom number 6~14 and carbon atom number 6~14,

R9, R9 ', R10, R10 ', R11, R11 ', R12 and R12 ' are each independently hydrogen atom, halogen atom or carbon atom The alkyl of the linear chain or branched chain of number 1~5,

M and n is respectively the integer for meeting 0≤m≤30,0≤n≤30,

Wherein, m and n is not 0 simultaneously,

In above-mentioned chemical formula 3,

R13 is identical as the definition of X and X ' in above-mentioned chemical formula 1 and 2,

R14 be methacrylate, vinyl or acrylate-based,

R15 is the reaction residue of the monomer represented by the following chemical formula 4,

The integer that r is 1~20,

[chemical formula 4]

In above-mentioned chemical formula 4,

R16 and R17 are same or different to each other, and are each independently

In addition, the present invention provides the colour filter manufactured by blue-sensitive resin combination above-mentioned and includes the colour filter Image display device.

Invention effect

Blue-sensitive resin combination of the invention have can assign excellent color reproduction characteristics and light efficiency this The advantages of sample, and have and pattern residue does not occur, the generation of pattern rectilinear propagation and inverted cone surface obtains due to excellent thermal fluidity The advantage that inhibiting, make the generation of outgassing to minimize.

In addition, being shown by the colour filter of blue-sensitive resin combination manufacture and the image comprising the colour filter of the invention Showing device has and can ensure the image quality of excellent antireflection efficiency bring high-quality, excellent visual angle, high-durability, reliable Property and the advantage that can reduce manufacturing cost.

Specific embodiment

Hereinafter, the present invention is described in more detail.

It not only include a certain component and another structure when pointing out that a certain component is located at another component "upper" in the present invention The case where part contacts, include thes case where that there are other components between two components.

In the present invention, when pointing out a certain constituent element of certain a part of "comprising", mean, as long as no especially opposite Record, then can further include other constituent elements, rather than other constituent elements are excluded.

< blue-sensitive resin combination >

A mode of the invention is related to a kind of blue-sensitive resin combination, and it includes alkali soluble resins, blue-colored The scattering particles of agent and the metal oxide containing 30~500nm of average grain diameter, above-mentioned alkali soluble resins include to contain followingization The Cardo system adhesive resin of at least one of 1~following chemical formula of formula 3 repetitive unit.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

In above-mentioned chemical formula 1 and 2,

X and X ' is each independently singly-bound ,-CO- ,-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、

Y is anhydride residue,

Z is acid dianhydride residue,

R ' is hydrogen atom, ethyl, phenyl ,-C₂H₄Cl、-C₂H₄OH or-CH₂CH=CH₂,

R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ', R6 and R6 ' are each independently hydrogen atom or methyl,

R7, R7 ', R8 and R8 ' are each independently the alkylidene of the linear chain or branched chain of carbon atom number 1~6, above-mentioned alkylidene It can be interrupted by least one of arlydene of ester bond, the cycloalkylidene of carbon atom number 6~14 and carbon atom number 6~14,

R9, R9 ', R10, R10 ', R11, R11 ', R12 and R12 ' are each independently hydrogen atom, halogen atom or carbon atom The alkyl of the linear chain or branched chain of number 1~5,

M and n is respectively the integer for meeting 0≤m≤30,0≤n≤30,

Wherein, m and n is not 0 simultaneously,

In above-mentioned chemical formula 3,

R13 is identical as the definition of X and X ' in above-mentioned chemical formula 1 and 2,

R14 be methacrylate, vinyl or acrylate-based,

R15 is the reaction residue of the monomer represented by the following chemical formula 4,

The integer that r is 1~20,

[chemical formula 4]

In above-mentioned chemical formula 4,

R16 and R17 are same or different to each other, and are each independently

Alkali soluble resins

Blue-sensitive resin combination of the invention include containing in 1~following chemical formula of following chemical formula 3 at least A kind of Cardo system adhesive resin of repetitive unit.

[chemical formula 1]

[chemical formula 2]

[chemical formula 3]

In above-mentioned chemical formula 1 and 2,

X and X ' is each independently singly-bound ,-CO- ,-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、

Y is anhydride residue,

Z is acid dianhydride residue,

R ' is hydrogen atom, ethyl, phenyl ,-C₂H₄Cl、-C₂H₄OH or-CH₂CH=CH₂,

R1, R1 ', R2, R2 ', R3, R3 ', R4, R4 ', R5, R5 ', R6 and R6 ' are each independently hydrogen atom or methyl,

R7, R7 ', R8 and R8 ' are each independently the alkylidene of the linear chain or branched chain of carbon atom number 1~6, above-mentioned alkylidene It can be interrupted by least one of arlydene of ester bond, the cycloalkylidene of carbon atom number 6~14 and carbon atom number 6~14,

R9, R9 ', R10, R10 ', R11, R11 ', R12 and R12 ' are each independently hydrogen atom, halogen atom or carbon atom The alkyl of the linear chain or branched chain of number 1~5,

M and n is respectively the integer for meeting 0≤m≤30,0≤n≤30,

Wherein, m and n is not 0 simultaneously,

In above-mentioned chemical formula 3,

R13 is identical as the definition of X and X ' in above-mentioned chemical formula 1 and 2,

R14 be methacrylate, vinyl or acrylate-based,

R15 is the reaction residue of the monomer represented by the following chemical formula 4,

The integer that r is 1~20,

[chemical formula 4]

In above-mentioned chemical formula 4,

R16 and R17 are same or different to each other, and are each independently

Preferably, above-mentioned R7, R7 ', R8 and R8 ' are each independently the alkylene of the linear chain or branched chain of carbon atom number 1~6 Base, above-mentioned alkylidene can by the arlydene of ester bond, the cycloalkylidene of carbon atom number 6~14 and carbon atom number 6~14 extremely A kind of few interruption, preferably can for ethylidene,

At this point, in above-mentioned chemical formula 3, it is residual comprising the reaction for deriving from monomer represented by above-mentioned chemical formula 4 by R15 Base shows excellent heat resistance, chemical resistance, intensity and hardness, energy so that curing degree increases and improves surface hardness Enough realize durability and colour filter excellent in reliability.

In one embodiment of the present invention, repetitive unit represented by above-mentioned chemical formula 3 is by following chemical formula 5~9 At least one indicates, however, not limited to this, meeting above-mentioned condition and the repetitive unit that is known in the art can be used.

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

In above-mentioned chemical formula 5~9,

R13 is identical as the definition in above-mentioned chemical formula 3,

R14 be methacrylate, vinyl or acrylate-based,

The integer that r is 1~20.

Preferably, in alkali-soluble binder resin of the invention, the total moles 100 relative to alkali-soluble binder resin are rubbed You are %, and it more preferably can be 5~70 moles of % that the content of the repetitive unit of above-mentioned chemical formula 5~9, which can be 3~80 moles of %,. Within the above range in the case where use, sensitivity and excellent adhesion and do not have figuratum removing in developing procedure, show The characteristic of excellent solvent resistance out.

It include the weight containing above-mentioned 1~chemical formula of chemical formula 3 in self-luminous blue-sensitive resin combination of the invention In the case where at least one of the multiple unit Cardo system adhesive resin of repetitive unit, with excellent in reliability between process Advantage.In addition, having the advantage that effect because that can adjust fastly by developing powder without generating pattern residue, because excellent Thermal fluidity without generating pattern rectilinear propagation and inverted cone surface, thus be conducive to show undesirable improvement, and make the production of outgassing Life minimizes and ghost does not occur in panel starting, can assign the picture of bring high-quality due to excellent anti-reflection effect Matter, excellent heat resistance, chemical resistance, durability and reliability.

All include by the repetitive unit of above-mentioned 1~chemical formula of chemical formula 3 in Cardo system adhesive resin of the invention In the case of, it more preferably can be 5/95~80/20 that molar ratio, which is not particularly limited, and m/n for example can be 1/99~90/10.

In the case where above-mentioned m/n is met the above range, it can suitably maintain the carboxyl-content of adhesive resin and incite somebody to action Alkali resistance maintains well, and exposure portion will not dissolve out in developing solution, shows excellent alkali-developable, so as to be formed Fine pattern.

The Y of above-mentioned chemical formula 1 is the residue of acid anhydrides, can make the synthesis as Cardo system adhesive resin of the invention The bisphenol epoxy acrylate compound of intermediate is reacted with anhydride compound to be obtained.The acid anhydrides chemical combination of residue Y can be imported Object is not particularly limited, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydro neighbour benzene two Formic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic tetrabydrophthalic anhydride, chlorendic anhydride, methyl tetrahydro neighbour benzene two Formic anhydride etc..

The Z of above-mentioned chemical formula 2 is the residue of acid dianhydride, can make the conjunction as Cardo system adhesive resin of the invention It reacts and obtains with acid dianhydride compounds at the bisphenol epoxy acrylate compound of intermediate.The acid two of residue Z can be imported Acid anhydride compound is not particularly limited, for example, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, bibenzene tetracarboxylic The aromatic polycarboxylic acids acid anhydrides such as dianhydride, Biphenyl Ether tetracarboxylic acid dianhydride, hexamethylene acid dianhydride, ring butyric acid dianhydride etc..

In the present invention, " singly-bound " is meant, the structure directly to link to no other functional groups, such as above-mentioned chemistry In formula 1, structure that the no ground X and X ' hydroxyphenyl directly links.

In addition, " acid dianhydride " is meant in the present invention, intramolecular contains the compound of 2 anhydride groups.

In the present invention, the manufacturing method of above-mentioned Cardo system adhesive resin is not particularly limited.For example, bis-phenol can be made Compound is reacted with epoxide after bisphenol synthesis epoxide, makes the bisphenol epoxy compound and acrylate of synthesis Compound reacts and bisphenol synthesis epoxy acrylic ester compounds, then makes bisphenol epoxy acrylate compound and acid anhydrides, acid Dianhydride or their mixture are reacted and are manufactured, and but not limited thereto.

The acid value of above-mentioned alkali-soluble binder resin can be 20~200mgKOH/g, preferably can for 30~ 150mgKOH/g.With acid value in above range, the dissolubility in developer solution is improved, and non-exposed portion is easy molten Solution, sensitivity increase, and as a result the pattern of exposure portion leaves in development and improves membrane left rate (film remaining ratio), Therefore preferably.

In the present invention, so-called " acid value " refers to, the amount of desired potassium hydroxide when as neutralization acrylic acid series polymeric compounds 1g (mg) value measured, can usually be titrated by using potassium hydroxide aqueous solution and be found out.

Furthermore it is preferred that passing through gel permeation chromatography (GPC；Using tetrahydrofuran as eluting solvent) measurement polystyrene change Calculating weight average molecular weight (hreinafter referred to as " weight average molecular weight ") is 2,000~200,000, preferably 3,000~100,000 Alkali soluble resins.If molecular weight is in above range, there are the raising of the hardness of coating film, membrane left rate is high, and non-exposed portion exists Dissolubility in developer solution is brilliant, the tendency that resolution ratio improves, therefore preferably.

The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of above-mentioned alkali soluble resins is preferably 1.0~ 6.0, more preferably 1.5~6.0.Meet in above-mentioned molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] above-mentioned In the case where range, developability is excellent, therefore preferably.

It is above-mentioned relative to whole 100 parts by weight of above-mentioned blue-sensitive resin combination in one embodiment of the present invention The content of Cardo system adhesive resin can be 1~50 parts by weight, preferably can be 5~40 parts by weight, more preferably can be 5 ~30 parts by weight.

The content of above-mentioned Cardo system adhesive resin within the above range in the case where, have the advantages that development Dissolubility in liquid sufficiently and non-pixel portion is not likely to produce development residue on substrate, when development, is not susceptible to the picture of exposure portion The film of plain part is reduced, thus the good tendency of deciduous with non-pixel portion, therefore preferably.

In another embodiment of the invention, above-mentioned alkali soluble resins can be further included containing selected from by following chemistry The Cardo system adhesive resin of the repetitive unit of one or more of the group that formula 10 and following chemical formula 11 form.

[chemical formula 10]

[chemical formula 11]

In above-mentioned chemical formula 10 and 11,

P is each independently

R19 and R20 is each independently hydrogen, hydroxyl, mercapto, amino, nitro or halogen atom,

Ar1 is each independently C6~C15 aryl,

Y ' is anhydride residue,

Z ' is acid dianhydride residue,

A be O, S, N, Si or Se,

A and b is each independently 1~6 integer,

P and q is each independently 0~30 integer,

Wherein, p and q is not 0 simultaneously.

Above-mentioned halogen atom is F, Cl, Br or I.

Above-mentioned aryl can be the monocyclic aryl or polycycle aryl of C6~C15.It, can be with as above-mentioned monocyclic aryl Phenyl, xenyl, terphenyl, stilbene radicals etc. are enumerated, but not limited thereto.As above-mentioned polycycle aryl, can enumerate naphthalene, Anthryl, phenanthryl, pyrenyl, base,Base, fluorenyl etc., but not limited thereto.

The Y ' of above-mentioned chemical formula 10 is the residue of acid anhydrides, and the acid anhydrides that can import residue Y ' can be applicable in related Y above-mentioned Content.

The Z ' of above-mentioned chemical formula 11 is the residue of acid dianhydride, and the acid dianhydride compounds that can import residue Z ' do not limit especially It is fixed, the content above-mentioned in relation to Z can be applicable in.

In the case where including Cardo system adhesive resin of the invention in blue-sensitive resin combination, there is energy Enough play the advantages of making luminous intensity, diffusivity and external light reflection rate more excellent effect.

It further includes in above-mentioned alkali soluble resins containing selected from being made of above-mentioned chemical formula 10 and above-mentioned chemical formula 11 It is whole relative to above-mentioned alkali soluble resins in the case where the Cardo system adhesive resin of more than one repetitive unit of composition 100 parts by weight, the content of above-mentioned Cardo system adhesive resin can be 1~50 parts by weight, preferably can be 5~40 parts by weight, It more preferably can be 5~30 parts by weight.

The content for the above-mentioned Cardo system adhesive resin that can further include within the above range in the case where, tool Have the advantages that luminous intensity, diffusivity, external light reflection rate are more excellent, therefore preferably.

Cardo system adhesive resin containing at least one of above-mentioned chemical formula 10 and above-mentioned chemical formula 11 repetitive unit Such as it can be manufactured by following such methods.

It can be by keeping any one of compound represented by 12~chemical formula of following chemical formula 16 and epichlorohydrin such Epoxide reacted under base catalyst or acid catalyst after, it is anti-with compound as benzenethiol, 1- sulphur naphthalene, 2- sulphur naphthalene It should be synthesized, to obtain the compound of following chemical formula 17~21.

Later, compound represented by following chemical formula 17~21 and carboxylic acid dianhydride is made to carry out polymerization reaction, so as to Obtain the Cardo system adhesive resin containing at least one of above-mentioned chemical formula 10 and above-mentioned chemical formula 11 repetitive unit.

[chemical formula 12]

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

In above-mentioned chemical formula 12~16, A, R19 and R20 are identical as the definition in chemical formula 10 and 11.

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

In above-mentioned chemical formula 17~21, the integer that c is 1~6,

A, Ar1, R19 and R20 are identical as the definition in chemical formula 10 and 11.

It can be pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylics two as the concrete example of above-mentioned carboxylic acid dianhydride Acid anhydride, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydrides, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylics Dianhydride, 2,2 ', bis- (3,4- dicarboxyphenyi) propane dianhydrides of 3,3 '-benzophenone tetracarboxylic dianhydrides, 2,2-, the bis- (2,3- of 2,2- Dicarboxyphenyi) propane dianhydride, bis- (3,4- dicarboxyphenyi) the ethane dianhydrides of 1,1-, bis- (2,3- dicarboxyphenyi) ethane of 1,1- Dianhydride, bis- (3,4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- dicarboxyphenyi) methane dianhydrides, bis- (3,4- dicarboxyphenyis) Sulfone dianhydride, bis- (3,4- dicarboxyphenyi) ether dianhydrides, 1,2,5,6- naphthalenetetracarbacidic acidic dianhydride, bis- (3,4- dicarboxyphenyi) fluorenes of 9,9- Acid dianhydride, 9,9- bis- { 4- (3,4- di carboxyl phenyloxy) phenyl } fluorenic acid dianhydrides, 2,3,6,7- naphthalenetetracarbacidic acidic dianhydride, 2,3,5,6- The fragrance such as bis- (3,4- dicarboxyphenyi) hexafluoropropane dianhydrides of pyridine tetracarboxylic acid dianhydride, 3,4,9,10- tetracarboxylic acid dianhydride, 2,2- Tetracarboxylic acid dianhydride, 1,2,3,4- cyclobutanetetracarboxylic dianhydride, the 1,2,3,4- cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4- ring of race's ring The alicyclic tetracarboxylic acid dianhydride such as hexane tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides etc..

Above-mentioned polymerization reaction can for example be implemented 2 hours~24 hours or 4 small at 100~130 DEG C or 110~120 DEG C When~12 hours.

Above-mentioned carboxylic acid dianhydride can for example be put on the basis of 100 parts by weight of monomer represented by above-mentioned chemical formula 17~21 5~40 parts by weight, 10~30 parts by weight or 10~20 parts by weight.

Cardo system adhesive resin containing at least one of above-mentioned chemical formula 10 and above-mentioned chemical formula 11 repetitive unit Manufacturing method for example may include put into after above-mentioned polymerization reaction starts end-capping reagent (end-capping agent) carry out it is anti- The step of answering.

Above-mentioned end capping reaction can for example be implemented 30 minutes~4 hours or 1 small at 100~130 DEG C or 110~120 DEG C When~3 hours.

2 can be put on the basis of 100 parts by weight of monomer represented by above-mentioned end-capping reagent example chemical formula 17~21 as described above ~10 parts by weight, 2~5 parts by weight or 3~5 parts by weight.

Above-mentioned end-capping reagent, which is preferably such as aromatic carboxylic acid acid anhydride as concrete example, phthalic anhydride etc., at this point, tool There are heat resistance, high-permeability and the excellent effect of high refracting characteristic.

Cardo system adhesive resin containing at least one of above-mentioned chemical formula 10 and above-mentioned chemical formula 11 repetitive unit Weight average molecular weight for example can be 1,000~100,000g/mol, preferably can be 2,000~50,000g/mol, more preferably It can be 3,000~10,000g/mol have excellent heat resistance, the developing powder of photosensitive material and utilization in the range The development of developer solution is appropriate, pattern forms and is easy such effect.

Above-mentioned weight average molecular weight can be measured by gel permeation chromatography (GPC) method.

Cardo system adhesive resin containing at least one of above-mentioned chemical formula 10 and above-mentioned chemical formula 11 repetitive unit Dispersion degree for example can be 1.0~5.0 range, preferably can be 1.5~4.0 range, in the range, have it is heat-resisting Property excellent, photosensitive material developing powder and using developer solution development is appropriate, pattern forms and is easy such effect.

Dispersion degree of the invention can be measured by GPC measuring method.

In another embodiment of the invention, above-mentioned alkali soluble resins can further include acrylic adhesive tree Rouge.It, being capable of pattern-free loss ground in the case where above-mentioned alkali soluble resins further includes above-mentioned acrylic adhesive resin The size of the minimum pattern of formation is small, thus has the advantages that be conducive to high-resolution pattern realization and pattern rectilinear propagation, because This is preferably.

Above-mentioned acrylic adhesive resin can enumerate carboxyl group-containing monomer and with can with the monomer be copolymerized other The copolymer etc. of monomer.

As carboxyl group-containing monomer, can enumerate in the molecules such as unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids Unsaturated carboxylic acids such as the unsaturated polybasic carboxylic acid with more than one carboxyl etc..Here, as unsaturated monocarboxylic, such as can To enumerate acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc..As unsaturated dicarboxylic, such as can be with Enumerate maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc..Unsaturated polybasic carboxylic acid may be acid anhydrides, specifically can be with Enumerate maleic anhydride, itaconic anhydride, citraconic anhydride etc..In addition, unsaturated polybasic carboxylic acid may be its single (2- methacryl Oxyalkyl) ester, for example, mono succinate (2- acrylyl oxy-ethyl) ester, mono succinate (2- methylacryoyloxyethyl) Ester, phthalic acid list (2- acrylyl oxy-ethyl) ester, phthalic acid list (2- methylacryoyloxyethyl) ester etc..

Unsaturated polybasic carboxylic acid may be list (methyl) acrylate of its two ends dicarboxyl based polyalcohol, such as can be with Enumerate ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc..These carboxyl group-containing monomers It can respectively individually or be use mixing two or more.As the above-mentioned other monomers that can be copolymerized with carboxyl group-containing monomer, such as Can enumerate styrene, α-methylstyrene, adjacent vinyltoluene, vinyltoluene, to vinyltoluene, to chlorobenzene second Alkene, o-methoxystyrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl Ylmethyl ether, to vinyl benzyl methyl ether, adjacent vinylbenzyl glycidyl base ether, vinylbenzyl glycidyl base Ether, to aromatic ethenyl compounds such as vinylbenzyl glycidyl ether, indenes；Methyl acrylate, methyl methacrylate, third Olefin(e) acid ethyl ester, ethyl methacrylate, n-propyl, n propyl methacrylate, isopropyl acrylate, methacrylic acid Isopropyl ester, n-butyl acrylate, n-BMA, isobutyl acrylate, Isobutyl methacrylate, acrylic acid Zhong Ding The secondary butyl ester of ester, methacrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid 2- hydroxy methacrylate, methacrylic acid 2- hydroxy methacrylate, acrylic acid 2- hydroxy propyl ester, methacrylic acid 2- hydroxy propyl ester, acrylic acid 3- hydroxy propyl ester, methacrylic acid 3- hydroxy propyl ester, acrylic acid 2- hydroxybutyl, methacrylic acid 2- hydroxybutyl, acrylic acid 3- hydroxybutyl, methacrylic acid 3- hydroxybutyl, acrylic acid 4- hydroxybutyl, methacrylic acid 4- hydroxybutyl, allyl acrylate, methacrylic acid allyl Ester, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, methyl-prop Olefin(e) acid phenyl ester, acrylic acid 2- methoxy acrylate, methacrylic acid 2- methoxy acrylate, acrylic acid 2- phenoxy ethyl, methyl-prop Olefin(e) acid 2- phenoxy ethyl, methoxyl group diethylene glycol acrylate, methoxyl group diethylene glycol methacrylate, three second of methoxyl group Butanediol acrylate, methoxy triethylene methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methyl Acrylate, methoxyl group dipropylene glycol acrylate, methoxyl group dipropylene glycol methyl acrylate, isobornyl acrylate, first Base isobornyl acrylate, acrylic acid bicyclopentadiene ester, methacrylic acid bicyclopentadiene ester, (methyl) acrylic acid adamantane Ester, (methyl) acrylic acid norbornyl ester, acrylic acid 2- hydroxyl -3- phenoxy-propyl, methacrylic acid 2- hydroxyl -3- phenoxy group third The unsaturated carboxylate types such as ester, glycerol mono-acrylate, glycerin monomethyl acrylic ester；Acrylic acid 2- amino ethyl ester, methyl-prop Olefin(e) acid 2- amino ethyl ester, acrylic acid 2- dimethylamino ethyl ester, methacrylic acid 2- dimethylamino ethyl ester, acrylic acid 2- amino Propyl ester, methacrylic acid 2- amino propyl ester, acrylic acid 2- dimethylamino propyl ester, methacrylic acid 2- dimethylamino propyl ester, Acrylic acid 3- amino propyl ester, methacrylic acid 3- amino propyl ester, acrylic acid 3- dimethylamino propyl ester, methacrylic acid 3- diformazan The unsaturated carboxylic acids aminoalkyl esters such as base amino propyl ester；Glycidyl acrylate, glycidyl methacrylate etc. are no Saturated carboxylic acid glycidyl esters；The carboxylic acids second such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Alkenyl esters；The unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether；Acrylonitrile, methyl-prop The vinyl cyanide compounds such as alkene nitrile, α-chloro-acrylonitrile, double cyanogen Asias ethylene；Acrylamide, Methacrylamide, α-chloropropene acyl The unsaturated acyls amines such as amine, N-2- hydroxyethyl acrylamide, N-2- hydroxyethyl methacrylamide；Maleimide, benzyl horse Carry out the unsaturated acyls imines such as acid imide, N-phenylmaleimide, N- N-cyclohexylmaleimide；1,3- butadiene, isoamyl The aliphatic conjugated dienes class such as diene, chlorobutadiene；And it is polystyrene, polymethyl acrylate, polymethyl methacrylate, poly- N-butyl acrylate, Vinalac 5920, polysiloxanes polymer molecular chain end have single acryloyl group or Polymeric monomer class of monomethacrylate acyl group etc..These monomers can respectively individually or be use mixing two or more.

In particular, there is the monomer of norborny skeleton, have as the above-mentioned monomer that can be copolymerized with carboxyl group-containing monomer The large volumes monomers such as the monomer of adamantane framework, monomer with rosin skeleton have the tendency for reducing relative dielectric constant, because This is preferably.

Relative to whole 100 parts by weight of above-mentioned alkali soluble resins, the content of above-mentioned acrylic adhesive resin for example may be used Think 10~90 parts by weight, preferably can be 20~80 parts by weight, more preferably can be 30~70 parts by weight, in this case, tool The advantages of being conducive to the processes such as high-resolution pattern realization and pattern rectilinear propagation.

Relative to whole 100 parts by weight of above-mentioned blue-sensitive resin combination, the content of above-mentioned alkali soluble resins is usual For 1~50 parts by weight, preferably 3~40 parts by weight, the range of more preferably 5~30 parts by weight.In above-mentioned alkali soluble resins Abundant for the dissolubility of developer solution in the case that content is met the above range, non-pixel portion is not likely to produce aobvious on substrate Shadow residue, the film that when development is not susceptible to the pixel portion of exposure portion are reduced, and the deciduous with non-pixel portion is good to incline To, therefore preferably.

Blue colorant

Blue-sensitive resin combination of the invention includes blue colorant.Blue-sensitive resin combination of the invention Object has the light for the light source that can prevent from being reflected by aftermentioned scattering particles because too due to further including blue colorant The outer light of sunlight etc and the phenomenon that reflect again, thus the advantage that realizing the image quality of high-quality.

Above-mentioned blue colorant specifically may include blue pigment, and above-mentioned blue pigment can specifically enumerate colour index (dye Se Jia association (The society of Dyers and Colourists) publishes) in be classified as the compound of pigment, more specifically The pigment of following such colour index (C.I.) number can be enumerated, but is not necessarily limited to this.

In another embodiment of the invention, above-mentioned blue colorant be may include selected from by C.I. pigment blue 15: 3,15: 4, the blue pigment of one or more of group of 15:6,16,21,28,60,64,76 and their combination composition.

Wherein, from the aspect of the effect of inhibitory effect and high colorrendering quality for realizing external light reflection, choosing is preferably comprised Free C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, one of the group that C.I. pigment blue 16 forms More than.

In another embodiment of the invention, above-mentioned blue colorant can be further included selected from by dyestuff and purple face Expect one or more of the group of composition.

Above-mentioned violet pigment for example can be for selected from by C.I. pigment violet 1,14,19,23,29,32,33,36,37,38 and One or more of the group of their combination composition, however, not limited to this, wherein, realizing Gao Yan from by low colorant content , it is preferable to use C.I. pigment Violet 23 from the perspective of the viewpoint and reliability of color reproduction.

Above-mentioned dyestuff can enumerate colour index (dyeing association, family (The Society of Dyers and Colourists) publish) in be classified as in the compound or dyeing handbook (Se Ran society) of dyestuff documented well known blue or Cudbear.

For example, can be enumerated as C.I. solvent dye:

C.I. solvent blue 5,35,36,37,44,45,59,67 and 70；And

C.I. solvent purple 8,9,13,14,36,37,47 and 49 etc..

Wherein, it preferably comprises selected from by C.I. solvent blue 35,36,44,45 and 70；And the group that C.I. solvent violet 13 forms One or more of.

In addition, can be enumerated as C.I. acid dyes:

C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87, 90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、 267,278,280,285,290,296,315,324:1,335 and 340；And

C.I. acid violet 6B, 7,9,17,19 and 66 etc..

Wherein, it preferably comprises selected from by C.I. acid blue 80 and 90；And one of the group that C.I. acid violet 66 forms More than.

In addition, can be enumerated as C.I. direct dyes:

C.I. directly indigo plant 38,44,57,70,77,80,81,84,85,86,90,93,94,95,97,98,99,100,101, 106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、 162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、 207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、 252,256,257,259,260,268,274,275 and 293；And

C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103 and 104 Deng.

In addition, can be enumerated as C.I. mordant dyes:

C.I. medium indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39, 40,41,43,44,48,49,53,61,74,77,83 and 84；

C.I. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53 and 58 etc..

Above-mentioned dyestuff can respectively individually or be used in combination of two or more.

In another embodiment of the invention, relative to whole 100 parts by weight of above-mentioned blue-sensitive resin combination, on The content for stating blue colorant preferably can be able to be 0.5~30 parts by weight for 0.1~50 parts by weight, more preferably can for 1~ 20 parts by weight.

If the content of above-mentioned blue colorant is less than above range, it is likely difficult to the external light reflection for ensuring to want Inhibitory effect, in contrast, be greater than above range in the case where, the increase of luminous intensity may decline, occur composition Viscosity stability decline problem, therefore be suitble to use within the above range.

Scattering particles

Blue-sensitive resin combination of the invention includes containing the metal oxide that average grain diameter is 30~500nm Scattering particles.

In another embodiment of the invention, above-mentioned metal oxide may include selected from by Li, Be, B, Na, Mg, Al, Si、K、Ca、Sc、V、Cr、Mn、Fe、Ni、Cu、Zn、Ga、Ge、Rb、Sr、Y、Mo、Cs、Ba、La、Hf、W、Tl、Pb、Ce、Pr、Nd、 In the group of Pm, Sm, Eu, Gd, Tb, DY, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and their combination composition More than one oxide.

In another embodiment of the invention, above-mentioned metal oxide be may include selected from by Al₂O₃、SiO₂、ZnO、 ZrO₂、BaTiO₃、TiO₂、Ta₂O₅、Ti₃O₅、ITO、IZO、ATO、ZnO-Al、Nb₂O₃, SnO, MgO and their combination composition One or more of group, optionally, also can be used by acrylate etc. there is the compound of unsaturated bond to have carried out surface The material of reason.

Above-mentioned scattering particles limits average grain diameter and entirety in a manner of the luminous intensity of colour filter can be made maximized Content in composition.

In the present invention, " average grain diameter " can refer to number average bead diameter, such as can be from utilizing field emission scanning electron microscope (FE-SEM) or picture obtained from transmission electron microscope (TEM) observation is found out.Specifically, can by from FE-SEM or Some samples are extracted in the observation image of TEM, and is measured and has been carried out the value of arithmetic average after the diameter of these samples and obtain.

The average grain diameter of above-mentioned metal oxide can be 30~500nm, preferably can be 30~300nm.In above-mentioned gold In the case that the average grain diameter of category oxide is met the above range, dispersion effect increases, the blue sense comprising above-mentioned scattering particles Even if photosensitive resin composition is free of blue quantum dot, it can also play the role of blue pixel by blue-light source, therefore It is preferred that the surface of the blue color patterns layer of uniform quality is obtained due to preventing deposited phenomenon in composition, thus can be above-mentioned It suitably adjusts and uses in range.

In another embodiment of the invention, relative to whole 100 parts by weight of above-mentioned blue-sensitive resin combination, on The content for stating scattering particles can be 0.1~50 parts by weight, preferably can be 5~30 parts by weight, it more desirable to can be 10~20 Parts by weight.The content of above-mentioned scattering particles within the above range in the case where, have to manufacture and have excellent shine The advantages of colour filter of intensity.Specifically, the content of above-mentioned scattering particles within the above range in the case where, have can It is easy to ensure that the advantages of luminous intensity, the stability of composite inhibiting wanted reduce.

In another embodiment of the invention, above-mentioned blue-sensitive resin combination can be further included selected from by light One or more of polymerizable compound, Photoepolymerizationinitiater initiater, solvent and group of additive composition.

Photopolymerizable compound

Photopolymerizable compound contained by blue-sensitive resin combination of the invention be can by light and after The effect for the Photoepolymerizationinitiater initiater stated and the compound polymerizeing, can enumerate that monofunctional monomer, two functional monomers, other are multifunctional Monomer etc..

As the concrete example of above-mentioned monofunctional monomer, nonylphenol acrylate phenyl carbitol ester, acrylic acid 2- hydroxyl can be enumerated Base -3- phenoxy-propyl, acrylic acid 2- ethylhexyl carbitol ester, acrylic acid 2- hydroxy methacrylate, n-vinyl pyrrolidone etc..

As the concrete example of above-mentioned two functional monomer, 1,6- hexylene glycol two (methyl) acrylate, ethylene glycol can be enumerated Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A it is double (acrylyl oxy-ethyl) ether, 3- methyl pentanediol two (methyl) acrylate etc..

As the concrete example of other above-mentioned polyfunctional monomers, can enumerate trimethylolpropane tris (methyl) acrylate, Pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc..Wherein, it is preferable to use more than two functions polyfunctional monomer.

Relative to whole 100 parts by weight of above-mentioned blue-sensitive resin combination, above-mentioned photopolymerizable compound can be with 1 ~30 parts by weight are preferably used with the ranges of 5~20 parts by weight.The case where above-mentioned photopolymerizable compound is met the above range Under, intensity, flatness with pixel portion become good tendency, therefore preferably.

Photoepolymerizationinitiater initiater

Above-mentioned Photoepolymerizationinitiater initiater used in the present invention preferably comprises acetophenone based compound.

As above-mentioned acetophenone based compound, for example, diethoxy acetophenone, 2- hydroxy-2-methyl -1- benzene Base propane -1- ketone, benzil dimethyl ketal, 2- hydroxyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -2- methylpropane -1- ketone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-(4- methyl thio phenyl)-2- morpholino propane-1- ketone, 2- benzyl-2- dimethyl Amino -1- (4- morphlinophenyl) butane -1- ketone, 2- hydroxy-2-methyl [4- (1- methyl ethylene) phenyl] propane -1- ketone Oligomer etc. can preferably enumerate 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl) butane -1- ketone etc..

Furthermore, it is possible to which the Photoepolymerizationinitiater initiater other than above-mentioned acetophenone system is applied in combination.Light other than above-mentioned acetophenone system Polymerization initiator can enumerate through irradiation light the living radical producing agent for generating living radical, sensitizer, acid agent Deng.

As above-mentioned living radical producing agent, for example, benzoin based compound, benzophenone based compound, Thioxanthones based compound, triazine based compound etc..As above-mentioned benzoin based compound, for example, benzoin, benzene are even Relation by marriage methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether etc..As above-mentioned benzophenone series chemical combination Object, for example, benzophenone, methyl o-benzoylbenzoate, 4- phenyl benzophenone, 4- benzoyl -4 '-methyl two Diphenyl sulfide, 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6- tri-methyl benzophenone etc..As above-mentioned Thioxanthones based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthone, 2, Chloro- 4- propoxythioxanthone of bis- clopenthixal ketone of 4-, 1- etc..As above-mentioned triazine based compound, for example, 2,4- bis- (three Chloromethyl) -6- (4- methoxyphenyl) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5- Bis- (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5- triazines of triazine, 2,4-, bis- (trichloromethyl) -6- [2- of 2,4- (5- methylfuran -2- base) ethylidene] -1,3,5- triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (furans -2- base) ethylidene] - Bis- (the trichloromethyl) -6- of 1,3,5- triazine, 2,4- [2- (4- diethylamino -2- aminomethyl phenyl) ethylidene] -1,3,5- triazine, Bis- (the trichloromethyl) -6- of 2,4- [2- (3,4 Dimethoxyphenyl) ethylidene] -1,3,5- triazine etc..Freely as above-mentioned activity Base producing agent, can be used such as 2,4,6- trimethylbenzoyl diphenyl phosphine oxides, bis- (Chloro-O-Phenyl) -4 2,2-, and 4 ', 5, 5 '--1,2 '-bisglyoxalines of tetraphenyl, 10- butyl -2- chloro-acridine ketone, 2- ethyl hydrazine, benzil, 9,10- phenanthrenequione, camphorquinone, Phenylglyoxalates methyl esters, titanocenes compound etc..

As above-mentioned acid agent, for example, 4- hydroxy phenyl dimethyl disulfideTosilate, 4- hydroxy benzenes Base dimethyl disulfideHexafluoro antimonate, 4- acetoxyl group phenyl dimethyl disulfideTosilate, 4- acetoxyl group phenyl first Base dibenzylsulfideHexafluoro antimonate, triphenyl sulphurTosilate, triphenyl sulphurHexafluoro antimonate, diphenyl iodineTosilate, diphenyl iodineHexafluoro antimonate etc.Salt, nitrobenzyl tosylat class, benzoin toluene Sulfonic acid esters etc..In addition, in above compound, also have as living radical producing agent while generating living radical and acid Compound, for example, triazine system Photoepolymerizationinitiater initiater is also used as acid agent.

On the basis of whole 100 parts by weight of solid component, relative to above-mentioned alkali soluble resins and above-mentioned optical polymerism chemical combination The content of the total amount of object, above-mentioned Photoepolymerizationinitiater initiater used in blue-sensitive resin combination of the invention is usually 0.1~40 parts by weight, preferably 1~30 parts by weight.If being in above range, there are above-mentioned blue-sensitive resin combinations Object high-sensitivity, the flatness on the surface of the intensity or pixel portion of the pixel portion formed using the composition are become good and inclined To, therefore preferably.In addition, photopolymerization initiator can be used in the present invention.Above-mentioned photopolymerization initiator sometimes with it is above-mentioned Photoepolymerizationinitiater initiater is applied in combination, and is the photopolymerizable compound in order to promote to cause polymerization because of above-mentioned Photoepolymerizationinitiater initiater Polymerization and the compound that uses.As above-mentioned photopolymerization initiator, amine compound, alkoxy anthracene system chemical combination can be enumerated Object, thioxanthones based compound etc..

As amine compound, for example, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethyl Methyl anthranilate, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid 2- dimethyl Amino ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, N, N- dimethyl-p-toluidine, 4,4 '-bis- (dimethylaminos) Benzophenone (common name, Michler's keton), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethylmethylamino) hexichol first Ketone etc., wherein preferably 4,4 '-bis- (diethylamino) benzophenone.As alkoxy anthracene based compound, for example, 9,10- dimethoxy anthracene, 2- ethyl -9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene Deng.As thioxanthones based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thiophene Ton ketone, bis- clopenthixal ketone of 2,4-, the chloro- 4- propoxythioxanthone of 1- etc..Such Photoepolymerizationinitiater initiater can individually or will be a variety of It is applied in combination.It, can be with as commercially available photopolymerization initiator in addition it is possible to use commercially available product is as photopolymerization initiator Enumerate trade name " EAB-F " [manufacturer: Baotugu Chemical Industrial Co., Ltd] etc..

Using these photopolymerization initiators, usage amount is usual in terms of every 1 mole of Photoepolymerizationinitiater initiater For 10 moles hereinafter, preferably 0.01~5 mole.If being in above range, there are above-mentioned blue-sensitive resin combinations The tendency that the sensitivity of object is further got higher, improved using the productivity of the colour filter of the composition formation, therefore preferably.

Solvent

Solvent contained in blue-sensitive resin combination of the invention is not particularly limited, and blue sense can be used Various organic solvents used in photosensitive resin composition field.As its concrete example, can enumerate ethylene glycol single methyl ether, The ethylene glycol monoalkyl ethers class such as ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl The diethylene glycol dialkyl ethers classes such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, first The ethylene glycol alkyl ethers acetate esters such as base cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, third Glycol list monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxybutyl acetic acid esters and methoxypentyl acetic acid esters etc. Aklylene glycol alkylether acetates class, benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon, methyl ethyl ketone, acetone, The ketones such as methyl amyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol etc. Alcohols, the esters such as 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate, ring-type esters such as gamma-butyrolacton etc..Above-mentioned solvent In, from coating, drying property viewpoint, can preferably enumerate above-mentioned solvent mid-boiling point is 100 DEG C~200 DEG C organic molten Agent can more preferably enumerate aklylene glycol alkylether acetates class, ketone, 3- ethoxyl ethyl propionate, 3- methoxypropionic acid The esters such as methyl esters can more preferably enumerate propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, cyclohexanone, 3- Ethoxyl ethyl propionate, 3- methoxy methyl propionate etc..Above-mentioned solvent can be respectively used in mixed way alone or in any combination.

About the content of the above-mentioned solvent in blue-sensitive resin combination of the invention, relative to including the above-mentioned of its Whole 100 parts by weight of blue-sensitive resin combination, usually 40~90 parts by weight, preferably 70~85 parts by weight.Upper State solvent content meet the above range in the case where, utilize roll coater, spin coater, slit spin coater, slit type coater When the apparatus for coating such as (otherwise referred to as die coating machine), ink-jet printer are coated, there is coating to become good tendency, therefore excellent Choosing.

Additive

In blue-sensitive resin combination of the invention, filler, other macromolecule chemical combination optionally also can be used together The additives such as object, pigment dispersing agent, closely sealed promotor, antioxidant, ultraviolet absorbing agent, anticoagulant.

The concrete example of above-mentioned filler can illustrate glass, silica, aluminium oxide etc..As other above-mentioned macromolecule chemical combination Object can specifically enumerate the curable resins such as epoxy resin, maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol Thermoplastic resins such as monoalky lether, poly- fluoroalkyl, polyester, polyurethane etc..As above-mentioned pigment dispersing agent, Ke Yili With commercially available surfactant, for example, organic silicon-type, fluorine system, ester system, cationic system, anionic system, nonionic system, Surfactants such as both sexes etc..They can respectively individually or be used in combination of two or more.As above-mentioned surfactant, example If any polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether, polyethylene glycol di class, sorbitan fatty ester Class, fatty acid modified polyesters, tertiary-amine modified polyurethanes, polyethyleneimine amine etc. in addition to this, can be with as trade name Enumerate KP (manufacture of chemical industrial company, SHIN-ETSU HANTOTAI), POLYFLOW (manufacture of chemical company, common prosperity society), EFTOP (Tohkem The manufacture of Products company), MEGAFAC (big Japanese ink chemical industrial company manufacture), Fluorad (Sumitomo 3M corporation Make), Asahi guard, Surflon (more than, Asahi Glass glass company manufacture), SOLSPERSE (manufacture of Zeneca company), EFKA (chemical company's manufacture), PB821 (manufacture of aginomoto company) etc..As above-mentioned closely sealed promotor, for example, second Alkenyl trimethoxy silane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxy) silane, N- (2- amino second Base) -3- aminopropylmethyldimethoxysilane, N- (2- amino-ethyl) -3- TSL 8330,3- aminopropan Ethyl triethoxy silicane alkane, 3- glycidoxy-propyltrimethoxy silane, 3- glycidoxypropyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilane, 3- r-chloropropyl trimethoxyl silicon Alkane, 3- methyl allyl acyloxypropyl trimethoxysilane, 3-mercaptopropyi trimethoxy silane etc..As above-mentioned antioxidant, 2,2 '-thiobis (4- methyl-6-tert-butylphenol), 2,6- di-t-butyl -4- methylphenol etc. can specifically be enumerated.As Ultraviolet absorbing agent can specifically enumerate 2- (3- tert-butyl -2- hydroxy-5-methyl base phenyl) -5- chlorobenzotriazole, alkoxy two Benzophenone etc..As anticoagulant, Sodium Polyacrylate etc. can be specifically enumerated.

About above-mentioned additive, those skilled in the art can be within the scope of the effect of the invention with appropriate Content additional use.

It, can be for example, by following such though the manufacturing method of above-mentioned blue-sensitive resin combination is not limited to this Method manufacture.

Scattering particles is mixed with solvent in advance and is dispersed to average grain diameter as 30~500nm using ball mill.At this point, Dispersing agent can be optionally further used, blue colorant, alkali soluble resins part or all can also be cooperated.Institute Remaining alkali solubility is further added in a manner of becoming scheduled concentration in the dispersion liquid (hereinafter, otherwise referred to as mill base) obtained Resin, photopolymerizable compound, Photoepolymerizationinitiater initiater, the other compositions optionally used and optionally additional solvent, thus It can obtain target photosensitive polymer combination.At this point, about blue colorant, it is preferable to use ball mill etc. and make its average grain Diameter has 0.2 μm of degree below.

< colour filter and image display device >

Another mode of the invention is related to the blue comprising the solidfied material containing blue-sensitive resin combination above-mentioned The colour filter containing spontaneous light pixel of pattern layer.

In the present invention, above-mentioned blue-sensitive resin combination can be blue color patterns layer formation blue-sensitive resin Composition.In the present invention, above-mentioned blue-sensitive resin combination is free of quantum dot.

Colour filter of the invention is by blue-sensitive resin combination above-mentioned rather than blue quantum dot manufactures, therefore has Manufacturing cost can be reduced, has the advantages that excellent visual angle.In addition, blue-sensitive resin combination of the invention is with excellent Different thermal fluidity, therefore have the advantage that not generate pattern straight using the colour filter of its manufacture and image display device Into property and inverted cone surface, inhibiting the generation of outgassing in manufacturing process and ghost does not occur in panel work, anti-reflection effect is excellent, Not only with image quality, the excellent heat resistance, chemical resistance of high-quality, durability and reliability are also excellent.

Blue color patterns layer of the above-mentioned colour filter comprising substrate and the top for being formed in aforesaid substrate.

Aforesaid substrate can be itself substrate of above-mentioned colour filter, or may be in display device etc. locating for colour filter Position is not particularly limited.Aforesaid substrate can be glass, silicon (Si), Si oxide (SiOx) or polymeric substrate, above-mentioned height Molecule substrate can be polyether sulfone (polyethersulfone, PES) or polycarbonate (polycarbonate, PC) etc..

Above-mentioned blue color patterns layer is the layer comprising blue-sensitive resin combination of the invention, can be for by coating It states blue-sensitive resin combination and is exposed in a predetermined pattern, develop and heat cure and the layer that is formed, above-mentioned figure Pattern layer can be formed by carrying out method commonly known in the art.

Above-mentioned colour filter can be further included selected from one of the group being made of red pattern layer and green pattern layer More than.That is, colour filter of the invention can contain comprising blue color patterns layer above-mentioned and further include selected from by red pattern The spontaneous light pixel of one or more of the group of layer and green pattern layer composition.

Above-mentioned red pattern layer or green pattern layer may include quantum dot and scattering particles.Specifically, of the invention Colour filter may include the red pattern layer containing red quantum dot or the green pattern layer containing green quantum dot, above-mentioned red Pattern layer or green pattern layer may include scattering particles.Above-mentioned red pattern layer or green pattern layer can pass through aftermentioned hair The light source of blue light issues respective red light or blue light out.

Above-mentioned scattering particles may include average grain diameter be 30~500nm metal oxide, with above-mentioned scattering particles and The related content of metal oxide can be applicable in scattering particles contained in blue-sensitive resin combination of the invention and The related content of metal oxide.

In the present invention, form, composition and its content of quantum dot contained in above-mentioned red pattern layer or green pattern layer It does not limit, the commonly used quantum dot in this field can be applied.

Colour filter comprising substrate as described above and pattern layer can further include be formed between each pattern every Wall, and black matrix can be further included, but not limited thereto.

Another mode of the invention is related to the image display dress comprising colour filter above-mentioned and the light source for issuing blue light It sets.That is, image display device of the invention includes the indigo plant with the solidfied material containing blue-sensitive resin combination above-mentioned The colour filter of chromatic graph pattern layer and the light source for issuing blue light.

Colour filter of the invention can be applied not only to common liquid crystal display device, can also be aobvious applied to electroluminescent The various image display devices such as showing device, plasm display device, field emission display device.

The case where above-mentioned image display device includes colour filter and above-mentioned light source containing blue color patterns layer of the invention Under, have and has the advantage that excellent luminous intensity or visual angle.In addition, the blue color patterns that colour filter of the invention is included Layer without blue quantum dot has the advantages that the low image display device of manufacturing cost can be manufactured.

Hereinafter, being described in detail to illustrate this specification by embodiment.But the embodiment of this specification Other various forms can be deformed into, should not be construed to the range of this specification by embodiment following detailed description of Restriction.The embodiment of this specification is provided to more completely illustrate this specification to those of ordinary skill in the art 's.In addition, " % " and " part " of following presentation content as long as no it is specifically mentioned then be weight basis.

Synthesis example: the synthesis of alkali soluble resins

Synthesis example 1: alkali soluble resins

Prepare the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe, on the other hand, As monomer dropping funel, in investment benzyl maleimide 74.8g (0.20 mole), acrylic acid 43.2g (0.30 mole), second Alkenyl toluene 118.0g (0.50 mole), tert-butyl hydroperoxide -2 ethyl hexanoic acid ester 4g, propylene glycol monomethyl ether (PGMEA) it is stirred and is prepared after 40g, as the dropwise adding tank of chain-transferring agent, n-dodecane mercaptan 6g, PGMEA is added It is stirred and is prepared after 24g.Then, PGMEA 395g is imported into flask, and the atmosphere in flask is made to become nitrogen from air After gas, the temperature of flask is warming up to 90 DEG C while stirring.Then, monomer and chain tra nsfer are added dropwise since dropping funel Agent.When dropwise addition, 2h is respectively carried out while maintaining 90 DEG C, 110 DEG C are warming up to after 1h and maintains 3h, later, imported gas and lead Enter pipe, starts the bubbling of the mixed gas of oxygen/nitrogen=5/95 (v/v).Then, by glycidyl methacrylate 28.4g [(0.10 mole), (carboxyl relative to the acrylic acid used in this reaction is 33 moles of %)], 2,2 '-methylene Bis- (4- methyl-6-tert-butylphenol) 0.4g, triethylamine 0.8g are put into flask, and at 110 DEG C, the reaction was continued 8 hours, obtains The acid value of solid component is the Resin A of 70mgKOH/g.Weight average molecular weight by the polystyrene conversion of GPC measurement is 16, 000, molecular weight distribution (Mw/Mn) is 2.3.

The synthesis of synthesis example 2:Cardo system adhesive resin (A-1)

(1) 9,9 '-bis- (4- glycidoxy phenyl) fluorenes (Hear as bisphenol epoxy compound are added in the reactor Chem company) 138g, acrylic acid 2- carboxyethyl (2-Carboxyethyl acrylate) 54g, benzyltriethylammoinium chloride (great Jing Hua King Company) 1.4g, triphenylphosphine (Aldrich) 1g, propylene glycol methyl ethyl acetic acid esters (Daicel Chemical company) 128g and quinhydrones 0.5g maintain 12 hours, after being warming up to 120 DEG C to synthesize following chemical formula 22 Represented compound.

(2) compound 60g, bibenzene tetracarboxylic dianhydride represented by above-mentioned chemical formula 22 are added in the reactor (Mitsubishi Gas company) 11g, tetrabydrophthalic anhydride (Aldrich) 3g, propylene glycol methyl ethyl acetic acid esters (Daicel Chemical company) 20g and N, N '-tetramethyl ammonium chloride 0.1g after being warming up to 120 DEG C, is maintained 2 hours, from And synthesize compound represented by following [chemical formulas 23].The weight average molecular weight of compound represented by resulting chemical formula 23 is 5,400g/mol。

[chemical formula 22]

[chemical formula 23]

The synthesis of synthesis example 3:Cardo system adhesive resin (A-2)

(1) 9,9 '-bis- (4- glycidoxy phenyl) fluorenes (Hear as bisphenol epoxy compound are added in the reactor Chem company) 138g, mono succinate -2- acryloyl-oxy ethyl ester (mono-2-acryloyloxyethyl succinate) 54g, Benzyltriethylammoinium chloride (great Jing Hua King Company) 1.4g, triphenylphosphine (Aldrich) 1g, propylene glycol methyl ethyl acetic acid Ester (Daicel Chemical company) 128g and quinhydrones 0.5g after being warming up to 120 DEG C, is maintained 12 hours, to synthesize following Compound represented by [chemical formula 24].

(2) compound 60g, bibenzene tetracarboxylic dianhydride represented by above-mentioned chemical formula 24 are added in the reactor (Mitsubishi Gas company) 11g, tetrabydrophthalic anhydride (Aldrich) 3g, propylene glycol methyl ethyl acetic acid esters (Daicel Chemical company) 20g and N, N '-tetramethyl ammonium chloride 0.1g after being warming up to 120 DEG C, is maintained 2 hours, from And synthesize compound represented by following [chemical formulas 25].The weight average molecular weight of compound represented by resulting chemical formula 25 is 5,400g/mol。

[chemical formula 24]

[chemical formula 25]

The manufacture of synthesis example 4:Cardo system adhesive resin A-3

In the 1000ml flask for having blender, thermometer, reflux condensing tube, addition 2,2 '-(4,4 '-(fluorenes -9 9H-, 9- diyl) bis- (4,1- phenylenes)) bis- (oxygen) bis- 10 parts by weight of (methylene) diepoxide for example, 30 parts by weight of acrylic acid, the third two 10 parts by weight of alcohol monomethyl ether acetate, are slowly increased to 100 DEG C for the temperature of flask while stirring.

Later, 0.3 parts by weight of tetramethyl ammonium chloride, 0.01 parts by weight of polymerization inhibitor are added, are then maintained 3 hours by temperature While be stirred.If reaction terminates, temperature is slowly dropped to room temperature, addition distilled water is precipitated.Filtering and only It, will be dry after sediment wash with distilled water 2~3 times after retained sediments object.

10 parts by weight of sediment obtained in this way are put into having blender, thermometer, reflux condensing tube, dropping funel In the 1000ml flask of nitrogen ingress pipe, 3 parts by weight of tetramethyl ammonium chloride, propylene glycol monomethyl ether second are then added thereto 50 parts by weight of acid esters, 5 parts by weight of phthalic anhydride, and carry out nitrogen displacement.

Later, so that temperature is risen to 110 DEG C, after rising while being stirred to react liquid, react 7 hours.After reaction, it is added Heterochromatic 5 parts by weight of alkene -1,3- diketone of 5,5 '-(perfluoropropane -2,2- diyl) dibenzo [de] are further reacted 6 hours.Purification Afterwards, obtain solid component acid value be 123mgKOH/g, by GPC measure weight average molecular weight be 12,300 alkali-soluble binder Resin A -3.

The manufacture of synthesis example 5:Cardo system adhesive resin A-4

In the 1000ml flask for having blender, thermometer, reflux condensing tube be added 2,2 '-(4,4 '-(fluorenes -9 9H-, 9- diyl) bis- (4,1- phenylenes)) bis- (oxygen) bis- 10 parts by weight of (methylene) diepoxide for example, 30 parts by weight of acrylic acid, the third two 10 parts by weight of alcohol monomethyl ether acetate, are slowly increased to 100 DEG C for the temperature of flask while stirring.

Later, 0.3 parts by weight of tetramethyl ammonium chloride, 0.01 parts by weight of polymerization inhibitor are added, then, temperature maintenance 3 is small When while be stirred.If reaction terminates, temperature is slowly dropped to room temperature, addition distilled water is precipitated.Filtering and It, will be dry after sediment wash with distilled water 2~3 times only after retained sediments object.

10 parts by weight of sediment obtained in this way are put into having blender, thermometer, reflux condensing tube, dropping funel In the 1000ml flask of nitrogen ingress pipe, 3 parts by weight of tetramethyl ammonium chloride, propylene glycol monomethyl ether second are then added thereto 50 parts by weight of acid esters, 5 parts by weight of phthalic anhydride, and carry out nitrogen displacement.

Later, so that temperature is risen to 110 DEG C, after rising while being stirred to react liquid, react 7 hours.After reaction, it is added 5,5 '-(perfluoropropane -2,2- diyls) bis- (hexahydro isobenzofuran -1,3- diketone) 5 parts by weight are further reacted 6 hours.Essence After system, the acid value for obtaining solid component is 130mgKOH/g, is bonded by the alkali solubility that the weight average molecular weight that GPC is measured is 12,000 Agent Resin A -4.

The manufacture of synthesis example 6:Cardo system alkali soluble resins A-5

In the 1000ml flask for having blender, thermometer, reflux condensing tube be added 2,2 '-(4,4 '-(fluorenes -9 9H-, 9- diyl) bis- (4,1- phenylenes)) bis- (oxygen) bis- 10 parts by weight of (methylene) diepoxide for example, 30 parts by weight of acrylic acid, the third two 10 parts by weight of alcohol monomethyl ether acetate, are slowly increased to 100 DEG C for the temperature of flask while stirring.

Later, it after adding 0.3 parts by weight of tetramethyl ammonium chloride, 0.01 parts by weight of polymerization inhibitor, is maintained 3 hours by temperature It is stirred simultaneously.If reaction terminates, temperature is slowly dropped to room temperature, addition distilled water is precipitated.Filtering and it is only residual It, will be dry after sediment wash with distilled water 2~3 times after staying sediment.

10 parts by weight of sediment obtained in this way are put into having blender, thermometer, reflux condensing tube, dropping funel In the 1000ml flask of nitrogen ingress pipe, 3 parts by weight of tetramethyl ammonium chloride, propylene glycol monomethyl ether second are then added thereto 50 parts by weight of acid esters, 5 parts by weight of phthalic anhydride, and carry out nitrogen displacement.

Later, so that temperature is risen to 110 DEG C, after rising while being stirred to react liquid, react 7 hours.After reaction, it is added 4,4 '-(hexafluoroisopropyli,ene) diphthalic anhydrides, 5 parts by weight are further reacted 6 hours.After purification, solid component is obtained Acid value be 120mgKOH/g, by GPC measure weight average molecular weight be 12,100 alkali-soluble binder resin A-5.

The synthesis (B-1, B-2) of synthesis example 7:Cardo system adhesive resin

(1) synthesis example 7-1:2,2 '-((((9H- fluorenes -9,9- diyl) bis- (4,1- phenylenes)) bis- (oxygen)) bis- (methylenes Base)) bis- (ethylene oxide) (2,2 '-((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) Bis (methylene)) bis (oxirane)) synthesis

9,9- bisphenol fluorene (9,9-bisphenolfluorene) 42.5g is added, with 2- (chloromethyl) ethylene oxide (2- (chloromethyl) oxirane) 220ml and tert-butyl ammonium bromide (t-butulammonium bromide) 100mg exist together Then 90 DEG C of stirrings are evaporated under reduced pressure until reactant all disappearances.30 DEG C are further cooled the temperature to, methylene chloride is injected (dichloromethane) after, NaOH is slowly put into.By high performance liquid chromatography (HPLC) method confirm product be 96% with After upper, 5%HCl be added dropwise, reaction terminates.It extracts reactant and after carrying out layer separation, washes with water organic layer, washing is to becoming It is neutral.Organic layer MgSO₄After drying, it is evaporated under reduced pressure and is concentrated using rotary evaporator.Into the product after concentration It is added methylene chloride (dichloromethane), is stirred while temperature is risen to 40 DEG C, while putting into methanol (methanol), then solution temperature is reduced, continues to stir.After solid generated filtering, vacuum is carried out at normal temperature It is dry, obtain white solid powder 52.7g (yield 94%).

(2) synthesis example 7-2:3,3 '-(((9H- fluorenes -9,9- diyl) bis- (4,1- phenylenes)) bis- (oxygen)) bis- (1- phenyl sulphur Generation) propane -2- alcohol) (3,3 '-(((9H-Fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2-ol)) synthesis of (BTCP)

The compound (1000g) of synthesis example 7-1, benzenethiol (thiophenol) 524g, ethyl alcohol 617g is added and is stirred It mixes.Triethylamine (triethylamine) 328g is slowly added dropwise into reaction solution.It is true by high performance liquid chromatography (HPLC) method After recognizing parent material disappearance, reaction is terminated.After reaction, ethyl alcohol is passed through into vacuum distillation removal.Organic matter is dissolved in two After chloromethanes (dichloromethane), after being washed with water, by being evaporated under reduced pressure methylene chloride (dichloromethane) Removal.After organic matter after concentration is dissolved in ethyl acetate (ethyl acetate), ether solvents are added dropwise, and stir 30 minutes.It will change Object vacuum distillation is closed, to obtain light yellow oil (pale yellow oil) 945g (yield 64%).

(3) synthesis (B-1) of synthesis example 7-3:Cardo system adhesive resin

The BTCP monomer 200g for being dissolved in 50%PGMEA solvent is added, is warming up to 115 DEG C.3,3 ', 4,4 '-are added dropwise at 115 DEG C After bibenzene tetracarboxylic dianhydride (3,3 ', 4,4 '-Biphenyltetracarboxylic dianhydride) 31.1g, at 115 DEG C It maintains to be stirred while 6 hours.Phthalic anhydride (Phthalic anhydride) 7.35g is added, futher stirs 2 After hour, reaction is terminated.After cooling, the adhesive resin that weight average molecular weight is 3,500g/mol is obtained.

(4) synthesis (B-2) of synthesis example 7-4:Cardo system adhesive resin

The BTCP monomer 200g for being dissolved in 50%PGMEA solvent is added, is warming up to 115 DEG C.In 115 DEG C of dropwise addition Pyromellitic Acids After dianhydride (Pyromellitic dianhydride) 21.1g, it is stirred while maintaining 6 hours for 115 DEG C.Adjacent benzene is added After futher stirring 2 hours, reaction is terminated by dicarboxylic acid anhydride (Phthalic anhydride) 7.35g.After cooling, weight is obtained Average molecular weight is the adhesive resin of 4,500g/mol.

At this point, the measurement of the weight average molecular weight (Mw) about bonding agent resin, using GPC method according to condition below come into Row.

Device: HLC-8120GPC (manufacture of Tosoh company)

Column: TSK-GELG4000HXL+TSK-GELG2000HXL (series connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow velocity: 1.0ml/ minutes

Injection rate: 50 μ l

Detector: RI

Measure sample solution concentration: 0.6 mass % (solvent=tetrahydrofuran)

Correction standard substance: TSK STANDARD POLYSTYRENE the F-40, (east F-4, F-1, A-2500, A-500 Cao company manufacture)

The ratio between weight average molecular weight obtained above and number-average molecular weight are set as molecular weight distribution (Mw/Mn).