CN101891845B - Application of carbazole oxime ester compound serving as photoinitiator in photopolymerisable acrylate composition - Google Patents
Application of carbazole oxime ester compound serving as photoinitiator in photopolymerisable acrylate composition Download PDFInfo
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Abstract
The invention relates to an application of a carbazole oxime ester compound serving as a photoinitiator in a photopolymerisable acrylate composition, the photopolymerisable acrylate composition containing the carbazole oxime ester compound and an application thereof. The composition presents excellent suitability by the combination of the specific photoinitiator and specific photopolymerisable acrylate monomer, and has high storage stability, higher light sensitivity in a short wave position, and excellent dissolvability performance; and when the composition is polymerized, the composition has the advantages of fast solidification speed, little pollution, energy conservation, high exposal efficiency and small exposal dosage, meanwhile, the solidified image pattern is fine and complete without defect and scum, and the membrane has good hardness.
Description
Technical field
The present invention relates to a kind of carbazole oxime ester compound purposes as light trigger in photopolymerization acrylate based composition, contain the above-mentioned photopolymerization acrylate based composition of this carbazole oxime ester compound, and use.
Background technology
Photocuring refers to monomer, oligomer or the polymer matrix solidification process under photoinduction, this technology has a wide range of applications in modern microelectronics, for example encapsulation of light-curable ink, liquid crystal panel, photosensitive printing version, spectral filter and photo-resist etc.The core of photocuring technology is photocurable polymerization single polymerization monomer and suitable light trigger.Under ultraviolet, X ray or the laser radiation of certain wavelength, light trigger produces active group, excites unsaturated group in the polymerisable monomer with polymerization reaction take place, thereby causes the curing of material.The light trigger of selecting suitable photocurable polymerization single polymerization monomer (or its composition) and matching with it is a research emphasis in the photocuring technology field always.
At present, esters of acrylic acid polymerization monomer is one of monomer classification that is most widely used in the photocuring technology.Along with the increase of photopolymerisable relevant report, the patent documentation of relevant photopolymerization acrylate based composition also increases thereupon, for example CN1337013, CN1424624, CN101052918 etc.But microelectronics is maked rapid progress, and its requirement to element is more and more higher.For example, the photopolymerizable composition that need to use is at i line (365nm) or g line (405nm) even more have higher photosensitive property under short wavelength's the light source, and prior composition can not satisfy urgent day by day demand.
As the main factor that influences the Photocurable composition photosensitive property, light trigger to the influence of photopolymerisable compositions photosensitive property not instrument be embodied in light trigger itself for the susceptibility of radiation, also be the suitability between it and the photopolymerizable monomer (or its composition).Therefore, when determining a kind of prescription of photopolymerisable compositions, optimum is seek a kind of and the polymerisable monomer that includes between have good effect () light trigger for example, synergistic effect, thereby the further photosensitive property of optimum combination thing.
Current, about light trigger very many reports have been arranged, for example st-yrax derivative, dibenzoyl ketal class, α, α-dialkoxy methyl phenyl ketone class, benzophenones/amines class, michaelis ketone, thiazolone/amine, aromatic diazo salt, three nitrogen piperazine classes, oxime ester class etc., typical example has commercially available Irgacure369, Darocure1173, OXE-1 and OXE-2.Yet, these light triggers exist more or less all in actual applications that light sensitivity low (rate of polymerization and exposure dose height), poorly soluble (transparency and photoetching residue are many), package stability are low, short wavelength's sensitivity deficiency, to defective such as the specific selectivity of photopolymerizable monomer is not strong, thereby influenced the performance of sensitive materials on the whole.
As preferred photopolymerisable compositions, require to have excellent stable storing performance on the one hand; To have highly sensitive to shortwave i line and g line on the other hand, in order to reduce exposure dose, improve exposure efficiency, thereby shorten the production cycle; Requirement is meticulous complete as pattern by the photocuring product important plan of photopolymerizable composition preparation on the one hand again, do not have defective and scum silica frost, and the hardness of photocuring film will be got well.These indexs are particularly important to the performance of spectral filter, photo-resist, and to reach this effect, the light trigger that at first just requires to use in the composition originally will have very high light sensitivity in the shortwave place, what whole composition system will be arranged in pairs or groups in addition is very reasonable, can bring into play optimum effect when namely light trigger is used in the polymerizable composition in the composition (monomer, resin) and the system.At present, at the research of this respect lacking very also.
Given this, the present invention will disclose a kind of oxime ester compound purposes as light trigger in specific photopolymerization acrylate based composition, and a kind of photopolymerization acrylate based composition that contains this oxime ester compound.By being used of specific light initiator and specific photopolymerization acrylic ester monomer, compositions table of the present invention has revealed very excellent suitability, and described oxime ester compound has shown performance far above other light trigger (for example other compound of disclosed similar among the CN101508744A) as light trigger in composition.
Summary of the invention
The object of the present invention is to provide formula (I) compound purposes as light trigger in photopolymerization acrylate based composition, and the photopolymerization acrylate based composition that contains this compound.When containing the photopolymerization acrylate based composition polymerization of described light trigger, curing speed is fast, less contamination, energy-conservation, exposure efficiency is high, exposure dose is little, the picture pattern of curing molding is meticulous complete simultaneously, does not have defective and scum silica frost, the hardness of film is fine.
In order to reach above-mentioned technique effect, technical scheme of the present invention is:
Formula (I) oxime ester compound as the purposes of light trigger, is characterized in that in photopolymerization acrylate based composition: the chemical structure of described formula (I) compound is as follows
Wherein
N=2, m=3 or 4;
Described photopolymerization acrylate based composition comprises
(A) alkali soluble resins of 20-45 mass parts, this resin be benzyl methacrylate, methacrylic acid, with the multipolymer of hydroxyethyl methylacrylate and/or methyl methacrylate, benzyl methacrylate in the multipolymer, methacrylic acid, with the mol ratio of hydroxyethyl methylacrylate and/or methyl methacrylate be 55-70: 5-10: 10-20, the weight-average molecular weight of multipolymer (Mw) is 5000-25000;
(B) dipentaerythritol acrylate of 10-20 mass parts;
(C) oxime ester compound shown in the formula of 5-7 mass parts (I).
The invention still further relates to a kind of photopolymerization acrylate based composition, it is characterized in that, comprise following component:
(A) alkali soluble resins of 20-45 mass parts, this resin be benzyl methacrylate, methacrylic acid, with the multipolymer of hydroxyethyl methylacrylate and/or methyl methacrylate, benzyl methacrylate in the multipolymer, methacrylic acid, with the mol ratio of hydroxyethyl methylacrylate and/or methyl methacrylate be 55-70: 5-10: 10-20, the weight-average molecular weight of multipolymer (Mw) is 5000-25000;
(B) dipentaerythritol acrylate of 10-20 mass parts;
(C) oxime ester compound shown in the formula of 5-7 mass parts (I).
In the described photopolymerization acrylate based composition, alkali soluble resins can also be benzyl methacrylate, methacrylic acid, with the multipolymer of acrylate shown in hydroxyethyl methylacrylate and/or methyl methacrylate and the formula (II),
Benzyl methacrylate in this multipolymer, methacrylic acid, with the mol ratio of acrylate shown in hydroxyethyl methylacrylate and/or methyl methacrylate and the formula (II) be 55-60: 5-10: 10-15: 10, the weight-average molecular weight of multipolymer is 5000-25000.
As the multipolymer of alkali soluble resins, its weight-average molecular weight is preferably 10000-15000; In photopolymerization acrylate based composition, be preferably the 25-35 mass parts.
In photopolymerization acrylate based composition, preferred dipentaerythritol acrylate is the 15-19 mass parts; Oxime ester compound shown in the preferred formula (I) is 6 mass parts.
Described photopolymerization acrylate based composition also can contain in the Photocurable composition other auxiliary agent commonly used, and for example representational have sensitizing agent, tinting material, tensio-active agent etc.
Sensitizing agent is not essential component among the present invention, and it helps out to photopolymerization reaction, himself any chemical transformation does not take place, mainly plays energy and shifts transfer function.In order to make photopolymerizable composition issue third contact of a total solar or lunar eclipse polyreaction in high lucifuge condition, need to add sensitizing agent sometimes.There is no particular limitation for spendable sensitizing agent in the present composition, for example can be coumarin derivatives and benzophenone derivates, and thioxanthone (TX) can be regarded the derivative of benzophenone as.Common sensitizing agent is as follows:
Can optionally in the present composition, add tinting material according to the needs of application system.Tinting material is to the painted material of photopolymerizable composition.Can be dyestuff and pigment as tinting material, preferred pigments.Tinting material is of a great variety, comprises pigment dyestuff and mineral dye, and there is no particular limitation to it in the present invention, can suitably select according to the purposes of gained colored filter or the purposes of colored composition film.In the present invention, if described photopolymerization acrylate based composition contains tinting material, then preferably contain the tinting material of 10-30 mass parts, more preferably the 15-20 mass parts.
In addition, for promoting composition system aim of even dispersion (particularly implementing in the coating process at the solution of composition), can optionally add tensio-active agent according to practical situation, for example commercially available FC-4430.This is known to those skilled in the art.Preferably, when described photopolymerization acrylate based composition contains tinting material, preferably also contain the tensio-active agent of 0.01-1 mass parts, more preferably the 0.01-0.5 mass parts.
The invention still further relates to the photoresist film and the colored filter film that are formed by above-mentioned photopolymerization esters of acrylic acid preparation of compositions.
Useful technique effect of the present invention:
Among the present invention, when formula (I) compound uses as light trigger in described photopolymerization acrylate based composition, has extraordinary storage stability, has very high light sensitivity at the shortwave place, superior solubility simultaneously, and the composition that comprises this light trigger has good stability and very high short wavelength's sensitivity, under very low exposure dose, composition system just can well crosslinking curing, and solidification effect is splendid.The smooth zero defect of made film edge, there are not scum silica frost, whole pattern integrity degree good, resist film hardness height, the spectral filter optical clarity height of making, not light leak.Especially make (the Black matrix of black matrix" in the colored filter, hereinafter to be referred as BM) time, because the existence of black pigment or dyestuff, light source utilize the effect extreme difference, and use this photopolymerizable composition, still can finish the making of BM under very low exposure dose, the BM that makes has precision, flatness and the weather resistance of high opacifying property, excellence.
Embodiment
To be example to make photoresist film and colored filter film below, the performance of the present composition will be described.
Photoresist film can use ordinary method preparation known in the field.For example: at first, composition dissolves of the present invention in appropriate organic solvent (for example 1-Methoxy-2-propyl acetate, 2 hydroxy propanoic acid ethyl ester), is obtained liquid composition; Utilize coating machine for example rotary coating machine, the excellent coating machine that winds the line, axle coating machine or spray coating machine etc. the liquid composition coating is dispersed on the substrate, and baking is dry before carrying out; Then, mask plate is attached on the sample exposes, develop subsequently and remove unexposed area; Carry out the back baking at last, just obtained the photo-resist dry film.
The photoresist film that contains black pigment is exactly BM; and on BM, add RGB (red, green, blue three looks) by same light polymerization process; just can form the key component chromatic photoresist of chromatic filter, add protective membrane and the ITO nesa coating just can be made into colored filter.
Embodiment 1-1
(1) colored curable (photopolymerization) composition No.1-1
Tinting material (carbon black) 300 mass parts
Alkali soluble resins 200 mass parts
(benzyl methacrylate/methacrylic acid/hydroxyethyl methylacrylate (mol ratio is 70/10/20) multipolymer (Mw:10,000))
Dipentaerythritol acrylate 100 mass parts
Formula (I) oxime ester compound [n=2, m=3] 60 mass parts
Tensio-active agent FC-4430 1 mass parts
(2) preparation spectral filter colour film
Each component of above-mentioned composition is mixed and be dissolved in the solvent 1-Methoxy-2-propyl acetate (PGMEA) of 1000 mass parts, form fluid composition.
Utilize the rotary coating machine that fluid composition is coated on the glass substrate, dry 2min under 90 ℃, forming thickness is filming of 1.5 μ m; For obtaining filming of above-mentioned thickness, coating procedure can be once to finish also to carry out several times.
Be cooled to room temperature then, enclose mask plate, use high voltage mercury lamp, by the slit of mask plate, expose to filming in the ultraviolet ray of 365nm, 405nm and 436nm wavelength.
Under 25 ℃ temperature, use 1% NaOH aqueous solution development, with the ultrapure water washing, air-dry again.
Afterwards, baking 30min in back obtains the pattern that mask plate shifts in 220 ℃ baking oven.
(3) performance evaluation
By the following method stability in storage and exposure sensitivity, the described coloured composition of use of painted photopolymerisable compositions are estimated at the sticking power that glass substrate forms development, integrity, pattern and the substrate of pattern, be the results are summarized in the table 1.
The stability in storage evaluation method
After the fluid composition of curable compositions at room temperature stored 1 month, visually estimate the precipitation degree of material according to following standard.
A: do not observe precipitation;
B: observe precipitation slightly;
C: observe precipitation.
The exposure sensitivity evaluation method
Will be in step of exposure photoirradiation zone 95% minimum exposure amount when above that back thickness becomes film thickness (100%) before the exposure of developing be evaluated as the exposure demand.The more little expression sensitivity of exposure demand is more high.
The sticking power evaluation method of development, pattern and substrate
Observe pattern on the substrate with scanning electron microscope (SEM), to estimate the sticking power of development, pattern and substrate, pattern integrity.
Development is according to following standard evaluation:
Zero: do not observe residue at unexposed portion;
◎: observe the small amount of residual thing at unexposed portion, but residual quantity can be accepted;
●: observe obvious residue at unexposed portion.
The sticking power of pattern and substrate is according to following standard evaluation:
Δ: do not observe pattern defect;
☆: observing the small portion pattern has a little defective;
▲: obviously observe many pattern defects.
Resolving power is according to following standard evaluation:
√: the minimum pattern size is smaller or equal to 10 μ m
*: the minimum pattern size is greater than 10 μ m
Embodiment 1-2
Use n=2, the formula of m=4 (I) oxime ester compound replaces the oxime ester compound among the embodiment 1-1, other constant, and preparation in an identical manner, and estimate with the identical method of embodiment 1-1.The results are shown in the table 1.
Comparing embodiment 1-3～1-13
Use the oxime ester compound among formula but oxime ester compound that n is different with the m value identical with formula (I) (can referring to CN101508744A) the replacement embodiment 1-1 among comparing embodiment 1-3～1-10; use benzil analog derivative 2-phenyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 (Irgacure369) among comparing embodiment 1-11～1-13 respectively; triazine derivative 2-(1; 3-benzo dioxolane-5-yl)-4; two (trichloromethyl)-1 of 6-; 3; 5-triazine (TAZ 107); carbazole oxime ester compound 1-(6-o-methyl-benzene formyl radical-9-ethyl carbazole-3-yl)-(3-ethyl ketone)-1-oxime acetic ester (OXE-02) replaces the oxime ester compound among the embodiment 1-1; other constant; prepare the spectral filter colour film in an identical manner, and estimate with the identical method of embodiment 1-1.The results are shown in the table 1.
Table 1
The result of table 1 shows that the prepared spectral filter photoresistance of the composition of embodiment 1-1～1-10 has good resolving power, development and substrate attachment power, and obviously there is deficiency in these areas in embodiment 1-11～1-13.Stability in storage integral body all well, but the diversity ratio of exposure dose is bigger.What pay particular attention to is the not enough 20mJ/cm of the exposure dose among embodiment 1-1 and the 1-2
2, far below comparing embodiment 1-3～1-13, shown extremely excellent photosensitivity.
Embodiment 2-1
(1) colored curable composition No.2-1
Tinting material C.I. Pigment red 254 60 mass parts
Alkali soluble resins 80 mass parts
[benzyl methacrylate/methacrylic acid/hydroxyethyl methylacrylate/formula (II) acrylate (mol ratio is 55/10/15/10) multipolymer] (Mw:12,000)
Dipentaerythritol acrylate 35 mass parts
Formula (I) oxime ester compound [n=2, m=3] 20 mass parts
Tensio-active agent FC-4430 0.1 mass parts
(2) preparation spectral filter colour film
Each component of above-mentioned composition is mixed and be dissolved in the solvent 1-Methoxy-2-propyl acetate (PGMEA) of 100 mass parts, form fluid composition.
Utilize the rotary coating machine that fluid composition is coated on the glass substrate, dry 2min under 90 ℃, forming thickness is filming of 1.5 μ m; For obtaining filming of above-mentioned thickness, coating procedure can be once to finish also to carry out several times.
Be cooled to room temperature then, enclose mask plate, use high voltage mercury lamp, by the slit of mask plate, expose to smearing in the ultraviolet ray of 365nm, 405nm and 436nm wavelength.
Under 25 ℃ temperature, use 1% NaOH aqueous solution development, with the ultrapure water washing, air-dry again.
Afterwards, baking 30min in back obtains the pattern that mask plate shifts in 220 ℃ baking oven.
(3) performance evaluation
Stability in storage and exposure sensitivity to painted photopolymerisable compositions, use described coloured composition to estimate at the sticking power that glass substrate forms development, integrity, pattern and the substrate of pattern, evaluation method is the same, and evaluation result is summarized in the table 2.
Embodiment 2-2
Use n=2, the formula of m=4 (I) oxime ester compound replaces the oxime ester compound among the embodiment 2-1, other constant, and preparation in an identical manner, and estimate with the identical method of embodiment 2-1.The results are shown in the table 2.
Comparing embodiment 2-3～2-13
Use the oxime ester compound among formula but oxime ester compound that n is different with the m value identical with formula (I) (can referring to CN101508744A) the replacement embodiment 2-1 among comparing embodiment 2-3～2-10, use Irgacure369, TAZ 107, OXE-02 to replace the oxime ester compound among the embodiment 2-1 among comparing embodiment 2-11～2-13 respectively, other constant, prepare in an identical manner, and estimate with the identical method of embodiment 2-1.The results are shown in the table 2.
Table 2
The result of table 2 shows that the prepared spectral filter photoresistance of the composition of embodiment 2-1～2-10 has good resolving power, development and substrate attachment power, and obviously there is deficiency in these areas in embodiment 2-11～2-13.Aspect exposure dose, the not enough 20mJ/cm of the exposure dose among embodiment 2-1 and the 2-2
2, far below comparing embodiment 2-3～2-13.On the other hand, the adding of formula (II) acrylate increases to the development of photoresistance film, resolving power and with substrate attachment power, has also changed the structural form of composition polymerizable body, makes the exposure sensitivity of composition that variation take place.By in the table 2 as seen, although the equal not enough 20mJ/cm of the composition exposure dose of No.2-1 and No.2-2
2, but get n=2, and the exposure dose of the No.2-2 composition of m=4 is than n=2, and the No.2-1 of m=3 is lower, and this situation with embodiment 1-1 and 1-2 is just in time opposite.
For Ming Dynasty style (II) acrylate furtherly adds the variation that causes, will contain n=2, m=3 and n=2, the composition of the formula of m=4 (I) oxime ester compound compares separately, as follows example.
Embodiment 3-1
(1) curable compositions No.3-1
Alkali soluble resins 36.7 mass parts
[benzyl methacrylate/methacrylic acid/methyl methacrylate (mol ratio is 70/10/20) multipolymer] (Mw:9,000)
Dipentaerythritol acrylate 15.8 mass parts
Formula (I) oxime ester compound [n=2, m=3] 5 mass parts
(2) preparation photo-resist
Each component of above-mentioned composition is mixed and be dissolved in the solvent of being formed by 20.2 mass parts 1-Methoxy-2-propyl acetates (PGMEA) and 30.0 mass parts 2 hydroxy propanoic acid ethyl esters the formation fluid composition.
Utilize the rotary coating machine that fluid composition is coated on the glass substrate, dry 2min under 90 ℃, forming thickness is filming of 1.5 μ m; For obtaining filming of above-mentioned thickness, coating procedure can be once to finish also to carry out several times.
Be cooled to room temperature then, enclose mask plate, use high voltage mercury lamp, by the slit of mask plate, expose to smearing in the ultraviolet ray of 365nm, 405nm and 436nm wavelength.
Under 25 ℃ temperature, use 1% NaOH aqueous solution development, with the ultrapure water washing, air-dry again.
Afterwards, baking 30min in back obtains the photo-resist dry film in 220 ℃ baking oven.
(3) performance evaluation
To stability in storage and the exposure sensitivity of painted photopolymerisable compositions, use described coloured composition to estimate at the sticking power that glass substrate forms development, integrity, pattern and the substrate of pattern, evaluation method is the same, the results are summarized in the table 3.
Embodiment 3-2
Use n=2, the formula of m=4 (I) oxime ester compound replaces the oxime ester compound among the embodiment 3-1, and other is constant, prepares in the same manner, and estimates with the identical method of embodiment 3-1.The results are shown in the table 3.
Table 3
Embodiment 4-1
(1) curable compositions No.4-1
Alkali soluble resins 36.7 mass parts
[benzyl methacrylate/methacrylic acid/methyl methacrylate/formula (II) acrylate (mol ratio is 60/10/10/10) multipolymer] (Mw:11,000)
Dipentaerythritol acrylate 15.8 mass parts
Formula (I) oxime ester compound [n=2, m=3] 5 mass parts
(2) preparation photo-resist
Each component of above-mentioned composition is mixed and be dissolved in the solvent of being formed by 20.2 mass parts 1-Methoxy-2-propyl acetates (PGMEA) and 30.0 mass parts 2 hydroxy propanoic acid ethyl esters the formation fluid composition.
Utilize the rotary coating machine that fluid composition is coated on the glass substrate, dry 2min under 90 ℃, forming thickness is filming of 1.5 μ m; For obtaining filming of above-mentioned thickness, coating procedure can be once to finish also to carry out several times.
Be cooled to room temperature then, enclose mask plate, use high voltage mercury lamp, by the slit of mask plate, expose to smearing in the ultraviolet ray of 365nm, 405nm and 436nm wavelength.
Under 25 ℃ temperature, use 1% NaOH aqueous solution development, with the ultrapure water washing, air-dry again.
Afterwards, baking 30min in back obtains the photo-resist dry film in 220 ℃ baking oven.
(3) performance evaluation
To stability in storage and the exposure sensitivity of painted photopolymerisable compositions, use described coloured composition to estimate at the sticking power that glass substrate forms development, integrity, pattern and the substrate of pattern, evaluation method is the same, the results are summarized in the table 4.
Embodiment 4-2
Use n=2, the formula of m=4 (I) oxime ester compound replaces the oxime ester compound among the embodiment 4-1, other constant, and preparation in an identical manner, and estimate with the identical method of embodiment 4-1.The results are shown in the table 4.
Table 4
Embodiment 5-1
(1) curable compositions No.5-1
Alkali soluble resins 36.7 mass parts
[benzyl methacrylate/methacrylic acid/methyl methacrylate/hydroxyethyl methylacrylate/formula (II) acrylate (mol ratio is 55/5/10/5/10) multipolymer] (Mw:10,000)
Dipentaerythritol acrylate 15.8 mass parts
Formula (I) oxime ester compound [n=2, m=3] 5 mass parts
(2) preparation photo-resist
Each component of above-mentioned composition is mixed and be dissolved in the solvent of being formed by 20.2 mass parts 1-Methoxy-2-propyl acetates (PGMEA) and 30.0 mass parts 2 hydroxy propanoic acid ethyl esters the formation fluid composition.
Utilize the rotary coating machine that fluid composition is coated on the glass substrate, dry 2min under 90 ℃, forming thickness is filming of 1.5 μ m; For obtaining filming of above-mentioned thickness, coating procedure can be once to finish also to carry out several times.
Be cooled to room temperature then, enclose mask plate, use high voltage mercury lamp, by the slit of mask plate, expose to smearing in the ultraviolet ray of 365nm, 405nm and 436nm wavelength.
Under 25 ℃ temperature, use 1% NaOH aqueous solution development, with the ultrapure water washing, air-dry again.
Afterwards, baking 30min in back obtains the photo-resist dry film in 220 ℃ baking oven.
(3) performance evaluation
To stability in storage and the exposure sensitivity of painted photopolymerisable compositions, use described coloured composition to estimate at the sticking power that glass substrate forms development, integrity, pattern and the substrate of pattern, evaluation method is the same, the results are summarized in the table 5.
Embodiment 5-2
Use n=2, the formula of m=4 (I) oxime ester compound replaces the oxime ester compound among the embodiment 5-1, other constant, and preparation in an identical manner, and estimate with the identical method of embodiment 5-1.The results are shown in the table 5.
Table 5
In sum, among the present invention, when formula (I) compound uses as light trigger in described photopolymerization acrylate based composition, when perhaps using photopolymerization acrylate based composition of the present invention, it is good to have development, the resolving power height, the advantage that stability in storage is good and good with substrate attachment power, particularly than the light trigger that uses other kind, the present invention has very high exposure sensitivity, under very low exposure dose, composition system just can well crosslinking curing, and solidification effect is splendid.The smooth zero defect of made film edge, there are not scum silica frost, whole pattern integrity degree good, resist film hardness height, the spectral filter optical clarity height of making, not light leak.Especially make in the colored filter, use photopolymerizable composition of the present invention, can finish the making of BM under very low exposure dose, the BM that makes has precision, flatness and the weather resistance of high opacifying property, excellence.
Claims (20)
1. formula (I) oxime ester compound as the purposes of light trigger, is characterized in that in photopolymerization acrylate based composition: the chemical structure of described formula (I) compound is as follows
Wherein
N=2, m=3 or 4;
Described photopolymerization acrylate based composition comprises
(A) alkali soluble resins of 20-45 mass parts, this resin be benzyl methacrylate, methacrylic acid, with the multipolymer of hydroxyethyl methylacrylate and/or methyl methacrylate, benzyl methacrylate in the multipolymer, methacrylic acid, with the mol ratio of hydroxyethyl methylacrylate and/or methyl methacrylate be 55-70:5-10:10-20, the weight-average molecular weight of multipolymer (Mw) is 5000-25000;
(B) dipentaerythritol acrylate of 10-20 mass parts;
(C) oxime ester compound shown in the formula of 5-7 mass parts (I).
2. purposes according to claim 1, it is characterized in that: in the described photopolymerization acrylate based composition, alkali soluble resins be benzyl methacrylate, methacrylic acid, with the multipolymer of acrylate shown in hydroxyethyl methylacrylate and/or methyl methacrylate and the formula (II)
Benzyl methacrylate in this multipolymer, methacrylic acid, with the mol ratio of acrylate shown in hydroxyethyl methylacrylate and/or methyl methacrylate and the formula (II) be 55-60:5-10:10-15:10, the weight-average molecular weight of multipolymer (Mw) is 5000-25000.
3. purposes according to claim 1 and 2 is characterized in that: the weight-average molecular weight of described multipolymer (Mw) is 10000-15000.
4. purposes according to claim 1 and 2, it is characterized in that: the amount of described alkali soluble resins is the 25-35 mass parts.
5. purposes according to claim 1 and 2, it is characterized in that: the amount of described dipentaerythritol acrylate is the 15-19 mass parts.
6. purposes according to claim 1 and 2, it is characterized in that: the amount of described formula (I) oxime ester compound is 6 mass parts.
7. purposes according to claim 1 and 2 is characterized in that: described photopolymerization acrylate based composition also contain in tinting material, sensitizing agent, the tensio-active agent a kind of, two or more.
8. purposes according to claim 1 and 2, it is characterized in that: described photopolymerization acrylate based composition contains the tinting material of 10-30 mass parts.
9. purposes according to claim 8, it is characterized in that: described photopolymerization acrylate based composition contains the tensio-active agent of 0.01-0.5 mass parts.
10. a photopolymerization acrylate based composition is characterized in that, comprises following component:
(A) alkali soluble resins of 20-45 mass parts, this resin be benzyl methacrylate, methacrylic acid, with the multipolymer of hydroxyethyl methylacrylate and/or methyl methacrylate, benzyl methacrylate in the multipolymer, methacrylic acid, with the mol ratio of hydroxyethyl methylacrylate and/or methyl methacrylate be 55-70:5-10:10-20, the weight-average molecular weight of multipolymer (Mw) is 5000-25000;
(B) dipentaerythritol acrylate of 10-20 mass parts;
(C) oxime ester compound shown in claim 1 Chinese style (I) of 5-7 mass parts.
11. composition according to claim 10 is characterized in that: described alkali soluble resins be benzyl methacrylate, methacrylic acid, with the multipolymer of acrylate shown in hydroxyethyl methylacrylate and/or methyl methacrylate and the formula (II),
Benzyl methacrylate in this multipolymer, methacrylic acid, with the mol ratio of acrylate shown in hydroxyethyl methylacrylate and/or methyl methacrylate and the formula (II) be 55-60:5-10:10-15:10, the weight-average molecular weight of multipolymer (Mw) is 5000-25000.
12. according to claim 10 or 11 described compositions, it is characterized in that: the weight-average molecular weight of described multipolymer (Mw) is 10000-15000.
13. according to claim 10 or 11 described compositions, it is characterized in that: the amount of described alkali soluble resins is the 25-35 mass parts.
14. according to claim 10 or 11 described compositions, it is characterized in that: the amount of described dipentaerythritol acrylate is the 15-19 mass parts.
15. according to claim 10 or 11 described compositions, it is characterized in that: the amount of described formula (I) oxime ester compound is 6 mass parts.
16. according to claim 10 or 11 described compositions, it is characterized in that: described photopolymerization acrylate based composition also contain in tinting material, sensitizing agent, the tensio-active agent a kind of, two or more.
17. according to claim 10 or 11 described compositions, it is characterized in that: described photopolymerization acrylate based composition contains the tinting material of 10-30 mass parts.
18. composition according to claim 17 is characterized in that: described photopolymerization acrylate based composition contains the tensio-active agent of 0.01-0.5 mass parts.
19. a photoresist film is characterized in that, it is to be formed by claim 10 or 11 described photopolymerization esters of acrylic acid preparation of compositions.
20. a colored filter film is characterized in that, it is to be formed by claim 17 or 18 described photopolymerization esters of acrylic acid preparation of compositions.
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| TWI438570B (en) * | 2010-03-11 | 2014-05-21 | Toyo Ink Mfg Co | Photosensitive coloring composition and color filter |
| JP5981159B2 (en) * | 2011-02-22 | 2016-08-31 | 東京応化工業株式会社 | Photosensitive resin composition, and color filter and display device using the same |
| JP6009774B2 (en) * | 2011-02-22 | 2016-10-19 | 東京応化工業株式会社 | Photosensitive resin composition, and color filter and display device using the same |
| JP5793924B2 (en) * | 2011-04-11 | 2015-10-14 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board |
| CN103064254B (en) * | 2011-10-20 | 2017-11-17 | 日立化成株式会社 | Photosensitive polymer combination, photosensitive element, the manufacture method of the forming method of resist pattern and printed circuit board (PCB) |
| CN102492059B (en) * | 2011-11-28 | 2013-04-17 | 常州强力先端电子材料有限公司 | Diphenyl sulfide ketone oxime ester photoinitiator as well as preparation method and application thereof |
| CN103044581B (en) * | 2012-04-05 | 2014-10-29 | 常州强力电子新材料股份有限公司 | Macromolecular photoinitiator as well as preparation method and application thereof |
| US8906594B2 (en) * | 2012-06-15 | 2014-12-09 | Az Electronic Materials (Luxembourg) S.A.R.L. | Negative-working thick film photoresist |
| CN103130919B (en) | 2013-02-08 | 2015-02-25 | 常州强力先端电子材料有限公司 | Carbazole ketone oxime ester high-photosensibility photoinitiator |
| CN103293855B (en) * | 2013-05-20 | 2015-12-23 | 常州强力先端电子材料有限公司 | A kind of esters of acrylic acid Photocurable composition |
| KR102649401B1 (en) * | 2015-10-09 | 2024-03-19 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
| KR20180014982A (en) * | 2016-08-02 | 2018-02-12 | 동우 화인켐 주식회사 | Carbazole Derivatives and Photocurable Composition Comprising the Same |
| KR102442066B1 (en) * | 2016-09-07 | 2022-09-13 | 메르크 파텐트 게엠베하 | Liquid-crystal media and light modulation devices |
| CN106397660B (en) * | 2016-10-28 | 2019-04-12 | 常州强力电子新材料股份有限公司 | Alkali soluble resins, photosensitive polymer combination, colored filter and photoresist comprising it |
| CN109305951A (en) * | 2017-07-26 | 2019-02-05 | 湖北固润科技股份有限公司 | Cumarin oxime ester compound and its preparation and application |
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| CN101508744A (en) * | 2009-03-11 | 2009-08-19 | 常州强力电子新材料有限公司 | Carbazole oxime ester lightlike initiating agent |
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| CN101508744A (en) * | 2009-03-11 | 2009-08-19 | 常州强力电子新材料有限公司 | Carbazole oxime ester lightlike initiating agent |
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