CN102212165A - Resin for alkali-soluble binder and photosensitive resin composition containing same - Google Patents
Resin for alkali-soluble binder and photosensitive resin composition containing same Download PDFInfo
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Abstract
本发明涉及一种具有出色可再溶解性的碱溶性树脂以及包含该树脂的光敏树脂组合物。本发明的碱溶性树脂具有出色的清洗溶剂溶解度，并且可使得狭缝喷嘴污染和基板中异物的产生最小化。
The present invention relates to an alkali-soluble resin having excellent resolubility and a photosensitive resin composition comprising the same. The alkali-soluble resin of the present invention has excellent solubility in cleaning solvents, and can minimize slit nozzle contamination and generation of foreign matter in substrates.
Description
Technical field
The present invention relates to have outstanding cleaning solvent again solvability (resolubility) and can make gap nozzle (slit nozzle) pollute and substrate in the minimized caustic solubility binder resin of production of foreign matters and make the method for this resin, reach a kind of photosensitive resin composition that comprises this resin.
Background technology
Use conventional photosensitive resin composition to prepare the method for colour filter along with the substrate size increase becomes slit rotational method (slit and spin method) or non-rotating method (spinless method) by existing spin-coating method gradually.Yet, in slit rotational method or non-rotating method, use gap nozzle to be coated with.Therefore, in the gap nozzle probably because of photosensitive resin composition pollutes, so need a kind of method of cleaning gap nozzle.
This purging method uses the main solvent in the photosensitive resin composition to clean the nozzle segment of slit.Herein, when resin combination hangs down for the solubleness (being commonly referred to solvability again) of main solvent, exist in the form of this photosensitive resin composition of nozzle segment exsiccant, and in substrate, produce foreign matter, thereby product yield is descended with ridge.
Therefore, in order to address this problem, the dried solvent of photosensitive resin composition solvability again becomes more and more important gradually.
Summary of the invention
Therefore, an object of the present invention is, by provide have remarkably can deliquescent again caustic solubility binder resin synthetic and a kind of photosensitive resin composition that comprises this resin, make in the method steps of preparation colour filter gap nozzle minimize contamination and avoid foreign matter to result from the substrate.
Another object of the present invention provides and a kind ofly is contained in the photosensitive resin composition and has the caustic solubility binder resin that can improve again deliquescent structure.
Another purpose of the present invention provide a kind of have remarkably can deliquescent again caustic solubility binder resin the preparation method.
A further object of the present invention provides a kind of when using the photosensitive resin composition comprise described caustic solubility binder resin to form pattern, has remarkably solvability again and do not produce in the nozzle segment of slit to pollute or the photosensitive resin composition of fault.
A further object of the present invention provides a kind of by the preparation of described photosensitive resin composition, and the colour filter because of can deliquescent again improvement having outstanding light sensitivity, developing property and chemical resistant properties etc.
In the present invention, when preparation is used for the caustic solubility binder resin of photosensitive resin composition, introduce in the reaction intermediate steps by the carboxylic acid cpd that will have long alkyl chain, preparation has the caustic solubility binder resin that alkyl chain is replaced in the structure in the side chain more longways.
When the caustic solubility binder resin that will have this structure is contained in this photosensitive resin composition and when using purging method to clean the nozzle segment of slit after forming the pattern of expectation, the snappiness of this caustic solubility binder resin is owing to the long alkyl chain that is replaced in the side chain improves, thereby the main solvent of resin combination solvability again can be improved, and this resin combination no longer persists in the nozzle segment of slit, has consoluet effect.
Caustic solubility binder resin of the present invention, because when keeping the desired fundamental characteristics of photosensitive resin composition such as light sensitivity, developing property and chemical resistant properties etc., have outstanding cleaning solvent solubleness, therefore can be used for making again the outstanding photosensitive resin composition of solvability.
In addition, when use has improvement again during deliquescent photosensitive resin composition, the defective of the finished product minimizes, and because do not need to implement repeatedly purging method, therefore has the effect that improves operation.
Description of drawings
Fig. 1-3 is the evaluation result of solvability again of the composition of embodiment 1, embodiment 2 and Comparative Examples 1.
Embodiment
Thereby preferably carboxylic acid cpd being added in the reaction intermediate steps makes caustic solubility binder resin of the present invention have long side-chain structure.Therefore, the alkyl chain with at least one carbon number is replaced in the side chain.
Particularly, caustic solubility binder resin of the present invention comprises by the represented repeating unit of following Chemical formula 1-3:
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
In described Chemical formula 1-3, X
1And X
2Be same to each other or different to each other and be selected from hydrogen separately, have the alkyl group and the alkoxy base of 1-3 carbon number; A is that one or more are selected from following group: benzyl oxygen base carbonyl group, phenyl, isobornyl, cyclohexyl and N-phenylmaleimide base; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number; Z is selected from alkylidene group, tetrahydrobenzene, hexanaphthene and the phenyl group with 1-5 carbon number; And n is 1-10.
In addition, the method for preparing caustic solubility binder resin of the present invention may further comprise the steps: a) monomer represented by described Chemical formula 1 of polymerization and the monomer that contains cycloalkyl groups; B) be aggregated in polymkeric substance and the carboxylic acid cpd that described step a) forms; And c) by adding cyclic anhydride acid groups is introduced in the polymkeric substance of described step b) formation.
In addition, photosensitive resin composition of the present invention comprises the caustic solubility binder resin that contains by the repeating unit of described Chemical formula 1-3 expression.
In addition, the invention still further relates to the colour filter for preparing by described photosensitive resin composition with pattern.
Below, the present invention is described in more detail.
Caustic solubility binder resin of the present invention comprises the repeating unit that Chemical formula 1-3 is represented.
[Chemical formula 1]
In described Chemical formula 1, X
1Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; A is that one or more are selected from following group: benzyl oxygen base carbonyl group, phenyl, isobornyl, cyclohexyl and N-phenylmaleimide base;
[Chemical formula 2]
In described Chemical formula 2, X
1And X
2Be same to each other or different to each other, be selected from hydrogen separately, have the alkyl group and the alkoxy base of 1-3 carbon number; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number; And n is 1-10;
[chemical formula 3]
In described chemical formula 3, X
1And X
2Be same to each other or different to each other, be selected from hydrogen separately, have the alkyl group and the alkoxy base of 1-3 carbon number; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number; Z is selected from alkylidene group, tetrahydrobenzene, hexanaphthene and the phenyl group with 1-5 carbon number; And n is 1-10.
The caustic solubility binder resin that comprises the repeating unit of being represented by described Chemical formula 1-3 can be by following chemical formula 4 expressions.
[chemical formula 4]
In described chemical formula 4, a, b and c are the mol ratio of each repeating unit and have the mol ratio of 10-90 separately, and the summation of described mol ratio is 100 mol ratios; X
1And X
2Be same to each other or different to each other and be selected from hydrogen separately, have the alkyl group and the alkoxy base of 1-3 carbon number; A is that one or more are selected from following group: benzyl oxygen base carbonyl group, phenyl, isobornyl, cyclohexyl and N-phenylmaleimide base; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number; Z is selected from alkylidene group, tetrahydrobenzene, hexanaphthene and the phenyl group with 1-5 carbon number; And n is 1-10.
Constitute in the component of caustic solubility binder resin of the present invention, the repeating unit a of described chemical formula 4 can comprise the repeating unit that one or more are represented by Chemical formula 1.
For example, have a certain proportion of benzyl oxygen base carbonyl group, N-phenylmaleimide base and three kinds of groups of phenyl and can be used as the compound of representing by A in the described chemical formula 4.Work as X
1Be hydrogen, Y is a methylene radical, and Z is that tetrahydrobenzene and n are 2.5 o'clock, can obtain following chemical formula 5.
[chemical formula 5]
In described chemical formula 5, a
1-a
3, b and c be the mol ratio of each repeating unit, a
1+ a
2+ a
3=10-90 mol ratio, the b=10-90 mol ratio, the c=10-90 mol ratio, and its summation is 100 mol ratios.
Specific examples with compound of the represented repeating unit of described Chemical formula 1 can comprise that one or more are selected from following compound: vinylbenzene, (methyl) benzyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate.
The represented repeating unit of described Chemical formula 1 can improve with alkali soluble resins in other components consistency and have coating characteristics and chemical resistant properties is improved effect.Therefore, preferably in the caustic solubility binder resin of 100 mol ratios, in the scope of 10-90 mol ratio, select suitable mol ratio according to the needed characteristic of each repeating unit.
In addition, the compound with the represented repeating unit of described Chemical formula 2 carries out polymerization by carboxylic acid cpd that following chemical formula 7 is represented and following polymkeric substance and prepares: described polymkeric substance produces by described Chemical formula 1 represented compound and the chemical formula 6 represented epoxy compounds reactions that contain.That is, the compound with the represented repeating unit of described Chemical formula 2 is a kind of compound by the 6 represented compound reactions that contain epoxy group(ing) that formed by polymer reaction of the represented compound of described chemical formula 7 and described chemical formula are prepared.
[chemical formula 6]
In described chemical formula 6, X
1Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number;
[chemical formula 7]
In described chemical formula 7, X
2Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; And n is 1-10.
The described chemical formula 6 represented compounds that contain cycloalkyl groups are to introduce the caustic solubility binder resin for the carboxylic acid cpd that will have long alkyl chain.Can most preferably use (methyl) glycidyl acrylate.Yet, any comprise can and carboxylic acid cpd---for example chemical formula 7 is represented and second synthesis step that introduce preparation alkali soluble resins of the present invention in those---monomer of the cycloalkyl groups of reaction all can be used as the compound that contains cycloalkyl groups.
Particularly, caustic solubility binder resin of the present invention comprises, from the carboxylic acid cpd in the component that constitutes the represented repeating unit of described Chemical formula 2 with long alkyl chain, and the compound that for example described chemical formula 7 is represented.Its purpose is, by introducing the long alkyl chain in the carboxylic acid cpd, and improves the snappiness (flexibility) of binder resin, thereby improves solvent solubility.
That is, the repeating unit n in the represented compound of described chemical formula 7 is 1-10, preferred 1-5.Even n is 1, but this alkyl chain of entire structure from final polymkeric substance still has extremely long structure after reaction finishes.We can say that this is highly effective, because when to compare this alkyl chain longer with conventional vinylformic acid.Under this alkyl chain was not contained in situation in the represented compound of described chemical formula 7, when using vinylformic acid as in the prior art, it was not enough to improve the snappiness of caustic solubility binder resin.Yet, oversize if the repeating unit n of this compound surpasses 10, though there is the effect that can have improved solubility again, there is the problem of other deterioration in characteristics such as light sensitivity and pattern planeness.
The described chemical formula 7 represented carboxylic acid cpds that satisfy above feature comprise that one or more are selected from following compound: succsinic acid 2-acryloxy ethyl ester, succsinic acid 2-methacryloxy ethyl ester, hexahydrophthalic acid 2-acryloxy ethyl ester, phthalic acid 2-acryloxy ethyl ester and ε-carboxyl polycaprolactone single-acrylate.In these compounds, preferred especially succsinic acid 2-acryloxy ethyl ester or ε-carboxyl polycaprolactone single-acrylate.
In addition, in the present invention, the structure of final binder resin and characteristic are controlled by the time point that adjusting adds the carboxylic acid cpd with long alkyl chain of the represented compound of chemical formula as described 7.In the prior art, owing to the carboxylic acid cpd that has than long alkyl chain adds at the reaction commitment of initial polymer preparation process, so have different structure by the binder resin that appends the reaction acquisition.
In the present invention, the carboxylic acid cpd with long alkyl chain is not contained in the initial polymer preparation process, thereby but its join the polymer chain that makes in the intermediate steps after the polyreaction and can extend more longways, thereby improve the snappiness of this polymer chain.Solvability is improved with snappiness owing to giving polymer chain again, but the realization of this effect is because the alkali-soluble polymer resin has different structure by the time point that control adds the carboxylic acid cpd with long alkyl chain.
In addition, the compound with the represented repeating unit of described Chemical formula 2 has the following advantages: alkali soluble resins is photocrosslinkable property and chemical resistant properties characteristic because of the unsaturated double-bond that is comprised in the chain has.
In addition, the compound with the represented repeating unit of described chemical formula 3 constitutes caustic solubility binder resin of the present invention, prepares by cyclic anhydride is reacted with the compound with the represented repeating unit of described Chemical formula 2.
That is, thus the oh group that cyclic anhydride is added in the represented compound of described Chemical formula 2 adds acid groups.Described cyclic anhydride is selected from following compound for one or more: succinyl oxide, adipic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, trimellitic acid 1,2-anhydride and cis-5-norbornylene-Nei-2,3-dicarboxylic anhydride.In these compounds, preferably use succinyl oxide or 3,4,5, the 6-Tetra Hydro Phthalic Anhydride.By the acid groups that described chemical formula 3 represented repeating units form, alkali soluble resins has developing property.
A kind of concrete grammar for preparing caustic solubility binder resin of the present invention is described below.
This method may further comprise the steps: a) compound that contains the monomer of cycloalkyl groups and comprise the repeating unit of being represented by described Chemical formula 1 by polymerization produces a kind of polymkeric substance; B) be aggregated in polymkeric substance and the carboxylic acid cpd that described step a) forms; And c) by adding cyclic anhydride acid groups is introduced in the polymkeric substance of described step b) formation.
The represented monomer of Chemical formula 1 can be one or more and is selected from following compound in the described step a): vinylbenzene, (methyl) benzyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate.
In addition, the monomer that contains cycloalkyl groups described in the described step a) can be any contain can with the monomer of the epoxy group(ing) of carboxylic acid cpd reaction, and the monomer of its following chemical formula 6 expressions of can serving as reasons
[chemical formula 6]
In described chemical formula 6, X
1Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; And Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number.
The described chemical formula 6 represented compounds that contain cycloalkyl groups are to introduce described caustic solubility binder resin for the carboxylic acid cpd that will have long alkyl chain.Most preferably can use (methyl) glycidyl acrylate.Can use any comprise can and carboxylic acid cpd---for example chemical formula 7 is represented and second synthesis step that add preparation alkali soluble resins of the present invention in those---monomer of the cycloalkyl groups of reaction.
In addition, described carboxylic acid cpd have long alkyl chain and its can be by following chemical formula 7 expressions.
[chemical formula 7]
In described chemical formula 7, X
2Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; And n is 1-10.
Described chemical formula 7 represented carboxylic acid cpds are selected from following compound for one or more: succsinic acid 2-acryloxy ethyl ester, succsinic acid 2-methacryloxy ethyl ester, hexahydrophthalic acid 2-acryloxy ethyl ester, phthalic acid 2-acryloxy ethyl ester and ε-carboxyl polycaprolactone single-acrylate.In these compounds, preferred especially succsinic acid 2-acryloxy ethyl ester or ε-carboxyl polycaprolactone single-acrylate.
Therefore, the carboxylic acid cpd of the represented monomer of Chemical formula 2 by making described chemical formula 7 expressions and described chemical formula 6 represented epoxy compoundss react and obtain.This alkali soluble resins has photocrosslinkable property and chemical resistant properties characteristic by the unsaturated double-bond in the monomer.
In addition, the represented monomer of chemical formula 3 is by making cyclic anhydride---for example the succinyl oxide of proper ratio or Tetra Hydro Phthalic Anhydride---, and the monomer reaction represented with Chemical formula 2 obtains.At this moment, alkali soluble resins has developing property by formed acid groups.
Alkali soluble resins of the present invention can be by using any preparation the in radical polymerization, cationoid polymerisation, anionoid polymerization and the condensation polymerization.Yet, consider the easy degree and the economy of preparation, preferably use radical polymerization.
When alkali soluble resins of the present invention uses radical polymerization to prepare, can use 2,2 '-Diisopropyl azodicarboxylate (AIBN), 2,2 '-azo two-(2, the 4-methyl pentane nitrile) or benzoyl peroxide etc. are as radical polymerization initiator.
In addition, the polymerization hours is preferably 1-48 hour, and polymerization temperature is preferably 50-150 ℃.
Use with preferred its acid number of the alkali soluble resins of upper type preparation and be 30-200KOHmg/g.When acid number during, produce hardly and develop less than 30KOH mg/g.When acid number during, there is cooked problem greater than 200KOH mg/g.Preferred alkali soluble resins of the present invention has 1,000-200, the weight-average molecular weight of 000g/mol.When weight-average molecular weight less than 1, during 000g/mol, react hardly.When weight-average molecular weight greater than 200, during 000g/mol, can not form fine pattern well.
Photosensitive resin composition of the present invention can provide and comprise a kind of alkali soluble resins of the present invention, a kind of photosensitive resin composition with the aggretion type compound of ethylene type unsaturated link(age), a kind of photoinitiator and a kind of solvent.
Described specific examples with aggretion type compound of ethylene type unsaturated link(age) can comprise following material, but is not limited thereto: tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, polyethyleneglycol (methyl) acrylate and polypropylene glycol list (methyl) acrylate.
Described photoinitiator can be one or more and is selected from following compound, but be not limited thereto: triaizine compounds, for example 2,4-trichloromethyl-(4 '-p-methoxy-phenyl)-6-triazine, 2,4-trichloromethyl-(4 '-methoxyl-styrene)-6-triazine and 2, the 4-trichloromethyl-(fipronil)-the 6-triazine; Based on the compound of methyl phenyl ketone, comprise 1-hydroxycyclohexylphenylketone and 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl) propyl group ketone; And, comprise benzophenone and 2,4,6-trimethylammonium aminobenzophenone based on the compound of benzophenone.
In addition, this solvent can be one or more and is selected from following compound, but is not limited thereto: methyl ethyl ketone, propylene glycol Anaesthetie Ether, propylene glycol monomethyl ether, pimelinketone, 2-heptanone, isobutyl acetate, isopropyl butyrate and acetate 3-methoxyl group butyl ester.
In the gross weight of photosensitive resin composition, the amount of alkali soluble resins can be 1-20wt%, described amount with aggretion type compound of ethylene type unsaturated link(age) can be 1-10wt%, and the amount of described photoinitiator can be 0.1-5wt%, and the amount of described solvent can be 65-95wt%.
When for photosensitizers that is used for the minus colour filter and the situation that is used for the photosensitizers of black matrix, also can further add tinting material.At this moment, can use one or more to be selected from following compound as tinting material: black pigment, red pigment, yellow ultramarine, blue pigments, violet pigment.Black pigment comprises that carbon black and titanium are black.Coloured pigment comprises phthalocyanine green, phthalocyanine blue, perylene indigo plant, thunder Nore Huang (linol yellow) difficult to understand and Victoria's ethereal blue.In addition, described tinting material can be contained in wherein with the amount of 1-20wt% in total resin composition.
Below with reference to embodiments of the invention the present invention is described in more detail.Following examples are for the purpose of illustration only explanation the present invention, and the present invention is not limited to following examples.It will be apparent to those skilled in the art that in using this embodiment used concrete material with and the situation of equivalent under, all can reach the effect identical with the present invention.
Synthetic embodiment 1
32g benzyl methacrylate, 5g N-phenylmaleimide, 4g vinylbenzene, 36g glycidyl methacrylate and 2.5g dodecyl mercaptans are mixed with the 300g propylene glycol methyl ether acetate, and under nitrogen atmosphere, the temperature of reactor is raised to 65 ℃.When the temperature of this mixture reached 65 ℃, input 4g thermal polymerization AIBN also stirred 12 hours.After 12 hours, obtain a kind of polymeric resin adhesive solution, its polymerization yield rate is 98%, molecular weight is 10,000g/mol and solid account for 20%.
To stir 30 minutes down in 0.5g bromination tetrabutylammonium and the 0.1g thermal polymerization inhibitor MEHQ input polymers soln and at 80 ℃.Next, drop into 40g succsinic acid 2-acryloxy ethyl ester and stirred 24 hours down at 120 ℃.After 24 hours, obtain a kind of polymeric resin adhesive solution, its molecular weight is 17,000g/mol and solid account for 30%.
As final synthesis step, the 20g Tetra Hydro Phthalic Anhydride is dropped in this polymers soln and at 90 ℃ to descend to stir 15 hours.Thereby, obtain the alkali soluble resins solution (1) of expectation, its molecular weight is 25,000g/mol, acid number be 100 and solid account for 35%.
Synthetic embodiment 2
32g benzyl methacrylate, 5g N-phenylmaleimide, 4g vinylbenzene, 36g glycidyl methacrylate and 2.5g dodecyl mercaptans are mixed with the 300g propylene glycol methyl ether acetate, and under nitrogen atmosphere, the temperature of reactor is raised to 65 ℃.When the temperature of this mixture reached 65 ℃, input 4g thermal polymerization AIBN also stirred 12 hours.After 12 hours, obtain a kind of polymeric resin adhesive solution, its polymerization yield rate is 98%, molecular weight is 10,000g/mol and solid account for 20%.
0.5g bromination tetrabutylammonium and 0.1g thermal polymerization inhibitor MEHQ are dropped in this polymers soln and at 80 ℃ to descend to stir 30 minutes.Next, drop into 65g ε-carboxyl polycaprolactone single-acrylate and stirred 24 hours down at 120 ℃.After 24 hours, obtain a kind of polymeric resin adhesive solution, its molecular weight is 19,000g/mol and solid account for 32%.
As final synthesis step, the 28g Tetra Hydro Phthalic Anhydride is dropped in this polymers soln and at 90 ℃ to descend to stir 15 hours.Thereby, obtain the alkali soluble resins solution (2) of expectation, its molecular weight is 27,000g/mol, acid number be 100 and solid account for 37%.
The synthetic embodiment 1 of contrast
32g benzyl methacrylate, 5g N-phenylmaleimide, 4g vinylbenzene, 36g glycidyl methacrylate and 2.5g dodecyl mercaptans are mixed with the 300g propylene glycol methyl ether acetate, and under nitrogen atmosphere, the temperature of reactor is raised to 65 ℃.When the temperature of this mixture reached 65 ℃, input 4g thermal polymerization AIBN also stirred 12 hours.After 12 hours, obtain a kind of polymeric resin adhesive solution, its polymerization yield rate is 98%, molecular weight is 10,000g/mol and solid account for 20%.
To stir 30 minutes down in 0.5g bromination tetrabutylammonium and the 0.1g thermal polymerization inhibitor MEHQ input polymers soln and at 80 ℃.Next, drop into 20g vinylformic acid and stirred 24 hours down at 120 ℃.After 24 hours, obtain a kind of polymeric resin adhesive solution, its molecular weight is 15,000g/mol and solid account for 28%.
As final synthesis step, the 15g Tetra Hydro Phthalic Anhydride is dropped in this polymers soln and at 90 ℃ to descend to stir 15 hours.Thereby, obtain the alkali soluble resins solution (3) of expectation, its molecular weight is 23,000g/mol, acid number be 100 and solid account for 33%.
Embodiment 1
Formed alkali soluble resins (1) among the described synthetic embodiment 1 of 5g is mixed with 30g veridian dispersion, 1.5g photoinitiator I-369,0.5g photoinitiator CGI-242,3.5g dipentaerythritol acrylate, 40g propylene glycol methyl ether acetate and 0.1g 2-methyl allyl acyloxypropyl trimethoxysilane (being additive) and stir about 1 hour, thereby prepare a kind of photosensitive resin composition.
Embodiment 2
Except using 5g formed alkali soluble resins (2) in described synthetic embodiment 2 to come the alkali soluble resins (1) in the alternate embodiment 1, mix stir about 1 hour and prepare a kind of photosensitive resin composition with the composition identical with embodiment 1.
Comparative Examples 1
Except using 5g formed alkali soluble resins (3) in the synthetic embodiment 1 of described contrast to come the alkali soluble resins (1) in the alternate embodiment 1, mix stir about 1 hour and prepare a kind of photosensitive resin composition with the composition identical with embodiment 1.
＜experimental example 1-developing property, chemical resistant properties and light sensitivity test 〉
Each prepared in embodiment 1, embodiment 2 and the Comparative Examples 1 photosensitive resin composition solution is spun on the glass substrate, handled 100 seconds at 90 ℃ of following preliminary dryings then, thereby preparation has the thick conductive film of 1.5 μ m.When keeping the exposing clearance of 200 μ m, use high voltage mercury lamp this film with 60mJ/cm with photomask
2Energy exposure after, used 0.04% KOH aqueous solution development substrate down 60 seconds at 25 ℃.After development step, clean with drying and after in 230 ℃ convection oven and dried by the fire 25 minutes.Next, monitoring pattern state (pattern state).
Use opticmicroscope that described each pattern state is monitored.Developing property, light sensitivity and the anti-nmp solution chemical of pattern are measured and as shown in table 1 below comparing.
The process that the substrate of developing property by monitoring exposure developed at 0.04% the KOH aqueous solution through 60 seconds is measured.Developing property arrives this substrate edge part based on developing with speed how soon and judges.When obviously developing, determine that it is qualified.
Light sensitivity obtains by measuring remaining minimum pattern size with described each the final pattern state of opticmicroscope monitoring.The more little light sensitivity of remaining minimum pattern size is then good.
In addition, chemical resistant properties is monitored the appearance change of filming and is recorded impregnated in a kind of nmp solution under 45 ℃ by each substrate that will obtain in described embodiment and the Comparative Examples after 30 minutes.When outward appearance does not change, be labeled as good (zero).Have when changing a little when detecting outward appearance, be labeled as general (△).When outward appearance is peeled off or during solvent color deterioration, is labeled as defective (*).
＜experimental example 2-solvability test again 〉
Each prepared in embodiment 1, embodiment 2 and the Comparative Examples 1 photosensitive resin composition solution is spun on respectively on the glass substrate, handled 300 seconds at 80 ℃ of following preliminary dryings then.Next, this substrate flooding 5 minutes in PGMEA solution under 25 ℃, is taken out from this PGMEA solution then.Afterwards, record solvability again by the monitoring solution state.Can deliquescent again evaluation result list in the table 1.When the conductive film of handling through preliminary drying obviously melts in PGMEA solution, be labeled as good (zero).When the conductive film of handling through preliminary drying only partial melting be labeled as general (△) in PGMEA solution and when some precipitations occurring.When the conductive film of handling through preliminary drying does not melt in PGMEA solution or many precipitations occur, be labeled as defective (*).In addition, solution state is listed among Fig. 1 to 3.
[table 1]
By above-mentioned table 1 as can be known, alkali soluble resins polymkeric substance of the present invention has developing property, chemical resistant properties and the light sensitivity with existing alkali soluble resins par, but, can improve the solvability again of photosensitive resin composition effectively because it has outstanding dissolution with solvents degree.
Particularly, in Fig. 1 to 3, the synthetic embodiment 1 (Fig. 3) of contrast is the long caustic solubility binder resin of alkyl chain of the carboxylic acid that comprised in a kind of its structure, compare with the caustic solubility binder resin (Fig. 1 and 2) that contains the carboxylic acid with long alkyl chain among the present invention, resin does not have good snappiness.Therefore, it is low to demonstrate the solvability again of resin.
Claims (20)
1. caustic solubility binder resin, wherein carboxylic acid cpd is added in the reaction intermediate steps, and the alkyl chain with at least one carbon number is replaced in the side chain.
2. caustic solubility binder resin comprises by the represented repeating unit of following Chemical formula 1-3:
[Chemical formula 1]
In described Chemical formula 1, X
1Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; A is that one or more are selected from following group: benzyl oxygen base carbonyl group, phenyl, isobornyl, cyclohexyl and N-phenylmaleimide base;
[Chemical formula 2]
In described Chemical formula 2, X
1And X
2Be same to each other or different to each other, be selected from hydrogen separately, have the alkyl group and the alkoxy base of 1-3 carbon number; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number; And n is 1-10;
[chemical formula 3]
In described chemical formula 3, X
1And X
2Be same to each other or different to each other, be selected from hydrogen separately, have the alkyl group and the alkoxy base of 1-3 carbon number; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number; Z is selected from alkylidene group, tetrahydrobenzene, hexanaphthene and the phenyl group with 1-5 carbon number; And n is 1-10.
3. the caustic solubility binder resin of claim 2, wherein said caustic solubility binder resin are by following chemical formula 4 expressions:
[chemical formula 4]
In described chemical formula 4, a, b and c are the mol ratio of each repeating unit, are respectively the mol ratio of 10-90, and the summation of their mol ratio is 100 mol ratios; X
1And X
2Be same to each other or different to each other and be selected from hydrogen separately, have the alkyl group and the alkoxy base of 1-3 carbon number; A is that one or more are selected from following group: benzyl oxygen base carbonyl group, phenyl, isobornyl, cyclohexyl and N-phenylmaleimide base; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number; Z is selected from alkylidene group, tetrahydrobenzene, hexanaphthene and the phenyl group with 1-5 carbon number; And n is 1-10.
4. the caustic solubility binder resin of claim 2 also comprises the repeating unit that one or more are represented by Chemical formula 1.
5. the caustic solubility binder resin of claim 4, wherein said caustic solubility binder resin are by following chemical formula 5 expressions:
[chemical formula 5]
In described chemical formula 5, a
1-a
3, b and c be the mol ratio of each repeating unit, a
1+ a
2+ a
3=10-90 mol ratio, the b=10-90 mol ratio, the c=10-90 mol ratio, and its summation is 100 mol ratios.
6. the caustic solubility binder resin of claim 2, the compound that wherein has the represented repeating unit of described Chemical formula 1 is selected from following compound for one or more: vinylbenzene, (methyl) benzyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate and (methyl) isobornyl acrylate.
7. the caustic solubility binder resin of claim 2, the compound that wherein has a represented repeating unit of described Chemical formula 2 carries out polymerization by carboxylic acid cpd that following chemical formula 7 is represented and following polymkeric substance and obtains: described polymkeric substance produces by described Chemical formula 1 represented compound and the following chemical formula 6 represented polyreactions that contain epoxy compounds
[chemical formula 6]
In described chemical formula 6, X
1Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number;
[chemical formula 7]
In described chemical formula 7, X
2Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; And n is 1-10.
8. the caustic solubility binder resin of claim 2, the compound that wherein has the represented repeating unit of described chemical formula 3 obtains by making cyclic anhydride carry out polymerization with the compound with the represented repeating unit of described Chemical formula 2.
9. the caustic solubility binder resin of claim 8, wherein said cyclic anhydride is selected from following compound for one or more: succinyl oxide, adipic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, trimellitic acid 1,2-anhydride and cis-5-norbornylene-Nei-2, the 3-dicarboxylic anhydride.
10. the caustic solubility binder resin of claim 2, wherein said caustic solubility binder resin has the acid number of 30-200KOH mg/g and has 1,000-200, the weight-average molecular weight of 000g/mol (Mw).
11. the preparation method of a caustic solubility binder resin may further comprise the steps:
A) compound that contains the monomer of cycloalkyl groups and comprise the repeating unit of being represented by described Chemical formula 1 by polymerization obtains a kind of polymkeric substance;
B) polymerization of carboxylic acid compound and the polymkeric substance that forms in described step a); And
C) by adding cyclic anhydride acid groups is added in the polymkeric substance of described step b) formation.
12. the method for claim 11, the monomer that contains cycloalkyl groups in the wherein said step a) is represented by following chemical formula 6:
[chemical formula 6]
In chemical formula 6, X
1Be selected from hydrogen, have the alkyl group of 1-3 carbon number; And Y is selected from alkylidene group, oxidation ethylidene and the oxypropylene with 1-5 carbon number.
13. the method for claim 11, the carboxylic acid cpd compound of following chemical formula 7 expressions of serving as reasons in the wherein said step b):
[chemical formula 7]
In described chemical formula 7, X
2Be selected from hydrogen, have the alkyl group and the alkoxy base of 1-3 carbon number; And n is 1-10.
14. the method for claim 13, wherein, described chemical formula 7 represented compounds are selected from following compound for one or more: succsinic acid 2-acryloxy ethyl ester, succsinic acid 2-methacryloxy ethyl ester, hexahydrophthalic acid 2-acryloxy ethyl ester, phthalic acid 2-acryloxy ethyl ester and ε-carboxyl polycaprolactone single-acrylate.
15. the method for claim 11, wherein, cyclic anhydride in the described step c) is selected from following compound for one or more: succinyl oxide, adipic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, trimellitic acid 1,2-anhydride and cis-5-norbornylene-Nei-2, the 3-dicarboxylic anhydride.
16. the method for claim 11, wherein, the caustic solubility binder resin prepares by radical polymerization.
17. the method for claim 11 was carried out 1-48 hour under the wherein said 50-150 of being aggregated in ℃.
18. photosensitive resin composition that comprises the caustic solubility binder resin of claim 1 or 2.
19. the photosensitive resin composition of claim 18, wherein, described photosensitive resin composition also comprises aggretion type compound, photoinitiator and the solvent with ethylene type unsaturated link(age).
20. the photosensitive resin composition of claim 19, wherein, described photosensitive resin composition comprises the alkali soluble resins of 1-20wt%, the aggretion type compound with ethylene type unsaturated link(age) of 1-10wt%, the photoinitiator of 0.1-5wt% and the solvent of 65-95wt%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100033743A KR101048328B1 (en) | 2010-04-13 | 2010-04-13 | Alkali-soluble binder resin excellent in re-dissolution property and photosensitive resin composition containing the same |
| KR10-2010-0033743 | 2010-04-13 |
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| Publication Number | Publication Date |
|---|---|
| CN102212165A true CN102212165A (en) | 2011-10-12 |
| CN102212165B CN102212165B (en) | 2015-04-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110092982.8A Active CN102212165B (en) | 2010-04-13 | 2011-04-13 | Resin for alkali-soluble binder and photosensitive resin composition containing same |
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| Country | Link |
|---|---|
| JP (1) | JP5510933B2 (en) |
| KR (1) | KR101048328B1 (en) |
| CN (1) | CN102212165B (en) |
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| TWI895274B (en) * | 2019-07-30 | 2025-09-01 | 日商富士軟片股份有限公司 | Colored resin composition, film, color filter, solid-state imaging element, and image display device |
| JP7673404B2 (en) * | 2019-12-26 | 2025-05-09 | 東亞合成株式会社 | Active energy ray curable composition and method for producing same |
| TW202534089A (en) * | 2024-02-28 | 2025-09-01 | 日商太陽控股股份有限公司 | Curable resin composition, dry film, cured product, and printed wiring board |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297954A (en) * | 1999-12-01 | 2001-06-06 | 大东树脂化学股份有限公司 | Polycarboxylic acid resin containing unsaturated double bond and its preparation and use |
| CN101573663A (en) * | 2006-12-26 | 2009-11-04 | Lg化学株式会社 | Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same |
| CN101578303A (en) * | 2007-01-15 | 2009-11-11 | Lg化学株式会社 | New polymer resin compounds and photoresist composition including new polymer resin compounds |
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| JP3006253B2 (en) * | 1992-01-29 | 2000-02-07 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, and method for producing plating resist |
| JPH09185166A (en) * | 1995-12-28 | 1997-07-15 | Taiyo Ink Mfg Ltd | Photosensitive prepolymer and photosetting and thermosetting soldering resist ink composition using the same |
| JP3634141B2 (en) * | 1998-03-02 | 2005-03-30 | 太陽インキ製造株式会社 | Photosensitive composition and fired product pattern obtained using the same |
| JP2008088394A (en) * | 2006-09-07 | 2008-04-17 | Showa Highpolymer Co Ltd | Alkali-developable photosensitive resin and photosensitive resin composition comprising the same |
| JP2008189792A (en) | 2007-02-05 | 2008-08-21 | Fujifilm Corp | Pigment dispersion composition, curable composition, color filter and method for producing the same |
| CN101663335B (en) * | 2007-05-11 | 2011-12-14 | 大赛璐化学工业株式会社 | Light and/or heat curable copolymer, curable resin composition and cured product |
| JP5241283B2 (en) | 2008-03-24 | 2013-07-17 | 富士フイルム株式会社 | Pigment dispersion composition, photocurable composition, color filter, liquid crystal display device, and solid-state imaging device |
| JP2009256572A (en) | 2008-03-17 | 2009-11-05 | Fujifilm Corp | Pigment dispersion composition, colored photosensitive composition, color filter, liquid crystal display element, and solid imaging device |
-
2010
- 2010-04-13 KR KR1020100033743A patent/KR101048328B1/en active Active
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2011
- 2011-04-12 JP JP2011088322A patent/JP5510933B2/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297954A (en) * | 1999-12-01 | 2001-06-06 | 大东树脂化学股份有限公司 | Polycarboxylic acid resin containing unsaturated double bond and its preparation and use |
| CN101573663A (en) * | 2006-12-26 | 2009-11-04 | Lg化学株式会社 | Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same |
| CN101578303A (en) * | 2007-01-15 | 2009-11-11 | Lg化学株式会社 | New polymer resin compounds and photoresist composition including new polymer resin compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5510933B2 (en) | 2014-06-04 |
| KR101048328B1 (en) | 2011-07-14 |
| CN102212165B (en) | 2015-04-15 |
| TWI450034B (en) | 2014-08-21 |
| TW201135364A (en) | 2011-10-16 |
| JP2011219759A (en) | 2011-11-04 |
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