CN101498894A - Photosensitive resin composition, optical spacer, protecting film, coloring pattern, display device and substrate thereof - Google Patents
Photosensitive resin composition, optical spacer, protecting film, coloring pattern, display device and substrate thereof Download PDFInfo
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- CN101498894A CN101498894A CNA2009100096183A CN200910009618A CN101498894A CN 101498894 A CN101498894 A CN 101498894A CN A2009100096183 A CNA2009100096183 A CN A2009100096183A CN 200910009618 A CN200910009618 A CN 200910009618A CN 101498894 A CN101498894 A CN 101498894A
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Abstract
The invention provides a light-sensitive resin composition containing resin, polymeric compound and initiator of polymerization. The dipole moment of the polymeric compound is preferably over 3.50 Debye. In addition, the resin is preferably having 5 element or 6 element annular structure component represented by C=0 and/or component represented by P=0, acidic radical and ethylenic unstructured key. The invention also provides a display device substrate making the light-sensitive resin composition form light separating objects, making the light-sensitive resin composition form protecting film and making the light-sensitive resin composition form colored patterns and preparing one of the items. The invention also provides a display device used for the display device substrate. The invention further provides a forming method for the light separating objects.
Description
Technical field
The present invention relates to photosensitive polymer combination, light spacer (photo spacer) and forming method thereof, diaphragm, colored pattern, base board for display device and display device.
Background technology
Liquid crystal indicator is widely used in showing in the display device of high resolution image.
Liquid crystal indicator usually between a pair of substrate (below be also referred to as " base board for display device ") configuration can carry out the liquid crystal layer that image shows by the orientation of regulation.Keep equably this substrate at interval, be that the thickness of liquid crystal layer is one of key element of decision image quality., the thickness with liquid crystal layer sets sept for keeping certain.Thickness between this substrate is commonly called " element thickness ".The thickness of the described liquid crystal layer of element thickness ordinary representation in other words, is illustrated in 2 interelectrode distances that applied electric field in the liquid crystal of viewing area.
Base board for display device (for example filter substrate, active-matrix substrate etc.) is following formation, promptly is formed with the formation of structures such as colored pattern or diaphragm on substrate.In these structures, as the formation method of colored pattern or diaphragm, the usability photosensitive resin composition becomes main flow by the method that photoetching process forms.
In addition, formed sept by scattering pearl (beads), but in recent years, also the usability photosensitive resin composition forms sept by photoetching process, therefore, can obtain the high sept of positional precision in the past.The sept that uses such photosensitive polymer combination to form is called as light spacer.
Summary of the invention
Up to now photosensitive polymer combination various researchs have been carried out.For example, the photosensitive polymer combination (for example opening 2007-No. 86565 referring to the spy) that the multipolymer that uses ethylenic unsaturated carboxylic acid etc. and ethylenically unsaturated compounds and specific Photoepolymerizationinitiater initiater obtain is disclosed.A kind of curable resin that is made of the multipolymer of fatty family cyclic hydrocarbon group is also disclosed, the multipolymer of described fatty family cyclic hydrocarbon group has following molecular structure, that is: will have the aliphatics cyclic hydrocarbon group of ad hoc structure structural unit, have the structural unit of acidic functionality and have the molecular structure (for example, opening the 2002-293837 communique) that the structural unit of free-radical polymerised base links referring to the spy.
In the above-mentioned existing photosensitive polymer combination,, use dipentaerythritol acrylate or dipentaerythritol five acrylate etc. to have the monomer of ethylenic unsaturated link usually as photopolymerization monomer.
But, use existing photosensitive polymer combination on substrate, to form patterning body (for example light spacer, colored pattern etc.Following word " patterning body " also comprises above-mentioned example) or during diaphragm, if only with exposure, then the polymerizing curable of photosensitive polymer combination is insufficient, sometimes in exposure, need to implement the heat treated of high temperature after developing.
The present invention obtains in view of the above fact, and following proposal is provided.
＜1〉a kind of photosensitive polymer combination, it contains resin, dipole moment is above polymerizable compound and Photoepolymerizationinitiater initiaters of 3.50 debye (Debye).
＜2〉according to＜1〉described photosensitive polymer combination, it is characterized in that, described polymerizable compound has the ring texture and the ethylenic unsaturated double-bond of 5 yuan or 6 yuan, and the ring texture of described 5 yuan or 6 yuan has bond sites that contains C=O and/or the bond sites that contains P=O.
＜3〉according to＜1〉described photosensitive polymer combination, it is characterized in that described resin has branching and/or alicyclic structure, acidic groups and ethylenic unsaturated link at side chain.
＜4〉according to＜1〉described photosensitive polymer combination, it is characterized in that, described polymerizable compound has the ring texture and the ethylenic unsaturated double-bond of 5 yuan or 6 yuan, the ring texture of described 5 yuan or 6 yuan has bond sites that contains C=O and/or the bond sites that contains P=O, and described resin has branching and/or alicyclic structure, acidic groups and ethylenic unsaturated link on side chain.
＜5〉a kind of photosensitive polymer combination, it contains resin, polymerizable compound and Photoepolymerizationinitiater initiater, wherein, described resin is the resin that has ring texture, acidic groups and the ethylenic unsaturated link of 5 yuan of the position that comprises the position represented by C=O and/or represented by P=O or 6 yuan at side chain.
＜6〉according to＜4〉described photosensitive polymer combination, it is characterized in that described resin also has branching and/or alicyclic structure on side chain.
＜7〉according to＜4〉or＜5〉described photosensitive polymer combination, it is characterized in that at least a kind of described polymerizable compound has 5 yuan or 6 yuan the ring texture and the ethylenic unsaturated double-bond at the position that comprises the position represented by C=O and/or represented by P=O.
＜8〉according to＜5〉described photosensitive polymer combination, it is characterized in that, described resin also has branching and/or alicyclic structure on side chain, at least a kind of described polymerizable compound has 5 yuan or 6 yuan the ring texture and the ethylenic unsaturated double-bond at the position that comprises the position represented by C=O and/or represented by P=O.
＜9〉a kind of light spacer, it is to use＜1～＜8 in each described photosensitive polymer combination form.
＜10〉a kind of formation method of light spacer, it comprises following operation (1)～(3) at least:
(1) on substrate, form＜1 〉～＜8 in the operation of tunicle of each described photosensitive polymer combination;
(2) operation that at least a portion of described tunicle is exposed;
(3) described after will exposing by the operation of film development.
＜11〉the formation method of basis＜10〉described light spacer is characterized in that, described formation method comprises that also the maximum temperature of this heating is more than 40 ℃ and below 145 ℃ with the operation of the described tunicle heating after developing.
＜12〉a kind of diaphragm, it is to use＜1～＜8 in each described photosensitive polymer combination form.
＜13〉a kind of colored pattern, it is to use＜1～＜8 in each described photosensitive polymer combination form.
＜14〉a kind of base board for display device, it possesses＜9 described in light spacer,＜12 described in diaphragm and＜13 described in colored pattern at least a.
＜15〉a kind of display device, it possesses＜and 14〉described base board for display device.
According to＜1 〉, can provide when exposure the polymerization-curable excellence, can or not have the photosensitive polymer combination that forms patterning body and diaphragm under the heat treated in low heating-up temperature.
According to＜2 〉, the photosensitive polymer combination that can provide the polymerization-curable in when exposure further to improve.
According to＜3 〉, following possible photosensitive polymer combination can be provided, its have under development, high polymerisation reactivity, excellent liquid keeping quality, the dry film through the time shape of patterning body of keeping quality, formation and thickness controlled, and the patterning body that forms when being subjected to external force compressive modulus of elasticity and from the elastic recovery height of compression deformation.
According to＜4 〉, following photosensitive polymer combination can be provided, it has the controlled of the shape of the patterning body of De Jing Time keeping quality, formation under the further development that has improved, high polymerisation reactivity, excellent liquid keeping quality, the dry film and thickness, and the compressive modulus of elasticity of the patterning body that forms and from the elastic recovery height of compression deformation.
According to＜5 〉, can provide when exposure the curable excellence, can or not have the photosensitive polymer combination that forms patterning body and diaphragm under the heat treated in low heating-up temperature.
According to＜6 〉, can provide formation the patterning body compressive modulus of elasticity and from the high photosensitive polymer combination of the elastic recovery of compression deformation.
According to＜7 〉, the photosensitive polymer combination that can provide the curable in when exposure further to improve.
According to＜8 〉, can provide the compressive modulus of elasticity of the patterning body that the curable in when exposure further improves and form and from the high photosensitive polymer combination of the elastic recovery of compression deformation.
According to＜9 〉, even in low heating-up temperature or do not have in the situation about forming under the heat treated, also can provide the light spacer of the homogeneity and the high homogeneity excellence of cross sectional shape.
According to＜10 〉, even in low heating-up temperature or do not have in the situation about forming under the heat treated, also can provide the manufacture method of the light spacer of the homogeneity of cross sectional shape and high homogeneity excellence.
According to＜11 〉, the manufacture method of light spacer of the deterioration of the deterioration of the light spacer that more effectively inhibition will form or patterning body (colored pattern etc.) that has formed or diaphragm can be provided.
According to＜12 〉, even in low heating-up temperature or do not have in the situation about forming under the heat treated, also can provide the diaphragm of film thickness uniformity excellence.
According to＜13 〉, even in low heating-up temperature or do not have in the situation about forming under the heat treated, also can provide the colored pattern of the homogeneity and the film thickness uniformity excellence of cross sectional shape.
According to＜14 〉, can be provided at and can suppress to show uneven base board for display device when being used for display device.
In addition, according to＜15 〉, can provide and suppress to show uneven display device.
Embodiment
Below, describe photosensitive polymer combination of the present invention in detail, and then, also to using light spacer that this photosensitive polymer combination obtains and forming method thereof, diaphragm, colored pattern, base board for display device and display device to describe.
" photosensitive polymer combination "
Photosensitive polymer combination of the present invention contains resin, dipole moment is above polymerizable compound and Photoepolymerizationinitiater initiaters of 3.50 debye.
Usually, when the usability photosensitive resin composition forms patterning body or diaphragm on substrate, if only with exposure, then solidify insufficient, so in order further to be cured, need implement the heat treated of high temperature in exposure, the back of developing.
But, by the heat treated of this high temperature, patterning body that will form sometimes or diaphragm generation deterioration or be formed on patterning body or diaphragm generation deterioration on the substrate.For example, when on having the filter substrate of colored pattern, forming light spacer, the light spacer generation deterioration that will form sometimes or be formed on colored pattern generation deterioration on the substrate.
So, by photosensitive polymer combination being set at the formation of the invention described above, can improve the curable in when exposure, in low heating-up temperature or do not have under the heat treated and also can form patterning body and diaphragm.Therefore, can effectively suppress the patterning body that will form or deterioration and the patterning body that on substrate, has formed or the deterioration of diaphragm of diaphragm.
Below, polymerizable compound contained in the photosensitive polymer combination of the present invention, resin, Photoepolymerizationinitiater initiater and other composition are described.
＜polymerizable compound 〉
In the photosensitive polymer combination of the present invention at least a (below be also referred to as " specific aggregation compound ") of contained polymerizable compound preferably dipole moment be the above polymerizable compounds in 3.50 debye.
Polymerizable compound is subjected to forming cured film from the effect polymerization reaction take place of the free radical of following Photoepolymerizationinitiater initiater, particularly reactive high, the polymerization-curable excellence when exposing of this specific aggregation compound polymerization.
Herein, the dipole moment of so-called specific aggregation compound is meant the value that (Fujitsu Ltd.'s manufacturing) calculates according to Scigress ExplorerProfessional Version 7.6.0.52.
The viewpoint of the polymerization-curable during from exposure is considered, as the dipole moment of specific aggregation compound, is preferably more than 3.80 debye, more preferably more than 4.40 debye.
The viewpoint of the polymerization-curable during from exposure is considered, the specific aggregation compound preferably has the ring texture (below be also referred to as " specific ring texture ") and the ethylenic unsaturated double-bond of 5 yuan or 6 yuan, and the ring texture of described 5 yuan or 6 yuan has bond sites that contains C=O and/or the bond sites that contains P=O.
As the described bond sites that contains C=O, can enumerate the position that following formula is represented.
In addition, in this instructions, bonding end (bonding hand) is represented with *.
As the described bond sites that contains P=O, can enumerate the position that following formula is represented.
In addition,, be not particularly limited, for example can enumerate the structure that following formula is represented as having the bond sites that contains C=O and/or containing the concrete example of the ring texture of 5 yuan of bond sites of P=O or 6 yuan.
Having the bond sites that contains C=O and/or containing in the ring texture of 5 yuan of bond sites of P=O or 6 yuan, consider more preferably have 5 yuan or 6 yuan ring texture of the bond sites that contains C=O from the viewpoint of polymerization-curable.
The specific aggregation compound preferably has the ethylenic unsaturated double-bond.
At this moment, consider that from the viewpoint of polymerization-curable the ethylenic unsaturated double-bond more preferably is contained in the specific aggregation compound as the part of (methyl) acryloyl group.
In addition; in this instructions; (methyl) acryloyl group is represented acryloyl group or methacryl; (methyl) acrylate is represented acrylate or methacrylate; (methyl) propenyl is represented propenyl or methylpropenyl; (methyl) acrylamide is represented acrylamide or Methacrylamide, and (methyl) acrylanilide is represented acrylanilide or metering system anilid.
Above-mentioned " polymerizable compound " for example can pass through macromolecules, the method of putting down in writing among Vol36, No.11,2003 the p3871 waits synthetic, wherein, described " polymerizable compound " has the ring texture and the ethylenic unsaturated double-bond of 5 yuan or 6 yuan, and the ring texture of described 5 yuan or 6 yuan has bond sites that contains C=O and/or the bond sites that contains P=O.
In addition, the specific aggregation compound also can contain a plurality of ethylenic unsaturated double-bonds.
Below, list concrete example (the exemplary compounds M-1～M-30), but the present invention is not limited to these compounds of polymerizable compound of the present invention.
About exemplary compounds M-1～M-30, the dipole moment that obtains by said method is respectively: M-1 is 3.87 debye, and M-2 is 4.12 debye, M-3 is 4.54 debye, and M-4 is 4.62 debye, and M-5 is 5.30 debye, M-6 is 5.92 debye, and M-7 is 6.50 debye, and M-8 is 3.70 debye, M-9 is 5.50 debye, M-10 is 5.10 debye, and M-11 is 4.70 debye, and M-12 is 3.90 debye, M-13 is 5.30 debye, M-14 is 4.30 debye, and M-15 is 4.90 debye, and M-16 is 3.87 debye, M-17 is 4.12 debye, M-18 is 4.54 debye, and M-19 is 4.62 debye, and M-20 is 5.30 debye, M-21 is 5.92 debye, M-22 is 6.50 debye, and M-23 is 3.70 debye, and M-24 is 5.50 debye, M-25 is 5.10 debye, M-26 is 4.70 debye, and M-27 is 3.90 debye, and M-28 is 5.30 debye, M-29 is 4.30 debye, and M-30 is 4.90 debye.
Photosensitive polymer combination of the present invention can also contain the polymerizable compound with ethylenic unsaturated link except that containing above-mentioned specific aggregation compound.
As described polymerizable compound, can from the polymerizable compound that constitutes known composition, select to use, for example can enumerate the composition of record in the composition of record in paragraph [0010]～[0020] that the spy opens 2006-No. 23696 communiques or paragraph [0027]～[0053] that the spy opens 2006-No. 64921 communiques.
As mentioned above, among the present invention, polymerizable compound preferably contains above-mentioned specific aggregation compound.But scope of the present invention is not limited to contain the scope of above-mentioned specific aggregation compound.For example, if in the photosensitive polymer combination of the present invention contained resin for the ring texture that has 5 yuan or 6 yuan at its side chain (promptly, described specific ring texture) and the resin of ethylenic unsaturated link, and the position that the ring texture of described 5 yuan or 6 yuan has the position represented by C=O, represented by P=O, contain the bond sites of C=O and/or contain the bond sites of P=O, thereby, also can obtain the effect that the present invention expects even then use the polymerizable compound be subjected to form cured film from the effect polymerization reaction take place of the free radical of following Photoepolymerizationinitiater initiater.
As above-mentioned polymerizable compound, can enumerate the polymerizable compound that can select from the compound of the polymerism that constitutes known composition, for example the spy opens the composition of record in the composition of record in paragraph [0010]～[0020] of 2006-No. 23696 communiques or paragraph [0027]～[0053] that the spy opens 2006-No. 64921 communiques.As the concrete example of above-mentioned polymerizable compound, can enumerate trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate.
Among the present invention, the quality ratio (total amount of the total amount/polymerizable compound of resin) that contains the total amount of the total amount of polymerizable compound of specific aggregation compound and following resin is preferably 0.5～2.0, more preferably 0.6～1.8, be preferably 0.7～1.5 especially.Quality ratio is in above-mentioned scope the time, can obtain having good development, the patterning body of mechanics Strong degree.
＜resin 〉
Photosensitive polymer combination of the present invention contains at least a kind of resin.
As above-mentioned resin, be not particularly limited, be preferably the compound that alkaline aqueous solution is shown swellability, more preferably alkaline aqueous solution is shown deliquescent compound.
As alkaline aqueous solution is shown swellability or deliquescent resin; for example can preferably enumerate resin, specifically be preferably the compound (epoxy acrylic ester compounds) that in epoxy compound, imported ethylenic unsaturated double-bond and acidic groups, at the ethylenic copolymer that has (methyl) acryloyl group and acidic groups on the side chain, epoxy acrylic ester compounds and on side chain, have potpourri, maleamic acid based copolymer of the ethylenic copolymer of (methyl) acryloyl group and acidic groups etc. with acidic groups.
As above-mentioned acidic groups, be not particularly limited, can suitably select according to purpose, for example can enumerate carboxyl, sulfonic group, phosphate etc., in the above-mentioned acidic groups, consider from the viewpoints such as buying property of raw material, can preferably enumerate carboxyl.
As the content of the resin in the photosensitive polymer combination of the present invention, with respect to the total solid composition of photosensitive polymer combination, be preferably 5～70 quality %, more preferably 10～50 quality %.This content is 5 quality % when above, can keep the film Strong degree of photosensitive resin layer, can keep the viscosity on the surface of this photosensitive resin layer well, and this content is 70 quality % when following, and exposure sensitivity is good.
＜resin (A) 〉
Resin among the present invention contains at least a resin that has acidic groups and ethylenic unsaturated link at side chain, preferably also contain from by (i) branched structure, (ii) alicyclic structure, (iii) comprise the position represented by C=O and/or group that the ring texture (that is above-mentioned specific ring texture) of 5 yuan of the position represented by P=O or 6 yuan constitutes at least a structure selected.Below, will have contain above-mentioned (i), (ii), the resin of the formation of at least a structure in (iii) is called " resin (A) ".
Described resin (A) has acidic groups and possesses development, and owing to have the ethylenic unsaturated link, so have high polymerisation reactivity, and have under excellent liquid keeping quality and the dry film state through the time keeping quality, the patterning body can be controlled to be the controlled of desired shape and thickness (height etc.) so can give.
In addition, when described resin (A) has branching and/or alicyclic structure, the compressive modulus of elasticity in the time of can improving formed patterning body and be subjected to external force, from the elastic recovery of compression deformation.Thus, when the patterning bodies such as light spacer that configuration example such as display device are used, be useful.
In addition, when described resin (A) had specific ring texture, the curable during exposure improved.
Herein, branched structure, alicyclic structure, specific ring texture, acidic groups and ethylenic unsaturated link can contain respectively in different side chains, also can a part ofly make up and contain in identical side chain, also can all contain in identical side chain.
(branched structure that can contain in the side chain of resin (A), alicyclic structure, specific ring texture)
Resin (A) with side chain that the main chain of resin combines on can contain at least a structure in branched structure, alicyclic structure and the specific ring texture.Branched structure, alicyclic structure and/or specific ring texture can contain a plurality of in the side chain of resin (A).In addition, branched structure, alicyclic structure and/or specific ring texture also can contain in the side chain of resin (A) with acidic groups and/or ethylenic unsaturated link.
In addition, branched structure, alicyclic structure and/or specific ring texture can directly combine with the main chain of resin (A) and only constitute the side chain of resin (A) with branched structure, alicyclic structure and/or specific ring texture, also can combine with the main chain of resin (A), constitute the side chain of resin (A) as group with branched structure, alicyclic structure and/or specific ring texture by the organic concatenating group of divalence.
As the organic concatenating group of above-mentioned divalence, be preferably selected from a kind of or combination in alkylidene, arlydene, ester group, amide group and the ether.As above-mentioned alkylidene, preferred total carbon atom number is 1～20 alkylidene, and more preferably total carbon atom number is 1～10 alkylidene.Can list methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, Ya Xinji, inferior dodecyl, inferior octadecyl etc. particularly, they can have branching/ring texture, functional group, more preferably methylene, ethylidene, Ya Xinji.As above-mentioned arlydene, preferred total carbon atom number is 6～20 arlydene, and more preferably total carbon atom number is 6～12 arlydene.Can list phenylene, biphenylene, naphthylene, anthrylene etc. particularly, they can have side chain, functional group, more preferably phenylene, biphenylene.
From the viewpoint of development, elastic recovery rate etc., preferably (COO-) main chain with resin (A) combines by ester group at least for branched structure and/or alicyclic structure.In addition, the viewpoint of the curable during from exposure, also preferably (COO-) main chain with resin (A) combines specific ring texture by ester group at least.This combining form is not limited to branched structure, alicyclic structure and/or specific ring texture, and only (COO-) form that combines with the main chain of resin (A) can also be that branched structure, alicyclic structure and/or specific ring texture are by containing the ester group (form that bivalence linking base COO-) combines with the main chain of resin (A) by ester group.That is, other atom or other concatenating group can be contained between branched structure, alicyclic structure and/or specific ring texture and the ester chain, in addition, between the main chain of ester chain and resin (A), other atom or other concatenating group can be contained.
As above-mentioned branched structure, can list carbon number and be 3～12 branch-like alkyl, preference such as isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 2-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, isopentyl, tertiary pentyl, 3-octyl group, uncle's octyl group etc.Wherein, more preferably isopropyl, sec-butyl, the tert-butyl group, isopentyl etc., preferred especially isopropyl, sec-butyl, the tert-butyl group etc.
As above-mentioned alicyclic structure, can list carbon number and be 5～20 ester ring type alkyl, preference such as cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl, adamantyl, three ring decyls, dicyclopentenyl, two cyclopentyl, three cyclopentenyls and three cyclopentyl etc. and groups with them.Wherein, more preferably dicyclopentenyl, cyclohexyl, norborny, isobornyl, adamantyl, three encircle decyls, three cyclopentenyls, three cyclopentyl etc., further preferred dicyclopentenyl, cyclohexyl, norborny, isobornyl, three cyclopentenyls etc., preferred especially dicyclopentenyl, three cyclopentenyls.
As group, preferably has the group of following general formula (3) expression and the form that constitutes with branched structure and/or alicyclic structure.
In the general formula (3), X represents the organic concatenating group of divalence, can also substituting group can be arranged by unsubstituted.Y represents 1 or 2, and n represents 0～15 integer.
As the organic concatenating group of above-mentioned divalence, be preferably selected from a kind of or combination in alkylidene, arlydene, ester group, amide group and the ether, they also can have substituting group.
As above-mentioned alkylidene, preferred total carbon atom number is 1～20 alkylidene, and more preferably total carbon atom number is 1～10 alkylidene.Can list groups such as methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, Ya Xinji, inferior dodecyl, inferior octadecyl particularly, they can have branching/ring texture, functional group, more preferably methylene, ethylidene, Ya Xinji.
As above-mentioned arlydene, preferred total carbon atom number is 6～20 arlydene, and more preferably total carbon atom number is 6～12 arlydene.Can list phenylene, biphenylene, naphthylene, anthrylene etc. particularly, they can have side chain, functional group, more preferably phenylene, biphenylene.
Substituting group when being substituted as above-mentioned group can list alkyl, hydroxyl, amino, halogen radical, fragrant cyclic group, have the group of alicyclic structure etc.
As the monomer that is used on the side chain of resin (A), importing branched structure and/or alicyclic structure, can list phenylethylene, (methyl) esters of acrylic acid, vinyl ethers, vinyl ester, (methyl) acrylic amide etc., preferably (methyl) esters of acrylic acid, vinyl ester, (methyl) acrylic amide, more preferably (methyl) esters of acrylic acid.
As the concrete monomer that is used on the side chain of resin (A), importing branched structure, can list (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid isopentyl ester, (methyl) acrylic acid tert-pentyl ester, the secondary isopentyl ester of (methyl) acrylic acid, (methyl) acrylic acid 2-monooctyl ester, (methyl) acrylic acid 3-monooctyl ester, (methyl) acrylic acid uncle monooctyl ester etc., wherein preferred (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, metering system tert-butyl acrylate etc., more preferably isopropyl methacrylate, metering system tert-butyl acrylate etc.
As the monomer that is used on the side chain of resin (A) importing alicyclic structure, can list and have (methyl) acrylate that carbon number is 5～20 an ester ring type alkyl.As concrete example, can list (methyl) acrylic acid (two the ring [2.2.1] heptan-2-alcohol) ester, (methyl) acrylic acid 1-diamantane ester, (methyl) acrylic acid 2-diamantane ester, (methyl) acrylic acid 3-methyl isophthalic acid-diamantane ester, (methyl) acrylic acid 3,5-dimethyl-1-diamantane ester, (methyl) acrylic acid 3-ethyl diamantane ester, (methyl) acrylic acid 3-methyl-5-ethyl-1-diamantane ester, (methyl) acrylic acid 3,5,8-triethyl-1-diamantane ester, (methyl) acrylic acid 3,5-dimethyl-8-ethyl-1-diamantane ester, (methyl) acrylic acid-2-methyl-2-diamantane ester, (methyl) acrylic acid 2-ethyl-2-diamantane ester, (methyl) acrylic acid 3-hydroxyl-1-diamantane ester, (methyl) acrylic acid octahydro-4,7-menthol indenes (menthanoindene)-5-base ester, (methyl) acrylic acid octahydro-4,7-menthol indenes-1-base methyl esters, (methyl) acrylic acid 1-menthyl ester, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems, (methyl) acrylic acid 3-hydroxyl-2,6,6-trimethyl-two ring [3.1.1] heptyl ester, (methyl) acrylic acid 3,7,7-trimethyl-4-hydroxyl-two ring [4.1.0] heptyl ester, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid turnip ester, (methyl) acrylic acid 2,2,5-3-methyl cyclohexanol ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid three cyclopentene esters etc.
In above-mentioned (methyl) acrylate, from making compressive modulus of elasticity by bulky functional group, the viewpoint that elastic recovery becomes good is set out, preferred (methyl) cyclohexyl acrylate, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid 1-diamantane ester, (methyl) acrylic acid 2-diamantane ester, (methyl) acrylic acid turnip ester, (methyl) acrylic acid 1-menthyl ester, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid three cyclopentene esters etc., preferred especially (methyl) cyclohexyl acrylate, (methyl) acrylic acid (falling) norbornene ester, (methyl) isobornyl acrylate, (methyl) acrylic acid 2-diamantane ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid three cyclopentene esters.
In addition, as the monomer that on the side chain of resin (A), imports alicyclic structure, can enumerate the compound of following general formula (4) or (5) expression.Herein, in general formula (4), (5), X represents the organic concatenating group of divalence, and R represents hydrogen atom or methyl.Y represents 1 or 2, and n represents 0～15.In general formula (4), (5), also preferred y=1 or 2, n=0～8, more preferably y=1 or 2, n=0～4 (further preferred n=0～2).As the preferred concrete example of the compound of general formula (4) or (5) expression, can enumerate following Compound D-1～D-11, T-1～T-12.
Wherein, from the viewpoint of elastic recovery rate, the compound of preferred following general formula (4) expression.
In general formula (4)～(5), the organic concatenating group of the divalence that X represents can not have replacement also can have substituting group, and with the organic concatenating group same meaning of divalence that the X of above-mentioned general formula (3) represents, preferred form is also identical.
As the monomer that is used on the side chain of resin (A), importing alicyclic structure, can use the monomer of suitable manufacturing, also can use commercially available product.
As above-mentioned commercially available product, can list FA-511A, FA-512A (S) that Hitachi Chemical Co., Ltd. makes, FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M etc.Wherein, from the viewpoint of development excellence, deformation-recovery rate excellence, preferred FA-512A (S), FA-512M.
The structure and the concrete example thereof of the specific ring texture that can contain in the structure of the specific ring texture that can contain in the side chain of resin (A) and concrete example thereof and the above-mentioned specific aggregation compound are identical.
As the monomer that is used on the side chain of resin (A), importing specific ring texture, can list phenylethylene, (methyl) esters of acrylic acid, vinyl ethers, vinyl ester, (methyl) acrylic amide etc., preferably (methyl) esters of acrylic acid, vinyl ester, (methyl) acrylic amide, more preferably (methyl) esters of acrylic acid.
Concrete monomer as be used for importing specific ring texture on the side chain of resin (A) can list above-claimed cpd M-1～M-7, M-9, M-16～M-22, M-24.But the present invention is not limited to these compounds.
As the monomer that is used on the side chain of resin (A), importing specific ring texture, can use suitably synthetic monomer, also can use commercially available product.
This monomer for example can pass through macromolecules, and the method for record waits synthetic in 3871 pages of Vol.36, No.11 (2003).
As above-mentioned commercially available product, for example,, can list 1-AdA of Xiao field Industry Co., Ltd as compound M-3, as compound M-10, can enumerate the GBLMA of Xiao field Industry Co., Ltd etc.
(acidic groups)
Resin (A) contains at least a acidic groups on the side chain that links with main chain.Acidic groups can contain a plurality of in side chain.In addition, acidic groups also can contain in the side chain of resin (A) with above-mentioned branched structure, above-mentioned alicyclic structure and/or above-mentioned specific ring texture and ethylenic unsaturated link.
In addition, above-mentioned acidic groups can directly combine with the main chain of resin (A) and only constitute the side chain of above-mentioned resin with acidic groups, also can combine with the main chain of resin (A), constitute the side chain of resin (A) as group with acidic groups by the organic concatenating group of divalence.Here, the example of the organic concatenating group of divalence and preference thereof are identical with the example and the preference thereof of the organic concatenating group of enumerating in the explanation of above-mentioned branched structure, above-mentioned alicyclic structure and above-mentioned specific ring texture of divalence.
As above-mentioned acidic groups, be not particularly limited, can from known acidic groups, suitably select, can list for example carboxyl, sulfonic group, sulfoamido, phosphate, phenol hydroxyl etc.Wherein, the viewpoint from the water tolerance excellence of development and cured film is preferably carboxyl, phenol hydroxyl.
As the object lesson that is used for importing the monomer of above-mentioned acidic groups to resin (A), can be from known monomer suitably select, for example can list the addition compound product, ω-carboxyl-polycaprolactone list (methyl) acrylate of (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, alpha-cyano cinnamic acid, acrylic acid dimer, monomer and cyclic acid anhydride etc. with hydroxyl.They can use the monomer of suitable manufacturing, also can use commercially available product.
As the monomer that in the addition compound product of above-mentioned monomer and cyclic acid anhydride, uses, for example can list (methyl) acrylic acid 2-hydroxy methacrylate etc. with hydroxyl with hydroxyl.As above-mentioned cyclic acid anhydride, can list for example maleic anhydride, phthalic anhydride, cyclohexyl dicarboxylic acid's acid anhydride etc.
Commercially available product as monomer, can list ア ロ ニ Star Network ス M-5300, ア ロ ニ Star Network ス M-5400, ア ロ ニ Star Network ス M-5500, ア ロ ニ Star Network ス M-5600 that East Asia synthetic chemical industry Co., Ltd. makes, NK エ ス テ Le CB-1, NK エ ス テ Le CBX-1 that Xin Zhong village chemical industry Co., Ltd. makes, HOA-MP, HOA-MS that oil chemistry Industrial Co., Ltd of common prosperity society makes, PVC ス コ-ト #2100 that Osaka Organic Chemical Industry Co., Ltd. makes etc.Wherein, from development excellence, viewpoint cheaply, preferred (methyl) acrylic acid etc.
(ethylenic unsaturated link)
Resin (A) contains at least a kind of ethylenic unsaturated link on side chain.
In the resin (A), the ethylenic unsaturated link preferably and between the main chain is configured by ester group.
This ethylenic unsaturated link can contain a plurality of in side chain.In addition, the ethylenic unsaturated link can contain in the side chain of resin (A) with above-mentioned branched structure, above-mentioned alicyclic structure, above-mentioned specific ring texture and/or above-mentioned acidic groups.
In addition, (COO-) combine, can only constitute the side chain of resin (A) by at least 1 ester group between the main chain of ethylenic unsaturated link and resin (A) by ethylenic unsaturated link and ester group.In addition, can also contain the organic concatenating group of divalence between the main chain of resin (A) and the ester group and/or between ester group and the ethylenic unsaturated link, the ethylenic unsaturated link can be used as the side chain that " have and main chain between the group of the ethylenic unsaturated link that is configured by ester group " constitutes resin (A).Here, the example of the organic concatenating group of divalence and preference thereof are identical with the example and the preference thereof of the organic concatenating group of illustrative divalence in the explanation of above-mentioned branched structure, alicyclic structure and above-mentioned specific ring texture.
In addition, the ethylenic unsaturated link preferably is configured in the side chain of resin (A) by importing (methyl) acryloyl group.
The method that imports (methyl) acryloyl group in the side chain of resin (A) can suitably be selected from known method, and for example can enumerate: addition has the method for (methyl) acrylate of epoxy radicals in having the repetitive of acidic groups; Addition has the method for isocyanate group (methyl) acrylate in having the repetitive of hydroxyl; Addition has the method for hydroxyl (methyl) acrylate etc. in having the repetitive of isocyanate group.
Wherein, addition has the easiest manufacturing of method of (methyl) acrylate of epoxy radicals in having the repetitive of acidic groups, considers and preferred from viewpoint cheaply.
(methyl) acrylate as having above-mentioned epoxy radicals is not particularly limited, the compound of the compound of for example preferred following structural formula (1) expression and following structural formula (2) expression.
Wherein, in the said structure formula (1), R
1Expression hydrogen atom or methyl.L
1The expression organic group.
Wherein, in the said structure formula (2), R
2Expression hydrogen atom or methyl.L
2The expression organic group.W represents the aliphatic alkyl of 4～7 yuan of rings.
In the compound that the compound and the structural formula (2) of said structure formula (1) expression are represented, compare with structural formula (2), more preferably the compound of structural formula (1) expression.Said structure formula (1) reaches in (2), more preferably L
1And L
2Be respectively that carbon number is the compound of 1～4 alkylidene independently.
As the compound of said structure formula (1) expression or the compound of structural formula (2) expression, be not particularly limited, for example can enumerate following exemplary compounds (1)～(10).
(other monomer)
In the resin among the present invention (A), can also use other monomer to import other group.
As above-mentioned other monomer, be not particularly limited, for example can list (methyl) acrylate, styrene, vinyl ether, have the monomer of dibasic acid anhydride base, vinyl ester group, hydrocarbon chain thiazolinyl etc. etc.
As above-mentioned vinyl ether group, be not particularly limited, can list for example butyl vinyl ether etc.
As above-mentioned dibasic acid anhydride base, be not particularly limited, can list for example maleic anhydride base, itaconic anhydride base etc.
As above-mentioned vinyl ester group, be not particularly limited, can list for example vinyl acetate ester group etc.
As above-mentioned hydrocarbon chain thiazolinyl, be not particularly limited, can list for example butadienyl, prenyl etc.
As the containing ratio of other monomer in the above-mentioned resin (A), ratio of components is preferably 1～40 quality %, more preferably 2～30 quality %.
As the object lesson of resin (A), can list the compound of for example representing (exemplary compounds P-1～P-56, Q-1～Q-15 and Q-39) with following structure.
In addition, the x in the exemplary compounds, y and z represent the ratio of components (mass ratio) of each repetitive, are preferably the form that constitutes in preferable range described later.In addition, the weight-average molecular weight of each exemplary compounds also is preferably the form that constitutes in preferable range described later.
(synthetic method of resin (A))
Resin (A) can be synthesized by the operation of (being total to) polyreaction of monomer and this two-stage operation of operation that imports the ethylenic unsaturated group.
At first, (being total to) polyreaction is undertaken by (being total to) polyreaction of various monomers.The material and the method for (being total to) polyreaction are not particularly limited, and can suitably select from material known and method.For example, as polymerization methods, can from free radical polymerization, cationic polymerization, anionic polymerisation, coordination polymerization etc., suitably select based on the spike classification.Wherein, from synthetic easily, viewpoint cheaply, preferred free radical polymerization.In addition,, also be not particularly limited, can from known method, suitably select for polymerization.Can suitably select for example mass polymerization, suspension polymerization, emulsion polymerization, solution polymerization process etc.Wherein, more preferably solution polymerization process.
(carbon number of resin (A))
Consider elasticity coefficient (hardness), the total carbon atom number as resin (A) is preferably more than 10.Wherein, total carbon atom number more preferably 10～30 is preferably 10～15 especially.
(molecular weight of resin (A))
The molecular weight of resin (A) is preferably 10,000～100,000 in weight-average molecular weight, and more preferably 12,000～60,000, be preferably 15,000～45,000 especially.If weight-average molecular weight in above-mentioned scope, is being preferred aspect the manufacturing adaptability of resin (being preferably multipolymer), the development then.In addition, aspect being difficult for that decline because of melt viscosity causes that formed shape caves in and be difficult for becoming crosslinked bad aspect, when developing, do not have the sept shape residue aspect be preferred.
Weight-average molecular weight is measured with gel permeation chromatography (GPC).Relevant GPC describes in detail among the embodiment described later.
(glass transition temperature of resin (A))
The glass transition temperature (Tg) of resin (A) is preferably 40～180 ℃, more preferably 45～140 ℃, is preferably 50～130 ℃ especially.If glass transition temperature (Tg) in above-mentioned preferred range, then can obtain having good development, the sept of mechanical strength.
(acid number of resin (A))
The acid number of resin (A) is according to the difference of resulting molecular structure, and its preferred range can change, but generally is preferably more than the 20mgKOH/g, more preferably more than the 40mgKOH/g, is preferably 50～130mgKOH/g especially.If acid number is in the above-mentioned preferred range, then can obtain having good development, the sept of mechanical strength.
Viewpoint from the sept that can obtain having good development, mechanical strength, the glass transition temperature (Tg) of above-mentioned resin (A) is preferably 40～180 ℃, and weight-average molecular weight is preferably 10,000～100,000, more preferably Tg is 45～140 ℃ (more preferably 50～130 ℃), and weight-average molecular weight is 12,000～60,000 (more preferably 15,000～45,000).
And then more preferably above-mentioned resin (A) has each condition of combination above-mentioned preferred above-mentioned molecular weight, above-mentioned preferred glass transition temperature (Tg) and above-mentioned preferred acid number.
The ethylenic unsaturated link that the viewpoint of the deformation-recovery rate when forming patterning body (for example color filter use sept), development residue, fine wrinkle (reticulation), the resin among the present invention (A) preferably will (1) branched structure, alicyclic structure and/or specific ring texturees, dispose by ester group between (2) acidic groups, (3) and the main chain contains the multipolymer more than the ternary polymerization in different separately repetitive (copolymerization units).
Particularly, above-mentioned resin (A) is preferably the above multipolymer of ternary polymerization that has following repetitive at least: the repetitive with branched structure, alicyclic structure and/or specific ring texture: X (x mole %); Repetitive with acidic groups: Y (y mole %); Have and main chain between the repetitive of ethylenic unsaturated link by ester group configuration: Z (z mole %).And then, can also have other repetitive: K (k mole %) as required.
Above-mentioned multipolymer for example can have branched structure by making, the monomer of alicyclic structure and/or specific ring texture, have acidic groups monomer, have and main chain between the monomer of ethylenic unsaturated link by the ester group configuration and other monomer generation copolymerization of adding as required obtain.
Resin of the present invention (A) is when having branched structure and/or alicyclic structure as the multipolymer of repetitive (copolymerization units), from the viewpoint that makes compressive modulus of elasticity, elastic recovery become good by bulky functional group, resin (A) is preferably following multipolymer: this multipolymer makes the monomer copolymerization of representing as above-mentioned above-mentioned general formula (4) with monomer of branched structure and/or alicyclic structure at least, thereby has imported the group with branched structure and/or alicyclic structure.At this moment, resin (A) has the structural unit from the monomer of above-mentioned general formula (4) expression on main chain.
Copolymerization ratio of components when relevant above-mentioned resin (A) is multipolymer can be considered to determine behind glass transition temperature and the acid number.Though can not can be set at following ranges without exception.
The ratio of components (x) of the repetitive with branched structure, alicyclic structure and/or specific ring texture in the resin (A) is preferably 10～70 moles of %, and more preferably 15～65 moles of % are preferably 20～60 moles of % especially.If ratio of components (x) is in the above-mentioned scope, then can obtain good development, and the developer solution patience of image portion is also good.
The ratio of components (y) of the repetitive with acidic groups in the resin (A) is preferably 5～70 moles of %, and more preferably 10～60 moles of % are preferably 20～50 moles of % especially.If ratio of components (y) is in the above-mentioned scope, then can obtain good curable, development.
The ratio of components (z) of the repetitive of having in the resin (A) " ethylenic unsaturated link " is preferably 10～70 moles of %, and more preferably 20～70 moles of % are preferably 30～70 moles of % especially.If ratio of components (z) is that then pigment-dispersing is good in the above-mentioned scope, and sensitivity and polymerization-curable are good, and the ageing stability when transferring long preservation under fluid preservation behind the liquid and the dry film state after coating is good.
And then, as resin (A), preferred following situation: ratio of components (x) is 10～70 moles of % (15～65 moles of % more preferably, be preferably 20～50 moles of % especially), ratio of components (y) is 5～70 moles of % (10～60 moles of % more preferably, be preferably 30～70 moles of % especially), ratio of components (z) is 10～70 moles of % (more preferably 20～70 moles of % are preferably 30～70 moles of % especially).
In addition, resin (A) have " branched structure and/or alicyclic structure " and " specific ring texture " both the time, the ratio of components (1) of " branched structure and/or alicyclic structure " is preferably 10～60 moles of %, more preferably 15～50 moles of %.Particularly, resin (A) for comprise repetitive X (x mole %), repetitive Y (y mole %) at least with acidic groups with specific ring texture, have and main chain between by the ester group configuration the ethylenic unsaturated link repetitive Z (z mole %), when having the multipolymer of repetitive L (1 mole of %) of branched structure and/or alicyclic structure, ratio of components (x) with repetitive of specific ring texture is preferably 10～70 moles of %, more preferably 10～65 moles of %; Ratio of components (y) with repetitive of acidic groups is preferably 5～70 moles of %, and more preferably 10～60 moles of % are preferably 10～50 moles of % especially; Ratio of components (z) with repetitive of ethylenic unsaturated link is preferably 10～70 moles of %, and more preferably 20～70 moles of % are preferably 30～60 moles of % especially; In addition, the ratio of components (1) with repetitive of branched structure and/or alicyclic structure is preferably 10～60 moles of %, and more preferably 10～50 moles of % are preferably 15～50 moles of % especially.
As the concrete example of above-mentioned resin (A), can enumerate the compound (exemplary compounds Q-16～Q-38 and Q-40) that following structure is represented.The ratio of components (mass ratio) of the x in the exemplary compounds, y, z and 1 each repetitive of expression, the preferably form of each ratio of components in above-mentioned preferable range.In addition, the also preferred form in above-mentioned preferable range of the weight-average molecular weight of each exemplary compounds.
More than, the preferred configuration of resin (A) has been described, but as the preferred configuration of photosensitive polymer combination of the present invention, can enumerate following form: as resin, use the preferred configuration of above-mentioned resin (A),, use above-mentioned exemplary compounds M-1～M-7 as the specific aggregation compound.When constituting photosensitive polymer combination of the present invention as mentioned above, can more effectively bring into play effect of the present invention.
When photosensitive polymer combination of the present invention contained above-mentioned resin (A), the content in the photosensitive polymer combination was preferably 5～70 quality % with respect to the total solid composition of composition, more preferably 10～50 quality %.
Resin (A) can with following other resin and usefulness, but contained resin preferably only is made of above-mentioned resin (A) in the photosensitive polymer combination of the present invention.
＜Photoepolymerizationinitiater initiater 〉
Photosensitive polymer combination of the present invention contains at least a Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater as among the present invention is not particularly limited, and can use known Photoepolymerizationinitiater initiater.As known Photoepolymerizationinitiater initiater, can list for example special paragraph [0010]～[0020] or the special initiating agent of putting down in writing in paragraph [0027]～[0053] of 2006-64921 communique of opening of opening the 2006-23696 communique.As the example of known Photoepolymerizationinitiater initiater, from the viewpoint of sensitivity, preferred above-mentioned glycyl benzene compounds, acylphosphine oxide based compound, oxime ester based compound in addition.
As the object lesson of glycyl benzene compounds, can list IRGACURE (Irg) 907 (manufacturing of Ciba Specialty Chemicals Co., Ltd.) etc.As the object lesson of acylphosphine oxide based compound, can list DAROCUR TPO, Irgacure (Irg) 819 (above is that Ciba Specialty Chemicals Co., Ltd. makes) etc.In addition, as the object lesson of oxime ester based compound, can list IRGACURE (Irg) OXE01 or CGI242 etc. (above is that Ciba Specialty Chemicals Co., Ltd. makes).Following table illustrates the structure of above-mentioned initiating agent.
＜glycyl benzene compounds 〉
＜acylphosphine oxide based compound 〉
＜oxime ester based compound 〉
The total amount of Photoepolymerizationinitiater initiater in photosensitive polymer combination is preferably 0.5～25 quality % with respect to the total solid composition of photosensitive polymer combination, more preferably 1～20 quality %.
＜particulate 〉
From the viewpoint of mechanical strength, when preferably containing resin, polymerizable compound, Photoepolymerizationinitiater initiater, photosensitive polymer combination of the present invention also contains at least a particulate.
As particulate, be not particularly limited, can suitably select according to purpose, but preference such as spy open the extender pigment of record in 2003-302639 communique [0035]～[0041], wherein, viewpoint from the light spacer that obtains having good development, mechanical strength is preferably cataloid.
From forming the viewpoint that can obtain high mechanical strength when light spacer etc. is subjected to the structure of external force easily, the mean grain size of above-mentioned particulate is preferably 5～50nm, and more preferably 10～40nm is preferably 15～30nm especially.
As the content of above-mentioned particulate in photosensitive polymer combination (when forming light spacer is light spacer or the photo-sensitive resin that constitutes it), viewpoint from the light spacer that obtains having high mechanical strength, be preferably 5～50 quality % with respect to the total solid composition (quality) in the photosensitive polymer combination, more preferably 10～40 quality % are preferably 15～30 quality % especially.
＜other 〉
In the photosensitive polymer combination of the present invention, except resin, specific aggregation compound, Photoepolymerizationinitiater initiater and the particulate that contains as required, can also contain photopolymerization as required and cause other compositions such as auxiliary agent.
Photosensitive polymer combination can also and cause auxiliary agent as other adding ingredient with photopolymerization.It is the polymerization that is used to promote to have been caused by Photoepolymerizationinitiater initiater the polymerizable compound of polymerization that photopolymerization causes auxiliary agent, can be used in combination with Photoepolymerizationinitiater initiater.Cause auxiliary agent as photopolymerization, preferably use at least a of amine compound.
As above-mentioned amine compound, can list for example triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (being commonly called as Michler's keton), 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., wherein, preferred 4,4 '-two (diethylamino) benzophenone.In addition, also can be used in combination various kinds of amine system or other photopolymerization and cause auxiliary agent.
Cause auxiliary agent as other photopolymerization beyond above-mentioned, can list for example alkoxy anthracene based compound, thioxanthones based compound, coumarin series compounds etc.As above-mentioned alkoxy anthracene based compound, for example can list 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.As above-mentioned thioxanthones based compound, can list for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
In addition, cause auxiliary agent, also can use commercially available product as photopolymerization.Cause auxiliary agent as commercially available photopolymerization, for example can list trade name " EAB-F " (Baotugu Chemical Industrial Co., Ltd's manufacturing) etc.
Cause the content of auxiliary agent in photosensitive polymer combination as photopolymerization,, be preferably 0.6 mass parts～20 mass parts, 1 mass parts～15 mass parts more preferably, especially preferred 1.5 mass parts～15 mass parts with respect to the above-mentioned Photoepolymerizationinitiater initiater of 1 mass parts.
In addition, as other composition, can from the composition that constitutes known composition, select to use, can list for example special paragraph [0010]～[0020] or the special composition of putting down in writing in paragraph [0027]～[0053] of 2006-64921 communique of opening of opening the 2006-23696 communique.
Photosensitive polymer combination of the present invention can also be suitable for forming dividing wall (for example black matrix" etc.), orientation control with other patterning body or tunicle such as projection except can being suitable for forming light spacer described later, colored pattern, diaphragm.
" light spacer and forming method thereof "
Light spacer of the present invention is to use the photosensitive polymer combination of the invention described above to form.For the details and the preferred configuration thereof of photosensitive polymer combination, as mentioned above.
Because light spacer of the present invention is to use photosensitive polymer combination of the present invention to constitute, so the excellent in uniformity of the homogeneity of cross sectional shape and height (being the inequality of the uneven or height of cross sectional shape).
And then, when photosensitive polymer combination of the present invention contains resin (A), can obtain having light spacer as the necessary high compression elastic modulus of light spacer, deformation-recovery.
Among the present invention,, be preferably in a plurality of positions (being preferably 3 more than the position) in substrate as the state of patterning bodies such as light spacer " cross sectional shape excellent in uniformity ", the cross sectional shape of patterning body becomes the state of the shape that is similar to rectangle.
As the above-mentioned shape that is similar to rectangle, more preferably following shape: on the cross section of patterning body, the line that is equivalent to the patterning body side surface and the line angulation that is equivalent to patterning body lower surface (below be also referred to as " coning angle ") are 40 °～100 °.
Here, the lower surface of above-mentioned patterning body is meant the surface of contact that contacts with the substrate that has formed this patterning body in the surface of patterning body.In addition, the side of above-mentioned patterning body is meant, in the surface of patterning body, neither the surface of the upper surface (, and being and the discontiguous face of above-mentioned substrate) that the lower surface of above-mentioned patterning body neither the patterning body with the parallel face of above-mentioned patterning body lower surface.
So long as used the method for photosensitive polymer combination of the present invention, just can form light spacer of the present invention, but comprise that by use the method (the formation method of light spacer of the present invention) of following operation (1)～(3) can form on optimum ground with any method.
The formation method of light spacer of the present invention is provided with following operation and constitutes: (1) is the operation of the tunicle of the photosensitive polymer combination that forms the invention described above on the substrate (below be also referred to as " tunicle formation operation "); (2) with the operation of at least a portion of described tunicle exposure (below be also referred to as " exposure process "); (3) described after will exposing by the operation of film development (below be also referred to as " developing procedure "), the operation of the described tunicle heating after (4) can also be set as required will develop (below be also referred to as " tunicle heating process ") and other operation.
(1) tunicle forms operation
It is the tunicle that forms the photosensitive polymer combination of the invention described above on substrate that tunicle forms operation.Can form photo-sensitive resin as tunicle, this photo-sensitive resin just constitutes the light spacer of holding unit thickness equably through other operations such as exposure process described later and developing procedures.The light spacer of the application of the invention can effectively be eliminated the particularly easy demonstration inequality that produces in the image that shows in the uneven display device (particularly liquid crystal indicator) that changes because of element thickness.
Method as form photo-sensitive resin on substrate can preferably list: (a) rubbing method that the photosensitive polymer combination that contains above-mentioned resin, polymerizable compound and Photoepolymerizationinitiater initiater at least is coated with; And (b) use photosensitive transfer printing material, the transfer printing that photo-sensitive resin is carried out lamination, transfer printing by heating and/or pressurization with above-mentioned photo-sensitive resin.
(a) rubbing method
The coating of photosensitive composite can be used the extrusion coated method of the use hopper that known rubbing method for example puts down in writing in spin-coating method, curtain coating method, slot coated method, dip coated method, airblade coating method, rolling method, coiling rod rubbing method, intaglio plate rubbing method or No. 2681294 instructions of United States Patent (USP) to wait to carry out.Wherein, the spy opens 2004-89851 communique, spy and opens 2004-17043 communique, spy and open 2003-170098 communique, spy and open 2003-164787 communique, spy and open 2003-10767 communique, spy and open 2002-79163 communique, spy to open the method for utilizing gap nozzle or slot coated device of record in the 2001-310147 communique etc. be preferred.
(b) transfer printing
Transfer printing is to use photosensitive transfer printing material, will form on the interim supporter membranaceous photo-sensitive resin use for example heat and/or pressurize after roller or dull and stereotyped by press sticking or add thermocompression bonded and desired real estate stickup after, thereby by peeling off interim supporter photo-sensitive resin is transferred on the substrate.Can list the spy particularly opens flat 7-110575 communique, spy and opens that flat 11-77942 communique, spy are opened the 2000-334836 communique, the spy opens laminate and the laminating method of putting down in writing in the 2002-148794 communique, from the viewpoint of few foreign, the special method of putting down in writing in the flat 7-110575 communique of opening of preferred use.
When forming photo-sensitive resin, can oxygen insulating course (below be also referred to as " oxygen partition film " or " middle layer ") be set further between photo-sensitive resin and the interim supporter.Can improve exposure sensitivity thus.In addition, in order to improve transfer printing, the thermoplastic resin with resiliency can also be set.
The method for making of interim supporter, oxygen insulating course, thermoplastic resin, other layer and this photosensitive transfer printing material of relevant formation photosensitive transfer printing material can be suitable for middle formation, the method for making of putting down in writing in paragraph [0024]～[0030] that the spy opens the 2006-23696 communique.
When passing through (a) rubbing method and (b) transfer printing forms photo-sensitive resin, all preferred its bed thickness is 0.5～10.0 μ m, more preferably 1～6 μ m.If bed thickness is above-mentioned scope, the generation of the pin hole when coating forms in then can preventing to make need not spend the development that just can carry out unexposed portion for a long time and remove.
As the substrate that forms photo-sensitive resin, can list transparency carrier (for example glass substrate or plastic base) for example, have nesa coating (for example ITO film) substrate, have color filter substrate (being also referred to as filter substrate), have the driving substrate of driving element (for example thin film transistor (TFT) (TFT)) etc.As the thickness of substrate, generally be preferably 700～1200 μ m.
(2) exposure process and (3) developing procedure
In exposure process, will form at least a portion exposure of the tunicle that forms in the operation at above-mentioned tunicle, form sub-image.In developing procedure thereafter, will in above-mentioned exposure process, expose by film development, can form the spacer patterns of desired shape.
As the object lesson of above-mentioned operation, formation example, the spy that can list record in paragraph [0071]～[0077] that the spy opens the 2006-64921 communique opens the operation of record in paragraph [0040]～[0051] of 2006-23696 communique etc. as preferred example among the present invention.
The formation method of light spacer of the present invention can be provided with following (4) tunicle heating process, but the exposure increase by making above-mentioned exposure etc. can not be provided with tunicle heating process (below be also referred to as " no heating process ") and form the light spacer with excellent cross sectional shape homogeneity and excellent high homogeneity.
By being set at " no heating process ", can more effectively suppress deterioration or the patterning body (colored pattern etc.) that has formed or the deterioration of diaphragm of the light spacer that will form.
Exposure when being set at " no heating process " is preferably 1～500mJ/cm
2, 10～300mJ/cm more preferably
2
(4) tunicle heating process
The formation method of light spacer of the present invention also can be provided with the tunicle heating process with the heating of the tunicle after the development of above-mentioned developing procedure.By heating, further promote the curing of tunicle, can obtain having the light spacer of high Strong degree.In addition, when photosensitive polymer combination contains above-mentioned resin (A), can obtain compressive modulus of elasticity, light spacer that elastic recovery is good.
Here, the maximum temperature of heating is according to heat time heating time and difference, but is preferably 40 ℃～145 ℃, more preferably 40 ℃～140 ℃, is preferably 80 ℃～140 ℃ especially.Maximum temperature is in 40 ℃～145 ℃ the scope time, can more effectively suppress deterioration or the patterning body (colored pattern etc.) that has formed or the deterioration of diaphragm of the light spacer that will form.
Wherein, more preferably the maximum temperature of heating is that 80 ℃～140 ℃, heat time heating time are 0.1 hour～3.0 hours (more preferably 0.2 hour～1 hour).
Can be produced on the base board for display device that possesses light spacer on the substrate as described above.Light spacer is preferably formed on the driving elements such as last or TFT of the black light shielding parts such as black matrix" that are formed on the substrate.In addition, between driving elements such as black light shielding parts such as black matrix" or TFT and light spacer, also can there be alignment films such as transparency conducting layers (transparency electrode) such as ITO or polyimide.
For example, when light spacer is arranged on black light shielding part or the driving element, can make base board for display device by the following method: cover the black light shielding part (black matrix" etc.) or the driving element that are provided in advance on this substrate, for example the photo-sensitive resin with photosensitive transfer printing material is laminated on the support dignity, peel off transfer printing and after forming photo-sensitive resin, it is implemented exposure, development, heat treated etc. to form light spacer.
The colored pixels of redness (R), blue (B), green (G) three looks etc. can also further be set on above-mentioned base board for display device as required.
Light spacer of the present invention forms after can containing the color filter of painted portions such as black shielding portion such as black matrix" and colored pixels in formation.
Above-mentioned black shielding portion and painted and light spacer can be by forming rubbing method and transfer printing combination in any, wherein said rubbing method is the photosensitive resin coating method for compositions, uses the transfer materials with the photo-sensitive resin that is formed by photosensitive polymer combination in the described transfer printing.
Above-mentioned black shielding portion and painted and above-mentioned light spacer can be formed by photosensitive polymer combination respectively, particularly, for example on the substrate directly the above-mentioned photosensitive polymer combination of coating liquid with after forming photo-sensitive resin, expose and develop, above-mentioned black shielding portion and painted portion are formed pattern-like, the above-mentioned photosensitive polymer combination of other liquid is set then to form photo-sensitive resin on the other substrate different with aforesaid substrate (interim supporter), make thus and obtain transfer materials, use this transfer materials, thereby make this transfer materials and the aforesaid substrate that is formed with above-mentioned black shielding portion and painted portion adhere to the transfer printing photo-sensitive resin, expose then and develop, light spacer can be formed pattern-like thus.
Can make the color filter that is provided with light spacer as mentioned above.
" diaphragm "
Diaphragm of the present invention is to use the photosensitive polymer combination of the invention described above to form.
Because diaphragm of the present invention uses photosensitive polymer combination of the present invention to constitute, so even in low heating-up temperature or not have under the situation about forming under the heat treated film thickness uniformity also good.
So long as used the method for photosensitive polymer combination of the present invention, just can form diaphragm of the present invention with any means, can form with the method identical with the formation method of above-mentioned light spacer of the present invention.Here, when diaphragm not being implemented patterning, promptly, when diaphragm is formed as the whole facial mask of what is called, and in above-mentioned (2) exposure process, the method for preferably tunicle being carried out whole exposure.
" colored pattern "
Colored pattern of the present invention is to use the photosensitive polymer combination of the invention described above to form.Here, photosensitive polymer combination is preferably the form that also further contains at least a colorant except that containing above-mentioned each composition.
As above-mentioned colorant, be not particularly limited, can from known colorant, suitably select.As known colorant, can list the spy particularly and open colorant that pigment, spy that the pigment of record in 2005-17716 communique [0038]～[0054] and dyestuff, spy open record in 2004-361447 communique [0068]～[0072] open record in 2005-17521 communique [0080]～[0088] etc.
Because colored pattern of the present invention uses photosensitive polymer combination of the present invention to constitute, so even in low heating-up temperature or do not have under the situation about forming under the heat treated, the homogeneity of cross sectional shape and film thickness uniformity are also good.
In addition, when colored pattern of the present invention during as the key element of color filter of the colored pattern with multiple color, as long as the colored pattern of at least a color uses photosensitive polymer combination of the present invention to form.
So long as used the method for photosensitive polymer combination of the present invention, just can form colored pattern of the present invention with any means, for example, can form with the method identical with the formation method of the light spacer of the invention described above.
" base board for display device "
Base board for display device of the present invention possesses at least a in light spacer of the present invention, diaphragm of the present invention and the colored pattern of the present invention and constitutes.
Base board for display device of the present invention is owing to possessing the structure that uses that photosensitive polymer combination of the present invention forms, cross sectional shape and thickness (highly) to have good uniformity (at least a in light spacer of the present invention, diaphragm of the present invention and the colored pattern of the present invention; the term implication that below simply is recited as " structure " is identical), so can suppress when being used for display device to show uneven.
Here so-called base board for display device is meant at least one of a pair of supporter that is used for constituting display device.
Object lesson as base board for display device, according to the difference of the formation of display element or display device and difference, can list and for example possess colored pattern the filter substrate of (below be also referred to as " colored pixels "), the band driving means substrate that possesses driving means (for example, the simple matrix substrate, active-matrix substrate etc.), the band dividing wall substrate (the band black matrix substrate etc. that for example, possesses black matrix") that possesses dividing wall, possesses the two color filter array (color filteron array) substrate of colored pattern and driving means, the glass substrate of patterning body or tunicle etc. is not set.
The above-mentioned colored pattern group (colored pixels group) of above-mentioned filter substrate can be made of the pixel of two looks that present different colours each other, also can be made of the pixel of three looks, pixel more than four looks.For example under the situation of three looks, constitute by red (R), green (G) and blue (B) these three kinds of tones.Under the situation of the pixel groups that disposes RGB three looks, the configuration of preferably inlaying (mosaic) type, triangle type etc., under the situation of the pixel groups more than configuration four looks, which type of configuration can.The making of filter substrate for example can be formed as described above black matrix" after having formed the pixel groups more than two looks, also can form pixel groups conversely after forming black matrix".The formation of relevant rgb pixel can be opened 2004-347831 communique etc. with reference to the spy.
" display element "
Use base board for display device of the present invention can form display element.
A kind of as display element can list the liquid crystal display cells that possesses liquid crystal layer and liquid crystal drive means (comprising simple matrix type of drive and driven with active matrix mode) between at least one is a pair of supporter (comprising base board for display device) of transmitance at least.
Under the situation of this liquid crystal display cells, base board for display device can be used as each pixel that has a plurality of rgb pixel groups, constitutes this pixel groups and is used by the filter substrate that black matrix" is divided each other.On this filter substrate, owing to be provided with the structure that cross sectional shape and thickness (highly) have good uniformity, so possess that the liquid crystal display cells of this filter substrate can effectively prevent because the color spot that the liquid crystal material skewness that the cell gap between filter substrate and the counter substrate (element thickness) change causes, low-temp foaming etc. cause etc. show the generation of inequality.Thus, the liquid crystal display cells of made can demonstrate distinct image.
In addition, more detailed form as liquid crystal display cells, can list the form of following formation: between at least one is a pair of supporter (comprising base plate for liquid crystal display device) of transmitance, possess liquid crystal layer and liquid crystal drive means at least, above-mentioned liquid crystal drive means have active component (for example TFT), and will be restricted to Rack between a pair of substrate by light spacer.
" display device "
Display device of the present invention possesses above-mentioned base board for display device.
Display device of the present invention owing to possess is provided with the base board for display device of the present invention of the structure that cross sectional shape and thickness (highly) have good uniformity, so can suppress to show uneven.
As display device, can list display device such as liquid crystal indicator, plasm display device, EL display device, CRT display device etc.About the definition of display device and the explanation of each display device, for example be documented in " electronic display unit (the clear husband's work of assistant 々 wood, Co., Ltd.'s census of manufacturing can be issued nineteen ninety) ", " display device (she blows along chapter work, the distribution in 1989 of industry books Co., Ltd.) " etc.
In display device, be preferably liquid crystal indicator.
The for example following formation of liquid crystal indicator: will be restricted to Rack between a pair of substrate that dispose with light spacer opposite to one anotherly, in the gap of restriction, enclose liquid crystal material (will enclose the position and be called liquid crystal layer).The thickness of liquid crystal layer (element thickness) is retained as desired uniform thickness.
As the liquid crystal display pattern of liquid crystal indicator, can preferably list STN type, TN type, GH type, ECB type, ferroelectric liquid crystals, anti ferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, other various patterns.Wherein, in liquid crystal indicator of the present invention, from bringing into play the viewpoint of effect of the present invention most effectively, be preferably easy element thickness change because of liquid crystal cells and cause the display mode that shows inequality, preferably constituting component thickness is VA type display mode, IPS type display mode, the OCB type display mode of 2～4 μ m.
In addition, as spendable liquid crystal among the present invention, can list nematic crystal, cholesteric crystal, smectic crystal, ferroelectric liquid crystals.
Basic comprising form as liquid crystal indicator, can list the form of following formation etc.: (a) will arrange driving side substrate that forms and the counter substrate that possesses opposite electrode (conductive layer) and clip light spacer and configuration relatively, and enclose liquid crystal material betwixt in the portion of crack by thin film transistor (TFT) driving elements such as (TFT) and pixel electrode (conductive layer); (b) driving substrate and the counter substrate that possesses opposite electrode (conductive layer) are clipped light spacer and configuration relatively, enclose liquid crystal material in the portion of crack betwixt.Liquid crystal indicator of the present invention can be suitable for various liquid crystal displays.
Relevant liquid crystal indicator, for example " lcd technology of future generation (Uchida Tatsuo compiles, the meeting of the side census of manufacturing, 1994 the distribution) " on the books.For liquid crystal indicator of the present invention, except possessing liquid crystal display cells of the present invention, be not particularly limited, can constitute the liquid crystal indicator of the variety of way of record in for example above-mentioned " lcd technology of future generation ".Wherein particularly effective for the liquid crystal indicator that constitutes colored TFT mode.The liquid crystal indicator of relevant colored TFT mode, on the books in for example " colored TFT liquid crystal display (altogether upright publish Co., Ltd., distribution in 1996) ".
Liquid crystal indicator generally can also use various members such as electrode base board, polarization film, phase-contrast film, backlight, light spacer, view angle compensation film, antireflective film, light diffusion film, anti-dazzle film to constitute except possessing above-mentioned light spacer, colored pattern, diaphragm, base plate for liquid crystal display device, liquid crystal display cells.Relevant these members for example are documented in " market of ' 94 liquid crystal display periphery material chemicals (island Itou Kentaro, the MC of Co., Ltd. C, distribution in 1994) ", " present situation in the related market of 2003 liquid crystal and prospect in future (last volume) (the good Ji of table, the キ メ ラ of Fuji of Co., Ltd. always grind, issued in 2003) ".
Embodiment
Below, be described more specifically the present invention by embodiment, but only otherwise exceed its purport, the present invention just is not limited to following embodiment.In addition, short of particularly pointing out, then " part " is to be benchmark with the quality.
In addition, weight-average molecular weight is to use gel permeation chromatography (GPC) to measure.Among the GPC, use HLC-8020GPC (manufacturing of TOSOH Co., Ltd.), as pillar, (TOSOH Co., Ltd. makes, 4.6mmID * 15cm), use THF (tetrahydrofuran) as eluent to use 3 TSKgel, Super Multipore HZ-H.In addition, as condition, sample solution concentration is set at 0.35 quality %, and flow velocity is set at 0.35ml/min, and the sample injection rate IR is set at 10 μ l, measures temperature and is set at 40 ℃, uses the IR detecting device to measure.In addition, " standard sample TSK standard, the polystyrene " that calibration curve is made by TOSOH Co., Ltd.: " F-40 ", " F-20 ", " F-4 ", " F-1 ", " A-5000 ", " A-2500 ", " A-1000 ", " n-propylbenzene " these 8 samples are made.
Synthesizing of＜resin (A) 〉
At first, as the resin in the photosensitive polymer combination, carry out the synthetic of resin (A) (exemplary compounds P-52, P-53, P-54, P-46, P-48, P-3).
(exemplary compounds P's-52 is synthetic)
In reaction vessel, add 7.48 parts of 1-methoxyl-2-propyl alcohol (MFG, Japanese emulsifying agent Co., Ltd. make) in advance, be warming up to 90 ℃, under nitrogen atmosphere, in 90 ℃ reaction vessel, dripped by 3.1 parts of styrene (St), the methacrylic acid three cyclopentene esters (TCPD-M that Hitachi Chemical Co., Ltd. makes with 2 hours; X) 4.28 parts, methacrylic acid (MAA; Y) 11.7 parts, azo are the mixed solution of 2.08 parts of polymerization initiators (make with the pure medicine of light Co., Ltd., V-601) and 1-methoxyl-55.2 parts of formations of 2-propyl alcohol.After the dropping, make its reaction 4 hours, obtain acrylic resin soln.
Then, in aforesaid propylene acid resin solution, add 0.34 part of 0.15 part of Hydroquinone monomethylether and tetraethylammonium bromide, then with 26.4 parts of (GLM-MAA of 2 hours dropping glycidyl methacrylate (GLM, Tokyo HuaCheng Industry Co., Ltd makes); Z).After the dropping, make its reaction 4 hours while injecting air at 90 ℃, then by adding solvent acetic acid 1-methoxyl-2-propyl ester (MMPGAc, DAICEL chemical industry Co., Ltd. makes) modulate, make solid component concentration reach 45%, obtain in having the following exemplary compounds P-51 of unsaturated group, having added resin solution (the solid constituent acid number: 76.0mgKOH/g of the exemplary compounds P-52 (resin (A)) that forms from cinnamic structural unit, Mw:25000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) (x:y:z:St=30mol%:27mol%:37mol%:6mol%).
Here, GLM-MAA is illustrated in the material (following identical) that combines glycidyl methacrylate on the methacrylic acid and obtain.
In addition, the molecular weight Mw of exemplary compounds P-52 represents weight-average molecular weight, (following identical) that the mensuration of weight-average molecular weight is to use gel permeation chromatography (GPC method) to carry out.
(exemplary compounds P's-53 is synthetic)
Except in above-mentioned exemplary compounds P-52 synthetic, not using styrene, methacrylic acid three cyclopentene esters are replaced with acrylic acid dicyclopentenyl oxidation ethyl ester (the FANCRYL FA that Hitachi Chemical Co., Ltd. makes-512A), change FA-512A (x), methacrylic acid (y), the addition of GLM-MAA (z), make that the x:y:z among the exemplary compounds P-53 is beyond the 46.2mol%:24.3mol%:29.5mol%, with synthesizing with the synthetic identical method of above-mentioned exemplary compounds P-52, obtain having resin solution (the solid constituent acid number: 71.2mgKOH/g of the exemplary compounds P-53 (resin (A)) of unsaturated group, Mw:25,500,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester).
(exemplary compounds P's-54 is synthetic)
Except in exemplary compounds P-52 synthetic, methacrylic acid three cyclopentene esters being replaced with acrylic acid two cyclopentene esters (the FANCRYL FA that Hitachi Chemical Co., Ltd. makes-511A), change FA-511A (x), methacrylic acid (y), GLM-MAA (z), the addition of styrene (St), make that the x:y:z:St among the exemplary compounds P-54 is beyond the 25mol%:25mol%:40mol%:10mol%, with synthesizing with the synthetic identical method of above-mentioned exemplary compounds P-52, obtain having resin solution (the solid constituent acid number: 78.7mgKOH/g of the exemplary compounds P-54 (resin (A)) of unsaturated group, Mw:28,000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester).
(exemplary compounds P's-46 is synthetic)
Remove in above-mentioned exemplary compounds P-52 synthetic, methacrylic acid three cyclopentene esters are replaced with ADMA (Idemitsu Kosen Co., Ltd.'s manufacturing), change ADMA (x), methacrylic acid (y), GLM-MAA (z) and cinnamic addition, make that having added in the Compound P-1 from the composition x:y:z:St behind the cinnamic structural unit is beyond the 30mol%:24mol%:38mol%:8mol%, with synthesizing with the synthetic identical method of above-mentioned exemplary compounds P-52, obtain in having the exemplary compounds P of unsaturated group-1, having added resin solution (the solid constituent acid number: 74.1mgKOH/g of the exemplary compounds P-46 (resin (A)) that forms from cinnamic structural unit, Mw:29,000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester).
(exemplary compounds P's-48 is synthetic)
Remove in above-mentioned exemplary compounds P-52 synthetic, methacrylic acid three cyclopentene esters are replaced with methacrylic acid norborneol ester, change methacrylic acid norborneol ester (x), methacrylic acid (y), GLM-MAA (z) and cinnamic addition, make that in Compound P-2 the composition x:y:z:St that adds from cinnamic structural unit is beyond the 40mol%:23mol%:35mol%:2mol%, with synthesizing with the synthetic identical method of exemplary compounds P-52, obtain in having the Compound P of unsaturated group-2, having added resin solution (the solid constituent acid number: 67.7mgKOH/g of the exemplary compounds P-48 (resin (A)) that forms from cinnamic structural unit, Mw:12,000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester).
(exemplary compounds P's-3 is synthetic)
Remove in above-mentioned exemplary compounds P-52 synthetic, do not use styrene, methacrylic acid three cyclopentene esters are replaced with cyclohexyl methacrylate, change cyclohexyl methacrylate (x), methacrylic acid (y), the addition of GLM-MAA (z), make that the x:y:z among the exemplary compounds P-3 is beyond the 45mol%:20mol%:35mol%, with synthesizing with the synthetic identical method of above-mentioned exemplary compounds P-52, obtain having resin solution (the solid constituent acid number: 74.0mgKOH/g of the exemplary compounds P-3 (resin (A)) of unsaturated group, Mw:30,700,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester).
(exemplary compounds Q's-1 is synthetic)
In reaction vessel, add 7.48 parts of 1-methoxyl-2-propyl alcohol (MFG, Japanese emulsifying agent Co., Ltd. make) in advance, be warming up to 90 ℃, under nitrogen atmosphere, with in 90 ℃ reaction vessel, dripping in 2 hours by as 4.28 parts of the above-claimed cpd M-1 (x), the methacrylic acid (MAA that are used for importing the monomer of specific ring texture at the side chain of resin; Y) 11.7 parts, azo are the mixed solution of 2.08 parts of polymerization initiators (make with the pure medicine of light Co., Ltd., V-601) and 1-methoxyl-55.2 parts of formation of 2-propyl alcohol.After the dropping, make its reaction 4 hours, obtain acrylic resin soln.
Then, in aforesaid propylene acid resin solution, add 0.34 part of 0.15 part of Hydroquinone monomethylether and tetraethylammonium bromide, then with 26.4 parts of (GLM-MAA of 2 hours dropping glycidyl methacrylate (GLM, Tokyo HuaCheng Industry Co., Ltd makes); Z).After the dropping, make its reaction 4 hours while injecting air at 90 ℃, modulate by adding solvent acetic acid 1-methoxyl-2-propyl ester (MMPGAc, DAICEL chemical industry Co., Ltd. make) then, make solid component concentration reach 45%, the resin solution (solid constituent acid number: 76.0mgKOH/g, Mw:28,000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) that obtains exemplary compounds Q-1 (resin (A)) (x:y:z=41mol%:24mol%:35mol%).
Here, GLM-MAA is illustrated in the material (following identical) that combines glycidyl methacrylate on the methacrylic acid and obtain.
In addition, the molecular weight Mw of exemplary compounds Q-1 represents weight-average molecular weight, (following identical) that the mensuration of weight-average molecular weight is to use gel permeation chromatography (GPC method) to carry out.
(exemplary compounds Q's-2 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 is replaced with beyond the above-claimed cpd M-2, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 74.0mgKOH/g, Mw:31,000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds P-2 (resin (A)).
Wherein, the addition of compound M-2, methacrylic acid and glycidyl methacrylate is the amount of 48 moles of %:22 mole %:30 mole % for making the copolymerization ratio x:y:z of exemplary compounds P-2.
(exemplary compounds Q's-3 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 is replaced with beyond the above-claimed cpd M-3, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 73.0mgKOH/g, Mw:28,000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-3 (resin (A)).
Wherein, the addition of compound M-3, methacrylic acid and glycidyl methacrylate is the amount of 45 moles of %:20 mole %:35 mole % for making the copolymerization ratio x:y:z of exemplary compounds Q-3.
(exemplary compounds Q's-4 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 is replaced with beyond the above-claimed cpd M-4, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 76.5mgKOH/g, Mw:25,500,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-4 (resin (A)).
Wherein, the addition of compound M-4, methacrylic acid and glycidyl methacrylate is the amount of 40 moles of %:25 mole %:35 mole % for making the copolymerization ratio x:y:z of exemplary compounds Q-4.
(exemplary compounds Q's-5 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 is replaced with beyond the above-claimed cpd M-5, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 77.0mgKOH/g, Mw:29,000,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-5 (resin (A)).
Wherein, the addition of compound M-5, methacrylic acid and glycidyl methacrylate is the amount of 42 moles of %:26 mole %:32 mole % for making the copolymerization ratio x:y:z of exemplary compounds Q-5.
(exemplary compounds Q's-6 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 is replaced with beyond the above-claimed cpd M-6, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 76.0mgKOH/g, Mw:27,800,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-6 (resin (A)).
Wherein, the addition of compound M-6, methacrylic acid and glycidyl methacrylate is the amount of 41 moles of %:24 mole %:35 mole % for making the copolymerization ratio x:y:z of exemplary compounds Q-6.
(exemplary compounds Q's-7 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 is replaced with beyond the above-claimed cpd M-7, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 76.0mgKOH/g, Mw:25,800,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-7 (resin (A)).
Wherein, the addition of compound M-7, methacrylic acid and glycidyl methacrylate is the amount of 48 moles of %:22 mole %:30 mole % for making the copolymerization ratio x:y:z of exemplary compounds Q-7.
(exemplary compounds Q's-36 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 (x) is replaced with above-claimed cpd M-3 (x), adding above-claimed cpd M-3 (x) and above-mentioned methacrylic acid (MAA; Y) in stage, further add methacrylic acid dicyclopentenyl oxidation ethyl ester (FANCRYL FA-512M that Hitachi Chemical Co., Ltd. makes; 1) in addition, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 76.0mgKOH/g, Mw:28,800,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-36 (resin (A)).
Wherein, the addition of FA-512M, compound M-3, methacrylic acid and glycidyl methacrylate is the amount of 23.2 moles of %:23 mole %:24.3 mole %:29.5 mole % for making the copolymerization ratio l:x:y:z of exemplary compounds Q-36.
(exemplary compounds Q's-37 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, above-claimed cpd M-1 (x) is changed to above-claimed cpd M-3 (x), adding above-claimed cpd M-3 (x) and above-mentioned methacrylic acid (MAA; Y) further add isopropyl methacrylate (i-PrMAA in stage; 1) in addition, synthetic identical with above-mentioned exemplary compounds Q-1, obtain the resin solution (solid constituent acid number: 79.0mgKOH/g, Mw:23,900,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-37 (resin (A)).
Wherein, the addition of i-PrMAA, compound M-3, methacrylic acid and glycidyl methacrylate is the amount of 25 moles of %:15 mole %:30 mole %:30 mole % for making the copolymerization ratio l:x:y:z of exemplary compounds Q-37.
(exemplary compounds Q's-31 is synthetic)
Remove in above-mentioned exemplary compounds Q-1 synthetic, adding above-claimed cpd M-1 (x) and above-mentioned methacrylic acid (MAA; Y) further add methacrylic acid two ring pentyl ester (FA-513M that Hitachi Chemical Co., Ltd. makes in stage; 1) in addition, synthetic identical with above-mentioned exemplary compounds P-1, obtain the resin solution (solid constituent acid number: 76.0mgKOH/g, Mw:25,500,45% solution of 1-methoxyl-2-propyl alcohol/acetate 1-methoxyl-2-propyl ester) of exemplary compounds Q-31 (resin (A)).
Wherein, the addition of FA-513M, compound M-1, methacrylic acid and glycidyl methacrylate is the amount of 35 moles of %:15 mole %:24 mole %:26 mole % for making the copolymerization ratio l:x:y:z of exemplary compounds Q-31.
[embodiment 1]
The making of＜filter substrate 〉
The method of opening record in paragraph [0084]～[0095] of 2005-3861 communique with the spy is made color filter with black matrix", R (redness) pixel, G (green) pixel, B (blueness) pixel (following it is called filter substrate).Here, the substrate size of filter substrate is 550mm * 650mm.
Then, on the R of the filter substrate that obtains pixel, G pixel, B pixel and black matrix", further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
Above-mentioned making pass through use spinner to carry out slot coated with coating fluid on the ito transparent electrode of filter substrate that sputter formed ito transparent electrode by the photo-sensitive resin that prescription shown in the following table 1 (being prescription 1 among the embodiment 1) constitutes.Then, use vacuum drier VCD (manufacturing of Tokyo Ying Hua company) in 30 seconds, to make the part of solvent dry, after coated film was lost flowability, prebake conditions was 3 minutes on 90 ℃ hot plate, and forming thickness is the photo-sensitive resin (tunicle formation operation) of 5.2 μ m.
Then, use have extra-high-pressure mercury vapour lamp near type exposure machine (manufacturing of the Ha イ テ of Hitachi Network Electricity ェ Application ジ ニ ア リ Application グ Co., Ltd.), make mask (having diameter is the quartzy exposed mask of the circular pattern of 15 μ m) with so that the filter substrate almost parallel that this mask mode relative with photo-sensitive resin disposes under the state that stands vertically, with the distance setting between the surface of mask face and photo-sensitive resin is 100 μ m, across this mask irradiation ultraviolet radiation, described ultraviolet ray is with 250W/m at 365nm
2Intensity see through the ultraviolet ray of ultraviolet transmission filtrator (UV-35, glass Co., Ltd. of Toshiba make) (exposure process, exposure be 200mJ/cm
2).
Then, using sodium carbonate is that developer solution (contains the sodium bicarbonate of 0.38 mol, the sodium carbonate of 0.47 mol, 5% nekal, anionic surfactant, defoamer and stabilizing agent, the product of commodity T-CD1 (Fuji Photo Film Co., Ltd.'s manufacturing) by name is diluted to 10 times and the solution that obtains with pure water), be to carry out drip washing under the condition of 0.15MPa to develop for 30 seconds at 29 ℃, conical nozzle pressure, form pattern image (developing procedure).Then, use washing agent (to contain phosphate, silicate, non-ionic surfactant, defoamer, stabilizing agent, commodity T-SD3 (Fuji Photo Film Co., Ltd.'s manufacturing) by name is diluted to 10 times and the solution that obtains with pure water), be to spray for 20 seconds with shower under the condition of 0.02MPa at 33 ℃, conical nozzle pressure, remove the residue of formed pattern image periphery, with on 300 μ m * 300 μ m at interval the mode of 1 sept form columned spacer patterns.
Then, the filter substrate that is provided with spacer patterns in 130 ℃ of following heat treated 60 minutes (heating process), is made light spacer thus on filter substrate.
Here, for 1000 resulting light spacers, (manufacturer: ZYGO company, model: New View 5022) mensuration (is parallel to 2 faces of substrate from the ito transparent electrode upper surface to use three-dimensional surface structure analysis microscope, face away from substrate-side) distance till the highest position of light spacer (below, also this distance is called " height of light spacer "), the mean value that will measure for 1000 light spacers is as the average height of light spacer.
In addition, the measurement of the floorage of resulting light spacer utilizes the SEM photo to carry out.Consequently diameter is 15.1 μ m, and average height is the cylindrical shape of 4.7 μ m.
The making of＜liquid crystal indicator 〉
In addition, prepare glass substrate, implementing the Butut that the PVA pattern is used on the transparency electrode of the above-mentioned filter substrate that obtains and on the counter substrate respectively, the alignment films that is made of polyimide further is set thereon as counter substrate.
Then, on the position of the black matrix" housing around the mode with the pixel groups of surrounding color filter of being equivalent to is arranged at, be coated with the sealant of ultraviolet curable resin by the divider mode, drip PVA pattern liquid crystal, after the counter substrate stickup, the substrate of pasting is carried out the UV irradiation, and thermal treatment makes sealant cures then.On the two sides of the liquid crystal cells that obtains like this, paste the polaroid HLC2-2518 of サ Application リ Star Star Co., Ltd. system.
Then, use FR1112H (chip-type LED that Stanley electric Co., Ltd. makes) to constitute the backlight of side lamp mode as green (G) LED, DB1112H (chip-type LED that Stanley electric Co., Ltd. makes) as blue (B) LED as red (R) LED, DG1112H (chip-type LED that Stanley electric Co., Ltd. makes), be disposed at the above-mentioned back side one side that is provided with the liquid crystal cells of polaroid, make liquid crystal indicator.
＜estimate
For resulting light spacer, liquid crystal indicator, carry out following evaluation.The results are shown in the following table 2 of evaluation of measuring.
(cross sectional shape of light spacer)
Observe formation with scanning electron microscope at above-mentioned＜light spacer〉in the cross sectional shape of light spacer after the heat treated that obtains.5 places that amount to substrate periphery portion 4 places (4 angles) and substrate center portion 1 place are observed.
And, according to the cross sectional shape of following benchmark evaluation light spacer.
Metewand
The A:5 place all forms has the light spacer that coning angle is 45 °～90 ° a cross sectional shape.
B: have the light spacer that coning angle is 45 °～95 ° a cross sectional shape though 5 places all form, do not meet above-mentioned A.
C: have the light spacer that coning angle is 40 °～100 ° a cross sectional shape though 5 places all form, do not meet among above-mentioned A and the B any.
1～4 place in the D:5 place forms the light spacer that coning angle departs from 40 °～100 ° scope.
The E:5 place all forms the light spacer that coning angle departs from 40 °～100 ° scope.
(high homogeneity of light spacer)
Formation from above-mentioned＜light spacer〉the result of height of 1000 light spacers measuring, calculate the poor of maximal value and minimum value, estimate according to following benchmark.
Difference is more little, and homogeneity is excellent more.
Metewand
A: the maximal value of the height of light spacer and the difference of minimum value are less than 0.2 μ m.
B: the maximal value of the height of light spacer and the difference of minimum value are more than the 0.2 μ m and less than 0.3 μ m.
C: the maximal value of the height of light spacer and the difference of minimum value are more than the 0.3 μ m and less than 0.4 μ m.
D: the maximal value of the height of light spacer and the difference of minimum value are more than the 0.4 μ m and less than 0.5 μ m.
E: the maximal value of the height of light spacer and the difference of minimum value are more than the 0.5 μ m.
(evaluation of heat treated condition)
Carry out the evaluation of heat treated condition according to following order.
At first, except that exposure is changed to 250mJ/cm
2Beyond exposing, with the formation of above-mentioned＜light spacer〉carry out residue treatment in the same manner after, the operation till before the heat treated, make evaluation sample with spacer patterns.
For the evaluation sample of gained, the cross sectional shape of the light spacer when being set at no heat treated and when changing each heating-up temperature and carrying out heat treated (the heat treated time was fixed as 60 minutes) and the high homogeneity of light spacer are estimated.The evaluation method of the cross sectional shape of light spacer and the high homogeneity of light spacer as mentioned above.
Based on the evaluation result of the high homogeneity of the cross sectional shape of light spacer and light spacer, carry out the evaluation of heat treated condition according to following benchmark.
In addition, in following benchmark, the state of so-called " excellent in uniformity of cross sectional shape " is meant in the metewand of the cross sectional shape of above-mentioned light spacer to be the state of A, B or C.
In addition, in following benchmark, it is the state of A, B or C that the state of so-called " excellent in uniformity of height " is meant in the metewand of the high homogeneity of above-mentioned light spacer.
Metewand
A: no heat treated obtains the homogeneity of cross sectional shape and the spacer patterns of excellent in uniformity of height.
B: heating-up temperature obtains the spacer patterns of the homogeneity and the excellent in uniformity highly of cross sectional shape less than 80 ℃.
C: heating-up temperature is more than 80 ℃ and less than 150 ℃, obtains the spacer patterns of the homogeneity and the excellent in uniformity highly of cross sectional shape.
D: heating-up temperature is more than 150 ℃ and less than 200 ℃, obtains the spacer patterns of the homogeneity and the excellent in uniformity highly of cross sectional shape.
E: heating-up temperature is more than 200 ℃, obtains the spacer patterns of the homogeneity and the excellent in uniformity highly of cross sectional shape.
(deformation-recovery rate)
Resulting light spacer with following mensuration of micro-hardness tester (DUH-W201, Shimadzu Scisakusho Ltd make), and is estimated.In the mensuration, adopt the frustum of a cone pressure head of 50 μ m φ, peak load is made as 50mN, retention time and was made as 5 seconds, with load-removing the lotus test method(s) carries out.Obtain deformation-recovery rate (%) by this measured value by following formula, estimate according to following metewand.Be determined under 22 ± 1 ℃, the environment of 50%RH and carry out.
Deformation-recovery rate (%)
=(reply volume [μ m] after load discharges/when applying load deflection [μ m]) * 100
Metewand
A: the deformation-recovery rate is more than 90%.
B: the deformation-recovery rate is more than 87% but is lower than 90%.
C: the deformation-recovery rate is more than 85% but is lower than 87%.
D: the deformation-recovery rate is more than 80% but is lower than 85%.
E: the deformation-recovery rate is more than 75% but is lower than 80%.
F: the deformation-recovery rate is lower than 75%.
(the demonstration inequality of liquid crystal indicator)
In the liquid crystal indicator of above-mentioned making, the grey during visual inspection input grey test signal shows, has or not according to following metewand evaluation inequality takes place to show.Evaluation result is shown in following table 2.
Metewand
A: show inequality, can obtain very good display image.
B: though in the marginal portion of glass substrate small inequality is arranged, to not influence of display part, display image is good.
C: see small inequality at display part, but in the scope that in practicality, allows.
D: on display part, see inequality.
(embodiment 2～12,19): rubbing method
Except that with the kind of polymerizable compound according to changing shown in the following table 2, identical with embodiment 1, make light spacer and liquid crystal indicator.
In addition, the prescription of photosensitive polymer combination is above-mentioned prescription 1 in embodiment 2～12, is above-mentioned prescription 4 in embodiment 19.
For the light spacer and the liquid crystal indicator of gained, estimate in the same manner with embodiment 1.Evaluation result is shown in table 2.
(embodiment 13～17): rubbing method
Except that with the kind of resin according to changing shown in the following table 2, identical with embodiment 1, make light spacer and liquid crystal indicator.
In addition, the prescription of photosensitive polymer combination is above-mentioned prescription 1 in embodiment 13～16, is above-mentioned prescription 2 in embodiment 17.
For the light spacer and the liquid crystal indicator of gained, estimate in the same manner with embodiment 1.Evaluation result is shown in table 2.
(embodiment 18): transfer printing
With the formula change of photosensitive polymer combination is prescription 3 in the table 1, used sept shown below transfer printing, formed photo-sensitive resin, in addition with photosensitive transfer film, identical with embodiment 1, make light spacer and liquid crystal indicator.The light spacer of gained is a cylindrical shape.For the light spacer and the liquid crystal indicator of gained, estimate in the same manner with embodiment 1.Evaluation result is shown in table 2.
＜sept the making of photosensitive transfer film 〉
At thickness is the last thermoplastic resin coating fluid that is made of following prescription A that is coated with of the interim supporter of polyethylene terephthalate film (the interim supporter of PET) of 75 μ m, makes its drying, forms the thermoplastic resin that dry bed thickness is 15.0 μ m.
The thermoplastic resin prescription A of coating fluid
Methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid copolymer ... 25.0 part
(=55/11.7/4.5/28.8[mol ratio], weight-average molecular weight be 90,000)
Styrene/acrylic acid co-polymer ... 58.4 part
(=63/37[mol ratio], weight-average molecular weight be 8,000)
2, two [4-(methacryloxy polyethoxy) phenyl] propane of 2-... 39.0 part
Following surfactant 1 ... 10.0 part
Methyl alcohol ... 90.0 part
1-methoxyl-2-propyl alcohol ... 51.0 part
MEK ... 700 parts
* surfactant 1
Following macromolecule 1 ... 30%
MEK ... 70%
Macromolecule 1
(n＝6、x＝55、y＝5、
Mw＝33940、Mw/Mn＝2.55
PO: epoxypropane EO: oxirane
Then, coating makes its drying by the middle layer coating fluid that following prescription B constitutes on the thermoplastic resin that forms, thereby stacked dry bed thickness is the middle layer of 1.5 μ m.
The middle layer prescription B of coating fluid
Polyvinyl alcohol (PVA) ... 3.22 part
(PVA-205 (saponification rate 80%), the Network ラ レ of Co., Ltd. make)
Polyvinyl pyrrolidone ... 1.49 part
(PVP K-30, ISP JAPAN Co., Ltd. make)
Methyl alcohol ... 42.3 part
Distilled water ... 524 parts
Then, further coating makes its drying by the photo-sensitive resin coating fluid that the prescription 3 shown in the above-mentioned table 1 constitutes on the middle layer that forms, thereby stacked dry bed thickness is the photo-sensitive resin of 5.0 μ m.
Constitute lit-par-lit structure (total bed thickness of 3 layers: 21.5 μ m) of the interim supporter/thermoplastic resin of PET/middle layer/photo-sensitive resin as described above, on the surface of photo-sensitive resin further by heating and pressurizing paste thickness be the polypropylene made membrane of 12 μ m as cover film, obtain the sept photosensitive transfer film.
The making of＜light spacer 〉
Peel off the cover film of resulting sept with photosensitive transfer film, the surface of the photo-sensitive resin that will expose overlaps similarly to Example 1 on the ito transparent electrode of filter substrate that the sputter of making is formed with ito transparent electrode, use laminating machine LamicII type (イ of Co., Ltd. Hitachi Application ダ ス ト リ イ ズ manufacturing), the travelling speed with 2m/ minute under line pressure 100N/cm, 130 ℃ pressurized, heated condition is pasted together them.Then, the interim supporter of PET is being removed with peeling off at the interface of thermoplastic resin, thus with photo-sensitive resin with thermoplastic resin and middle layer transfer printing (tunicle formation operation).
Then, use have extra-high-pressure mercury vapour lamp near type exposure machine (manufacturing of the Ha イ テ of Hitachi Network Electricity ェ Application ジ ニ ア リ Application グ Co., Ltd.), make mask (quartzy exposed mask) with picture pattern with so that this mask mode relative and the filter substrate almost parallel that disposes with thermoplastic resin under the state that stands vertically, with mask face and the distance setting that contacts with the middle layer of photo-sensitive resin between the surface of a side is 100 μ m, across this mask from the thermoplastic resin side with 150mJ/cm
2Exposure carry out near the exposure (exposure process).
Then, with triethanolamine is that developer solution (contains 30% triethanolamine, the solution that the product of commodity T-PD2 (Fuji Photo Film Co., Ltd.'s manufacturing) by name is diluted to 12 times (mixing with the ratio of 11 parts of pure water with 1 part of T-PD2) with pure water and obtains) under 30 ℃, flat burner pressure are the condition of 0.04MPa, carry out drip washing and developed for 50 seconds, remove thermoplastic resin and middle layer.Then, the upper surface of this glass substrate is blowed air with after removing liquid, spray 10 seconds of pure water with shower, carry out pure water drip washing, blow air is accumulated with the liquid that reduces on the substrate.Then, using sodium carbonate is that developer solution (contains the sodium bicarbonate of 0.38 mol, the sodium carbonate of 0.47 mol, 5% nekal, anionic surfactant, defoamer and stabilizing agent, the product of commodity T-CD1 (Fuji Photo Film Co., Ltd.'s manufacturing) by name is diluted to 10 times and the solution that obtains with pure water), be to carry out drip washing under the condition of 0.15MPa to develop for 30 seconds at 29 ℃, conical nozzle pressure, form pattern image (developing procedure).
Then, use washing agent (to contain phosphate, silicate, non-ionic surfactant, defoamer, stabilizing agent, trade name: T-SD3 (Fuji Photo Film Co., Ltd.'s manufacturing) is diluted to 10 times and the solution that obtains with pure water), be to spray for 20 seconds with shower under the condition of 0.02MPa at 33 ℃, conical nozzle pressure, remove the residue of formed pattern image periphery, with on 300 μ m * 300 μ m at interval the mode of 1 sept form columned spacer patterns.
Then, the filter substrate that is provided with spacer patterns in 130 ℃ of following heat treated 60 minutes (tunicle heating process), is made light spacer thus on filter substrate.Resulting light spacer is that diameter is that 15.1 μ m, average height are the cylindrical shape of 4.7 μ m.
Then, use the filter substrate of light spacer, make the PVA mode LCD similarly to Example 1.
(comparative example 1)
Except that polymerizable compound being changed to following comparative compound Z-1, identical with embodiment 1, make light spacer and liquid crystal indicator.For light spacer and liquid crystal indicator, estimate in the same manner with embodiment 1.Evaluation result is shown in table 2.
Comparative compound Z-1
(comparative example 2)
Remove by composition and change to prescription 5, polymerizable compound is changed to DPHA (dipentaerythritol acrylate) in addition thus photosensitive polymer combination, identical with embodiment 1, make light spacer and liquid crystal indicator.For light spacer and liquid crystal indicator, estimate in the same manner with embodiment 1.Evaluation result is shown in table 2.
(embodiment 20～29)
Remove in the formation of light spacer, is the prescription 6 shown in the above-mentioned table 1 with photo-sensitive resin with the formula change of coating fluid, and beyond the kind of resin (A) changed shown in above-mentioned table 2, identical with embodiment 1, make light spacer and liquid crystal indicator.For the light spacer and the liquid crystal indicator of gained, estimate in the same manner with embodiment 1.Evaluation result is shown in table 2.
(embodiment 30): rubbing method
Remove in embodiment 20, photo-sensitive resin is changed to beyond the prescription 7 with the prescription 6 of prescription from table 1 of coating fluid, identical with embodiment 20, making light spacer and liquid crystal indicator.To the sept and the liquid crystal indicator of gained, estimate in the same manner with embodiment 20.Evaluation result is shown in table 2.
(embodiment 31): transfer printing
Remove in embodiment 20, replace the coating of photo-sensitive resin with coating fluid (prescription 6), use with embodiment 18 in same sept with the transfer printing of photosensitive transfer film, form beyond the photo-sensitive resin thus, identical with embodiment 20, make light spacer and liquid crystal indicator.The light spacer of gained is a cylindrical shape.For the light spacer and the liquid crystal indicator of gained, estimate in the same manner with embodiment 20.Evaluation result is shown in table 2.
(comparative example 3)
Remove in embodiment 20, resin (A) is changed to beyond the synthetic comparative compound Z-2 as described below, identical with embodiment 20, make light spacer and liquid crystal indicator.To the light spacer and the liquid crystal indicator of gained, estimate in the same manner with embodiment 20.Evaluation result is shown in table 2.
(comparative compound Z's-2 is synthetic)
The mixed solvent that in reaction vessel, adds 1-methoxyl-2-propyl alcohol 25g and acetate 1-methoxyl-2-propyl ester 25g in advance, be warming up to 90 ℃, under nitrogen atmosphere, in 90 ℃ reaction vessel, dripped by styrene (1) 32.1g, methacrylic acid (MAA with 2 hours; Y) 36.5g, azo are the mixed solution that polymerization initiator (with the pure medicine of light Co., Ltd. system, V-601) 6.73g, 1-methoxyl-2-propyl alcohol 25g and acetate 1-methoxyl-2-propyl ester 25g constitute.Make its reaction 4 hours after the dropping, obtain acrylic resin soln.
Then, in aforesaid propylene acid resin solution, add Hydroquinone monomethylether 0.5g and tetraethylammonium bromide 0.015g, then with 2 hours dropping glycidyl methacrylate 31.3g (GLM-MAA; Z).After the dropping, make its reaction 4 hours at 90 ℃, obtain the solution of comparative compound Z-2 (y:z:l=45mol%:23mol%:32mol%, Mw:12000) while inject air.Solid constituent in the solution of this comparative compound Z-2 is 50%.
Comparative compound Z-2
(comparative example 4): rubbing method
Remove in embodiment 20, photo-sensitive resin is changed to beyond the prescription 9 with the prescription 6 of prescription from table 1 of coating fluid, identical with embodiment 20, making light spacer and liquid crystal indicator.For the light spacer and the liquid crystal indicator of gained, estimate in the same manner with embodiment 20.Evaluation result is shown in table 2.
In the table 2, symbolic representation exemplary compounds such as M-1, P-52, the Z-1 on polymerizable compound hurdle and resin hurdle numbering or comparative compound numbering.
In addition, the dipole moment on polymerizable compound hurdle is the value that (Fujitsu Ltd.'s manufacturing) obtains according to Scigress Explorer ProfessionalVersion 7.6.0.52.
As shown in table 2, the light spacer of embodiment has the homogeneity of excellent cross sectional shape and the homogeneity of height.In addition, in possessing the liquid crystal indicator of light spacer, suppressed to show inequality.
(embodiment 32)
The formation of＜diaphragm 〉
Among the embodiment 10; in the making of filter substrate; after forming black matrix", R pixel, G pixel and B pixel; on black matrix" and each pixel, further be coated with the photosensitive polymer combination that constitutes by above-mentioned prescription 1; staying out of under the situation of mask expose (whole exposure), form diaphragm after the heat treated.Here, the condition of coating, exposure, heat treated is, except stay out of expose under the situation of mask, identical with the condition of coating during the light spacer of embodiment 10 forms, exposure, heat treated.
Then, on resulting protective seam, further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
Except on the ito transparent electrode of above-mentioned formation, use the photosensitive polymer combination that uses among the embodiment 10 as beyond the photosensitive polymer combination, with method formation light spacer similarly to Example 10.
The making of＜liquid crystal indicator and evaluation 〉
Then, use the filter substrate that is formed with above-mentioned light spacer, make liquid crystal indicator with method similarly to Example 10.
For resulting diaphragm and liquid crystal indicator, estimate with method similarly to Example 1.Evaluation result is shown in Table 3.
(embodiment 33)
The formation of＜diaphragm 〉
Among the embodiment 27; in the making of filter substrate; after forming black matrix", R pixel, G pixel and B pixel; on black matrix" and each pixel, further be coated with the photosensitive polymer combination that constitutes by above-mentioned prescription 6; staying out of under the situation of mask expose (whole exposure), form diaphragm after the heat treated.Here, the condition of coating, exposure, heat treated is, except stay out of expose under the situation of mask, identical with the condition of coating during the light spacer of embodiment 27 forms, exposure, heat treated.
Then, on resulting protective seam, further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
Except on the ito transparent electrode of above-mentioned formation, use the photosensitive polymer combination that uses in the comparative example 4 as beyond the photosensitive polymer combination, with method formation light spacer similarly to Example 20.
The making of＜liquid crystal indicator and evaluation 〉
Then, use the filter substrate that is formed with above-mentioned light spacer, make liquid crystal indicator with method similarly to Example 1.
For resulting diaphragm and liquid crystal indicator, estimate with method similarly to Example 1.The mensuration of the film thickness uniformity of diaphragm is measured by the method identical with the elevation measurement of the light spacer of embodiment 1.Evaluation result is shown in Table 3.
(embodiment 34)
The formation of＜colored pattern 〉
Except in embodiment 11, in the making of filter substrate,, make filter substrate similarly to Example 11 with beyond the following method formation R pixel.
That is, in above-mentioned prescription 1, further add paratonere 254 (19.4 parts) and paratonere 177 (4.83 parts), modulation R pixel photosensitive polymer combination.
Except using the R pixel modulated to use the R pixel with the photomask, use with the same method of the formation method of the light spacer of embodiment 11 and form the R pixel with photosensitive polymer combination and as photomask.
After R pixel, G pixel and the B pixel of the filter substrate of made form, on each pixel, further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
Except on the ito transparent electrode of above-mentioned formation, use the photosensitive polymer combination that in embodiment 11, uses as photosensitive polymer combination beyond, form light spacer with similarly to Example 11 method.
The making of＜liquid crystal indicator and evaluation 〉
Then, use the filter substrate that is formed with above-mentioned light spacer, make liquid crystal indicator with method similarly to Example 11.
For resulting diaphragm and liquid crystal indicator, estimate with method similarly to Example 1.Evaluation result is shown in Table 3.
(embodiment 35)
The formation of＜colored pattern 〉
Except in embodiment 20, in the making of filter substrate,, make filter substrate similarly to Example 20 with beyond the following method formation R pixel.
That is, in above-mentioned prescription 6, further add paratonere 254 (19.4 parts) and paratonere 177 (4.83 parts), modulation R pixel photosensitive polymer combination.
Except using the R pixel modulated to use the R pixel with the photomask, use with the same method of the formation method of the light spacer of embodiment 20 and form the R pixel with photosensitive polymer combination and as photomask.
After R pixel, G pixel and the B pixel of the filter substrate of made form, on each pixel, further form the transparency electrode of ITO (tin indium oxide) by sputter.
The formation of＜light spacer 〉
Except on the ito transparent electrode of above-mentioned formation, use the photosensitive polymer combination that in comparative example 4, uses as photosensitive polymer combination beyond, form light spacer with similarly to Example 20 method.
The making of＜liquid crystal indicator and evaluation 〉
Then, use the filter substrate that is formed with above-mentioned light spacer, make liquid crystal indicator with method similarly to Example 1.
For resulting diaphragm and liquid crystal indicator, estimate with method similarly to Example 1.Evaluation result is shown in Table 3.
[comparative example 5,6]
In the comparative example 5; except that the polymerizable compound M-10 that uses polymerizable compound Z-1 replacement embodiment 10; in addition; in the comparative example 6; except that the polymerizable compound M-13 that uses DPHA replacement embodiment 11; make diaphragm, coloured material in the same manner with embodiment 10 and 11 respectively, obtain colored pattern and liquid crystal indicator, estimate in the same manner.
[comparative example 7,8]
In the comparative example 7 and 8, except that the prescription 6 that uses prescription 9 to replace among the embodiment 33 and 35, make diaphragm, coloured material in the same manner respectively with embodiment 33 and 35 respectively, obtain colored pattern and liquid crystal indicator, estimate in the same manner.
Table 3
[table 3] continues embodiment 33,35, comparative example
As shown in table 3, using photosensitive polymer combination of the present invention to form under the situation of diaphragm and colored pattern, also can obtain and same good result when forming light spacer.
Claims (15)
1, a kind of photosensitive polymer combination, it contains resin, dipole moment is above polymerizable compound and Photoepolymerizationinitiater initiaters of 3.50 debye.
2, photosensitive polymer combination according to claim 1, wherein, described polymerizable compound has the ring texture and the ethylenic unsaturated double-bond of 5 yuan or 6 yuan, and the ring texture of described 5 yuan or 6 yuan has bond sites that contains C=O and/or the bond sites that contains P=O.
3, photosensitive polymer combination according to claim 1, wherein, described resin has branched structure and/or alicyclic structure, acidic groups and ethylenic unsaturated link on side chain.
4, photosensitive polymer combination according to claim 1, wherein, described polymerizable compound has the ring texture and the ethylenic unsaturated double-bond of 5 yuan or 6 yuan, and the ring texture of described 5 yuan or 6 yuan has bond sites that contains C=O and/or the bond sites that contains P=O; Described resin has branched structure and/or alicyclic structure, acidic groups and ethylenic unsaturated link on side chain.
5, a kind of photosensitive polymer combination, it contains resin, polymerizable compound and Photoepolymerizationinitiater initiater, and described resin has 5 yuan or 6 yuan ring texture, acidic groups and the ethylenic unsaturated link at the position that comprises the position represented by C=O and/or represented by P=O on side chain.
6, photosensitive polymer combination according to claim 5, wherein, described resin also has branching and/or alicyclic structure on side chain.
7, photosensitive polymer combination according to claim 5, wherein, at least a kind of described polymerizable compound has 5 yuan or 6 yuan the ring texture and the ethylenic unsaturated double-bond at the position that comprises the position represented by C=O and/or represented by P=O.
8, photosensitive polymer combination according to claim 5, wherein, described resin also has branching and/or alicyclic structure on side chain; At least a kind of described polymerizable compound has 5 yuan or 6 yuan the ring texture and the ethylenic unsaturated double-bond at the position that comprises the position represented by C=O and/or represented by P=O.
9, a kind of light spacer, it is to use, and each described photosensitive polymer combination forms in the claim 1～8.
10, a kind of formation method of light spacer, it comprises following operation (1)～(3) at least:
(1) on substrate, forms the operation of the tunicle of each described photosensitive polymer combination in the claim 1～8;
(2) operation that at least a portion of described tunicle is exposed;
(3) described after will exposing by the operation of film development.
11, the formation method of light spacer according to claim 10, wherein, described formation method comprises that also the maximum temperature of this heating is 40 ℃～145 ℃ with the operation of the described tunicle heating after developing.
12, a kind of diaphragm, it is to use, and each described photosensitive polymer combination forms in the claim 1～8.
13, a kind of colored pattern, it is to use, and each described photosensitive polymer combination forms in the claim 1～8.
14, a kind of base board for display device; it possesses at least a in light spacer, diaphragm and the colored pattern, and described light spacer, described diaphragm and described colored pattern are to use that each described photosensitive composite forms in the claim 1～8.
15, a kind of display device, it possesses the described base board for display device of claim 14.
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| JP016890/2008 | 2008-01-28 | ||
| JP2008016890A JP5191244B2 (en) | 2008-01-28 | 2008-01-28 | Photosensitive resin composition, photospacer and method for forming the same, protective film, coloring pattern, substrate for display device, and display device |
| JP027994/2008 | 2008-02-07 |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2604715B1 (en) * | 1986-10-02 | 1988-11-25 | Poudres & Explosifs Ste Nale | METHOD FOR MANUFACTURING RADIORETICULATION COATINGS |
| FR2649111B1 (en) * | 1989-06-29 | 1991-09-13 | Poudres & Explosifs Ste Nale | METHOD FOR MANUFACTURING RADIORETICULATING COATINGS, NEW RADIORETICULABLE COMPOSITIONS AND NEW CARBONATES |
| JP2004514759A (en) * | 2000-11-22 | 2004-05-20 | ディーエスエム エヌ．ブイ． | Irradiation-curable composition |
| JP2002293837A (en) * | 2001-03-30 | 2002-10-09 | Dainippon Printing Co Ltd | Hardenable resin and its production method |
| WO2008026465A1 (en) * | 2006-08-30 | 2008-03-06 | Konica Minolta Medical & Graphic, Inc. | Photosensitive lithographic printing plate material |
| US8362103B2 (en) * | 2007-05-11 | 2013-01-29 | Mitsui Chemicals, Inc. | Resin composition, dry film, and processed product made using the same |
-
2008
- 2008-01-28 JP JP2008016890A patent/JP5191244B2/en not_active Expired - Fee Related
-
2009
- 2009-01-23 CN CNA2009100096183A patent/CN101498894A/en active Pending
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| CN102789020B (en) * | 2011-05-19 | 2016-07-06 | Jsr株式会社 | The manufacture method of colored filter, liquid crystal display cells and colored filter |
| CN102955188A (en) * | 2011-08-17 | 2013-03-06 | Jsr株式会社 | Color filter, liquid crystal display element, and method for producing the color filter |
| CN102955188B (en) * | 2011-08-17 | 2015-12-09 | Jsr株式会社 | The manufacture method of colored filter, liquid crystal display cells and colored filter |
| CN107272341A (en) * | 2016-03-31 | 2017-10-20 | 新日铁住金化学株式会社 | Photomask photosensitive polymer combination, base plate for displaying and its manufacture method |
| CN107272341B (en) * | 2016-03-31 | 2022-04-01 | 日铁化学材料株式会社 | Photosensitive resin composition for light-shielding film, substrate for display, and method for producing same |
| CN114690473A (en) * | 2020-12-31 | 2022-07-01 | 上海仪电显示材料有限公司 | Color filter substrate, liquid crystal box and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5191244B2 (en) | 2013-05-08 |
| JP2009175647A (en) | 2009-08-06 |
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Application publication date: 20090805 |