CN1325477C - Hexaarylbiimidazole compounds and photopolymerization initiator compositions containing the same - Google Patents
Hexaarylbiimidazole compounds and photopolymerization initiator compositions containing the same Download PDFInfo
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- CN1325477C CN1325477C CNB2003801014251A CN200380101425A CN1325477C CN 1325477 C CN1325477 C CN 1325477C CN B2003801014251 A CNB2003801014251 A CN B2003801014251A CN 200380101425 A CN200380101425 A CN 200380101425A CN 1325477 C CN1325477 C CN 1325477C
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- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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Abstract
The present invention provides a novel hexaarylbiimidazole compound of the following formula (1): wherein each R>1< represents a halogen, and each R>2< represents an optionally substituted C<1-4> alkyl group. The hexaarylbiimidazole compound of the present invention is useful as photoradical generators in photopolymerizable compositions used as resists and is characterized by low sublimating thermal decomposition products. The photopolymerizable compositions may be suitably used as resists or as color filters for color liquid crystal display elements, cameras and the like.
Description
The cross reference of relevant application
The application is the application documents according to 35U.S.C. § 111 (a) application, according to 35U.S.C. § 119 (e), requires the applying date of the provisional application 60/419,093 of application on October 18th, 2002, and this provisional application proposes according to 35 U.S.C. § 111 (b).
Invention field
The present invention relates to new Hexaarylbiimidazole compound.More particularly, the present invention relates to and in being used as the photopolymerizable composition of resist, to produce the Hexaarylbiimidazole compound that agent is used as optical free radical, and it is characterized by the pyrolysis product of low distillation, relate to the photopolymerization initiator composition that contains optical free radical generation agent and relate to the photopolymerizable composition that utilizes them.Photopolymerizable composition of the present invention is suitable for use as resist or is used as the colored filter of color liquid crystal display device, photographic camera etc.
Background of invention
Photopolymerizable composition (photosensitive composition) is widely used for some fields, comprises resist field (photoresist, solder resist, anti-etching dose, or the like).
In recent years, particularly the requirement for the photopolymerizable composition that can be used as the use of colored filter resist improves, and said composition will satisfy stability, high resolving power and high heat resistance and the sunproof requirement that comprises highly sensitive, prolongation for outstanding characteristic at the colored filter that is used for colour liquid crystal display device, color video camera or the like.
Colored filter is normally by for example forming black matix on the surface of glass in transparent substrates, forms for example red, green and blue three kinds or more kinds of colored striped mutually or mosaic pattern then to reach several microns precision.
A kind of typical production method of colored filter is exactly to utilize the colo(u)rant dispersion method of coloured composition, and this coloured composition is by preparing colo(u)rant dispersion in photosensitive composition.Because the precision height of the colored filter location of pixels of colo(u)rant dispersion method and film thickness, wearing quality (comprising photostabilization and thermotolerance) is outstanding and production rate defective (for example aperture) is low, it is widely used.
The colo(u)rant dispersion method contains the photosensitive composition of pigment and utilizes photoetch method by applying in substrate, forms various color layers according to the appointed pattern pattern.Particularly, it is for example on glass that the photosensitive composition that will be used for a kind of color filter color is coated in transparent substrates, and make it carry out pattern exposure, by developing with solvent or alkaline aqueous solution unexposed part removed, and forms first kind of multi color pattern.Then all color filter colors are repeated this method, to finish the manufacturing of colored filter.Consider the character of colored filter and many materials, photosensitive composition is the negativity type normally, and for fear of environmental problem, with an organic solvent develops hardly, and promptly most of photographic developers are to use the alkaline-based developer of alkaline aqueous solution.
In these production stages, drying after development step is (the back oven dry) that is in daily use.That is to say that after development treatment, the transparent substrates that will have the curing photoactive layer (having another name called color layer, pixel layer or resist layer) of formed pattern was for example heating (oven dry) about 10-120 minute under about 160-250 ℃.The wearing quality of color layer with chemistry and physics given in the back oven dry.
Yet the conventional photosensitive composition that is used for resist usually produces distillation during the oven dry after developing.These sublimates stick on the vapor pipe etc., and in case adhere to, and will drop on the resist layer and give rise to trouble.This instructs people to want to develop even the photosensitive composition, particularly development that can anti-sublimate during baking step generate use the photosensitive composition of the Photoepolymerizationinitiater initiater of high sensitive, low distillation.
Is known (referring to following patent documentation 1) based on the compound of Hexaarylbiimidazole as the purposes of the component of the photopolymerization initiator composition that is used for photosensitive composition, for example, use 2,2 '-two (2-chloro-phenyl-s)-4,4 '-5,5 '-tetraphenyl-1,2 '-diimidazole (HABI) is as the photosensitive composition of colored filter, by following formula (4) expression, it is disclosed among open HEI No.6-75372 (referring to following patent documentation 2) of Japanese unexamined patent publication No. and the open No.2000-249822 (referring to following patent documentation 3) of Japanese unexamined patent publication No. as the component in the photopolymerization initiator composition.Yet the distillation problem during the oven dry of back does not relate in these documents, certainly, does not propose the substituent Hexaarylbiimidazole compound of the present invention that has that can address this problem yet.
[patent documentation 1]
Japan has examined patent disclosure SHO No.45-37277
[patent documentation 2]
The open HEI No.06-075373[patent documentation 3 of Japanese unexamined patent publication No.]
The open No.2000-249822 of Japanese unexamined patent publication No.
Summary of the invention
The purpose of this invention is to provide optical free radical and produce agent, use their photopolymerization initiator composition and even during baking step, produce sublimate seldom and be particularly suitable for the photopolymerizable composition of colored filter with highly sensitive and low distillation.
Through effort research for the problems referred to above, the inventor finds to adhere to vapor pipe during the oven dry of back sublimate be included in the photopolymerization initiator composition of photosensitive composition, as the pyrolysis product crystallization based on the Hexaarylbiimidazole compound of Photoepolymerizationinitiater initiater, and finished the present invention, find the photopolymerization initiator composition of the problems referred to above can be by producing agent as optical free radical new Hexaarylbiimidazole compound and overcome by the photopolymerizable composition that comprises them with ad hoc structure.
In other words, the invention provides the Hexaarylbiimidazole compound according to following [1] to [8], the optical free radical that comprises them produces agent, uses this optical free radical to produce the photopolymerization initiator composition of agent and contains their photopolymerizable composition.
[1] as shown in the formula (1) defined Hexaarylbiimidazole compound:
Each R wherein
1Represent halogen atom, each R
2The optional substituted C of representative
1-4Alkyl.
[2] as shown in the formula (2) defined Hexaarylbiimidazole compound:
[3] use is characterized in that producing agent used as optical free radical according to the method for the Hexaarylbiimidazole compound of [1] or [2].
[4] a kind of photopolymerization initiator composition, it contains the Hexaarylbiimidazole compound according to [1].
[5] according to the photopolymerization initiator composition of [4], it is characterized in that it contains one or more and be selected from following compound: based on the compound of benzophenone, based on the compound of thioxanthone with based on the compound of ketone group tonka bean camphor.
[6], it is characterized in that it contains mercaptan compound and/or as shown in the formula the hydrogen donor of (3) defined dicarbonyl compound as the Hexaarylbiimidazole compound according to the photopolymerization initiator composition of [4]:
R wherein
3And R
4Each represents the optional alkyl that replaces independently, the optional alkoxyl group that replaces, the optional amino that replaces, the optional aralkyl that replaces, the optional aryl that replaces, the optional aryloxy that replaces, or have the organic group of polymerisable unsaturated group or polymer residue or a R
3And R
4Can be bonded together and form ring.R
5Represent hydrogen, the optional alkyl that replaces, the optional aralkyl that replaces or the optional aryl that replaces.
[7] a kind of photopolymerizable composition is characterized in that it comprises following component at least:
(A) according to each the photopolymerization initiator composition of [4] to [6]; With
(B) have the compound of ethylenically unsaturated group.
[8] a kind of photopolymerizable composition that is used for the colored filter resist is characterized in that it comprises following component at least:
(A) according to each the photopolymerization initiator composition of [4] to [6]; With
(B) have the compound of ethylenically unsaturated group.
Brief description of drawings
Fig. 1 is MHABI
1The H-NMR spectrum.
Fig. 2 is MHABI
13The C-NMR spectrum.
Fig. 3 is (amplification) MHABI's
13The C-NMR spectrum.
Fig. 4 is the mass spectrum of mHABI.
Fig. 5 is the stainless photo of the heating among the embodiment 1.
Fig. 6 is the stainless photo of the heating among the comparative example 1.
Detailed description of the invention
2,2 '-two (2-chlorphenyls)-4,4 '-5,5 '-tetraphenyl-1,2 '-diimidazole (formula (4), be abbreviated as HABI), be typically used as component for the photopolymerization initiator composition of photosensitive composition as the Hexaarylbiimidazole compound, during post-drying, carry out thermal decomposition become below the compound of formula (5) expression. This compound very easily distils, and its crystal adheres to blast pipe easily.
The present invention is the compound of at first finding in finishing process of the present invention by the Hexaarylbiimidazole compound of formula (1) representative. Different from HABI, being characterized as of the catabolite of these compounds of formula (1) representative is difficult for distillation, therefore is difficult for crystallization at blast pipe during post-drying. According to the present invention, find that at first these new Hexaarylbiimidazole compounds can be used for producing as optical free radical the photosensitive composition of agent, avoiding at Binding during the post-drying on blast pipe, and therefore prevented by the caused trouble of such crystal.
To describe embodiment of the present invention in detail now.
1. Hexaarylbiimidazole compound
Hexaarylbiimidazole compound of the present invention is represented by following formula (1):
Each R wherein
1Represent halogen, each R
2The optional C that replaces of representative
1-4Alkyl.
In formula (1), as R
1The preferred chlorine of halogen.Each R
2The optional C that replaces of representative
1-4Alkyl, preferable methyl, ethyl or sec.-propyl, more preferably methyl.As R
2Substituting group may mention be: methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy or the like.
By having that particularly preferred compound in the Hexaarylbiimidazole compound of formula (1) representative may be mentioned: by 2,2 '-two (2-chloro-phenyl-)-4,4 '-5,5 '-four (4-aminomethyl phenyls)-1,2 of following formula (2) representative '-diimidazole (MHABI):
Hexaarylbiimidazole compound of the present invention can be produced agent as optical free radical suitably at the photosensitive composition (photopolymerizable composition) that is used for highly sensitive colored filter etc.
2. photopolymerization initiator composition
2-(1) Hexaarylbiimidazole compound
According to being characterized as of photopolymerization initiator composition of the present invention: comprise any Hexaarylbiimidazole compound by top formula (1) representative.Blending ratio for the Hexaarylbiimidazole compound in photopolymerization initiator composition has no particular limits, but preferred 20-60 weight %, and more preferably 30-50 weight %.If the ratio of Hexaarylbiimidazole compound is too low, then the amount of free radical generation reduces, and has weakened photosensitivity thus or has caused the curing of photopolymerizable composition insufficient sometimes.If consumption is too high, the relative content of sensitizing agent or hydrogen donor reduces, and can cause undesirable minimizing of photosensitivity equally.
Photopolymerization initiator composition of the present invention can also comprise be generally used for photopolymerization initiator composition other component (for example, hydrogen donor, sensitizing agent, fill-in light polymerization starter, or the like), this without any concrete restriction, is needed only it and contain Hexaarylbiimidazole compound described above as basal component.Such component can be introduced, demonstrating repertoire as Photoepolymerizationinitiater initiater, but the compound below preferred the adding.
2-(2) one or more be selected from compound based on benzophenone, based on the compound of thioxanthone and
Based on the compound in the compound of ketone group tonka bean camphor
In order to improve susceptibility, photopolymerization initiator composition of the present invention preferably uses one or more to be selected from following compound as sensitizing agent: based on the compound of benzophenone, based on the compound of thioxanthone with based on the compound of ketone group tonka bean camphor.
Example based on the compound of benzophenone can be mentioned: benzophenone, 2; 4; 6-tri-methyl benzophenone, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4,4 '-two (dimethylamino) benzophenone and 4,4 '-two (diethylamino) benzophenone.
Example based on the compound of thioxanthone can be mentioned: thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-di-isopropyl thioxanthone and 2-chloro thioxanthone.
Example based on the compound of ketone group tonka bean camphor can be mentioned: 3-ethanoyl tonka bean camphor, 3-ethanoyl-7-diethyl amino coumarin, 3-benzoyl tonka bean camphor, 3-benzoyl-7-diethyl amino coumarin, 3-benzoyl-ayapanin, 3; 3 '-carbonyl diurethane tonka bean camphor, 3; 3 '-carbonyl diurethane (ayapanin) and 3; 3 '-carbonyl diurethane (5, the 7-escoparone).
Blending ratio for the sensitizing agent in photopolymerization initiator composition has no particular limits, but is preferably the 5-40 weight % of photopolymerization initiator composition total amount, and more preferably 10-30 weight %.If ratio of mixture is too low, possible desensitising, however if ratio is too high, enough light can not reach the lower part of resist, can cause the curing of those parts insufficient.
2-(3) mercaptan compound and/or carbonyl compound
Photopolymerization initiator composition of the present invention can use mercaptan compound and/or carbonyl compound as the hydrogen donor that is used for above-mentioned Hexaarylbiimidazole compound equally.
[1] mercaptan compound
Have no particular limits for being used for mercaptan compound of the present invention,, and can select to be generally used for any mercaptan compound of photopolymerization initiator composition as required as long as it is the compound that has thiol group in the molecule.
The example of such mercaptan compound can be mentioned: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, the 2-mercaptobenzoxazole, 5-chloro-2-mercaptobenzothiazole, 2-sulfydryl-5-methoxyl group benzo thiazole, the 5-methyl isophthalic acid, 3,4-thiadiazoles-2-mercaptan, 5-sulfydryl-1-methyl tetrazolium, 3-sulfydryl-4-methyl-4H-1,2, the 4-triazole, 2-sulfydryl-1-Methylimidazole, 2-mercaptothiazoline, spicy thioalcohol, ethanthiol, the last of the ten Heavenly stems two mercaptan, 1,4-dimethyl sulfydryl benzene, 1,4-butyleneglycol two (3-mercaptopropionic acid ester), 1,4-butyleneglycol two (mercaptoacetate), ethylene glycol bisthioglycolate (3-mercaptopropionic acid ester), glycol dimercaptoacetate, trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris (mercaptoacetate), tetramethylolmethane four (3-mercaptopropionic acid ester) and tetramethylolmethane four (mercaptoacetate).
Viewpoint from the stability in storage of photopolymerizable composition, the particularly preferred mercaptan compound of the present invention comprises: the α of thiol group-and/or β-carbon on have the mercaptan compound of branched structure, or has wherein α at thiol group-and/or " side chain " mercaptan compound of β-carbon and the structure of 3 atomic linkages except hydrogen, for example can mention such mercaptan compound, wherein at least one α with respect to mercaptan-and/or the non-main chain substituting group of β-position be alkyl.Here, the structure of the long-chain that comprises thiol group formed by non-hydrogen atom of main chain representative.
In these compounds, particularly preferably be, wherein contain the mercaptan compound of the structure division of thiol group by following formula (6) representative:
-(CH
2)
mC(R
6)(R
7)(CH
2)
nSH (6)
(R wherein
6And R
7Each represents hydrogen or alkyl independently, and condition is R
6And R
7Two not all is hydrogen, and m represents the integer of 0-2, and n represents 0 or 1 integer.)
Here, the alkyl (R in formula (6)
6Or R
7) straight or branched C preferably
1-3Alkyl.Particularly, that may mention has: methyl, ethyl, n-propyl, sec.-propyl or the like, more preferably methyl or ethyl.
From improving the viewpoint of photosensitivity, be used for multi-functional thiol's compound that mercaptan compound of the present invention more preferably has two or more sulfydryls, and, especially preferably has multi-functional thiol's compound of structure shown in the formula of the present invention (6) for photosensitivity and the stability in storage that reaches photosensitive composition.Particularly, can mention following compound.
The example of hydrocarbon two mercaptan comprises 2,5-ethanthiol, 2,9-mercaptan in the last of the ten Heavenly stems two, 1,4-two (1-mercaptoethyl) benzene or the like.
Contain having that the compound of ester bond structure can mention: phthalic acid two (1-sulfydryl ethyl ester), phthalic acid two (2-sulfydryl propyl ester), phthalic acid two (3-sulfydryl butyl ester), phthalic acid two (3-sulfydryl isobutyl), ethylene glycol bisthioglycolate (3-sulfydryl butyric ester), Diethylene Glycol two (3-sulfydryl butyric ester), propylene glycol two (3-sulfydryl butyric ester), 1,4-butyleneglycol two (3-sulfydryl butyric ester), 1,3-butyleneglycol two (3-sulfydryl butyric ester), 1,2-butyleneglycol two (3-sulfydryl butyric ester), trimethylolpropane tris (3-sulfydryl butyric ester), tetramethylolmethane four (3-sulfydryl butyric ester), Dipentaerythritol six (3-sulfydryl butyric ester), ethylene glycol bisthioglycolate (2-mercaptoisobutyric acid ester), Diethylene Glycol two (2-mercaptoisobutyric acid ester), propylene glycol two (2-mercaptoisobutyric acid ester), 1,4-butyleneglycol two (2-mercaptoisobutyric acid ester), trimethylolpropane tris (2-mercaptoisobutyric acid ester), tetramethylolmethane four (2-mercaptoisobutyric acid ester), Dipentaerythritol six (2-mercaptoisobutyric acid ester), ethylene glycol bisthioglycolate (3-mercaptoisobutyric acid ester), Diethylene Glycol two (3-mercaptoisobutyric acid ester), propylene glycol two (3-mercaptoisobutyric acid ester), 1,4-butyleneglycol two (3-mercaptoisobutyric acid ester), trimethylolpropane tris (3-mercaptoisobutyric acid ester), tetramethylolmethane four (3-mercaptoisobutyric acid ester) and Dipentaerythritol six (3-mercaptoisobutyric acid ester).
These mercaptan compounds can use separately or two or more mix use.
When using such mercaptan compound, there is not special restriction for the blending ratio of the mercaptan compound in photopolymerization initiator composition, but preferably with respect to the 20-70 weight % of photopolymerization initiator composition total amount, and more preferably 30-60 weight %.If the mercaptan compound ratio is too low, the surface cure performance of resist may reduce, and if ratio is too high, the degree of crosslinking of the chain transfer meeting reduction cured product of sulfydryl.
[2] carbonyl compound
The carbonyl compound that is preferably used as hydrogen donor of the present invention is represented by following formula (3):
R wherein
3And R
4Each represents the optional alkyl that replaces independently, the optional alkoxyl group that replaces, the optional amino that replaces, the optional aralkyl that replaces, the optional aryl that replaces, the optional aryloxy that replaces, or have the organic group of polymerisable unsaturated group or polymer residue or a R
3And R
4Can be bonded together and form ring.R
5Represent hydrogen, the optional alkyl that replaces, the optional aralkyl that replaces or the optional aryl that replaces.
For as R in the formula (3)
3And R
4Having of can mentioning of alkyl: preferred 1-8 the carbon and the more preferably straight or branched alkyl of 1-6 carbon.Concrete example comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl.These groups are replacements such as alkoxy, halogen further.
For as R in the formula (3)
3And R
4Having of can mentioning of alkoxyl group: preferred 1-8 the carbon and the more preferably straight or branched alkoxyl group of 1-6 carbon, concrete example comprise methoxyl group, oxyethyl group, propoxy-, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, just hexyloxy, n-octyloxy and 2-ethylhexyl oxygen base.These groups are replacements such as alkoxy, halogen further.
As R in the formula (3)
3And R
4Amino can for example alkyl, aralkyl or aryl replace so that their hydrogen atom is by the hydro carbons group.The alkyl of the hydrogen in the substituted-amino can preferably have 1-4 carbon atom, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or the tertiary butyl.That can mention equally has alicyclic hydrocarbon group, for example cyclohexyl and a cyclopentyl.
As the aralkyl of substituted-amino hydrogen have mention benzyl, styroyl or the like arranged.As the aryl of substituted-amino hydrogen have mention phenyl, tolyl, xylyl, cumenyl, mesityl, anisyl and naphthyl arranged.The heterocyclic amino group that has nitrogen-atoms in ring also is suitable, and what this amino may be mentioned has: morpholinyl, piperidino-(1-position only) and pyrrolidyl.
As R in the formula (3)
3And R
4Aralkyl can mention benzyl and styroyl arranged.These groups can be by replacements such as alkyl, alkoxyl group, aryl, halogens.
As R in the formula (3)
3And R
4Having of can mentioning of aryl: phenyl, tolyl, xylyl, cumenyl, mesityl, anisyl, naphthyl or the like.As having that aryloxy can be mentioned: phenoxy group and naphthyloxy.These groups can be by replacements such as alkyl, alkoxyl group, aryl, halogens.
As R in formula (3)
3And R
4The organic group with polymerisable unsaturated group can mention is for example vinyl, vinylidene, acryl, methacryloyl of organic group, or the like.
As R in the formula (3)
3And R
4The organic group that has polymer residue be organic group with polymeric groups, this polymeric groups comprises the some repeating units by polymerization or polycondensation bonding.For example, what can mention is following radicals, and the organic group that wherein has polymerizable unsaturated group forms macromolecular compound in the place's polymerization of polymerisable unsaturated group.In other words, these groups can be by these compounds R in formula (3)
3And R
4The polymer substance that the copolymerization at place forms.
Particularly, that can mention has: 2-acetoacetoxy groups Jia Jibingxisuanyizhi, 2-acetoacetoxy groups ethyl propenoate, 2-acetoacetoxy groups butenoic acid ethyl or the like as the monomer that has carbonyl in 1,3 position with have the monomer multipolymer of methacrylic acid or methyl methacrylate for example that contains unsaturated group.Weight-average molecular weight for polymer residue does not have concrete restriction, but preferred 1000 to 100 ten thousand.
R in the formula (3)
3And R
4Can also be combined together to form ring texture, under these circumstances, preferably have the compound of 5-to 7-unit ring texture.
R in the formula (3)
5Expression hydrogen, the optional alkyl that replaces, the optional aralkyl that replaces or the optional aryl that replaces.
The alkyl that can mention has: preferred 1-8 the carbon and the more preferably straight or branched alkyl of 1-4 carbon, object lesson comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl.
Aralkyl comprises benzyl and styroyl.These groups can be further by replacements such as alkyl, aryl, alkoxyl group, halogens.The aryl that can mention has: phenyl, tolyl, xylyl, cumenyl, mesityl, anisyl, naphthyl or the like.These groups equally can be by replacements such as alkyl, aryl, alkoxyl group, halogens.
As having that the compound of formula (3) can be mentioned: dimethyl malonate; diethyl malonate; two-n-propyl malonic ester; the di-isopropyl malonic ester; the di-n-butyl malonic ester; the diisobutyl malonic ester; two-n-hexyl malonic ester; two-n-octyl malonic ester; methyl acetoacetate; methyl aceto acetate; etheric acid n-propyl ester; ISOPROPYL ACETOACETATE; the etheric acid n-butyl; the etheric acid isobutyl; etheric acid n-hexyl ester; etheric acid n-octyl ester; the etheric acid benzyl ester; etheric acid 2-methoxy ethyl ester; the acetoacetoxy groups Jia Jibingxisuanyizhi; N-methyl aceto-acetamide; N-ethyl aceto-acetamide; N; N-dimethyl aceto-acetamide; N; N-diethyl aceto-acetamide; N-acetoacetyl-N-morpholine; alpha.-acetylacetanilide; N-acetoacetyl-2-chloroaniline; N-acetoacetyl-2; the 5-dichlorphenamide bulk powder; N-acetoacetyl-right-Tolylamine; N-acetoacetyl-Ortho Toluidine; hydroresorcinol and methone.
When the compound of use formula (3), the ratio of mixture of the carbonyl compound in the photopolymerization has no particular limits, but preferred 20-70 weight % and more preferably 30-60 weight %.If the carbonyl compound ratio is too low, the surface cure performance of resist may reduce, and if ratio is too high, may reduce the degree of crosslinking of cured product.
Other component of 2-(4)
Except that aforesaid component, photopolymerization initiator composition of the present invention can also contain organic boron salt compound.
Be used for organic boron salt compound of the present invention and can be the ordinary light polymerization initiator composition normally used any, but what preferably can mention is those of structure with following formula (7) expression:
In formula (7), R
8, R
9, R
10And R
11Each represents optional alkyl, aryl, aralkyl, alkenyl, alkynyl, silyl or the heterocycle that replaces independently, and Z
+The positively charged ion of representing any hope.Following is to mention that conduct is by R
8, R
9, R
10And R
11The example of the group of representative.
As preferred alkyl, the replacement or the unsubstituted straight or branched alkyl that have 1-12 carbon atom specifically can be used as having that example mentions: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-octyl, dodecyl, cyano methyl, 4-chlorobutyl, 2-ethyl aminoethyl and 2-methoxy ethyl.
As having that the example of aryl can be mentioned: replace or unsubstituted phenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, 4-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-n-butylphenyl, 4-tert-butyl-phenyl, naphthyl, 4-methyl naphthyl, anthryl, phenanthryl, 4-nitrophenyl, 4-trifluoromethyl, 4-fluorophenyl, 4-chloro-phenyl-and 4-dimethylaminophenyl.
As having that the example of aralkyl can be mentioned: replace or unsubstituted benzyl, styroyl, 1-naphthyl methyl, 2-naphthyl methyl and 4-methoxy-benzyl.
As having that the example of alkenyl can be mentioned: replace or unsubstituted vinyl, propenyl, butenyl and octenyl.
As having that the example of heterocyclic group can be mentioned: replace or unsubstituted pyridine base, 4-picolyl, quinolyl and indyl.
As having that the example of alicyclic radical can be mentioned: replace or unsubstituted cyclohexyl, 4-methylcyclohexyl, cyclopentyl, suberyl or the like.
R in the formula (7)
8Preferable methyl, ethyl, n-propyl or normal-butyl, and R
9-R
11Each preferred phenyl, tolyl, the 4-tertiary butyl, naphthyl or 4-methyl naphthyl.
Z
+Preferred ammonium cation, sulfonium cation, oxo sulfonium cation, pyridylium, positively charged ion, oxygen positively charged ion or iodine positively charged ion.
As having that the object lesson of ammonium cation can be mentioned: tetramethylammonium cation, tetraethylammonium cation, four n-propyl ammonium cations, tetra-n-butyl ammonium cation, normal-butyl triphenyl ammonium cation, tetraphenyl ammonium cation and benzyl triphenyl ammonium cation.
As having that the object lesson of sulfonium cation can be mentioned: triphenylsulfonium positively charged ion, three (4-tolyl) sulfonium cation and 4-tert-butyl-phenyl phenylbenzene sulfonium cation.
As having that the object lesson of oxo sulfonium cation can be mentioned: triphenyl oxo sulfonium cation, three (4-tolyl) oxo sulfonium cation and 4-tert-butyl-phenyl diphenyloxide are for sulfonium cation.
As having that the object lesson of pyridylium can be mentioned: N-picoline positively charged ion and N-normal-butyl pyridylium.
As having that the cationic object lesson of can be mentioned: tetramethyl- positively charged ion, tetra-n-butyl positively charged ion, four n-octyl positively charged ions, tetraphenyl positively charged ion and benzyl triphenyl positively charged ion.
As having that the cationic object lesson of oxygen can be mentioned: triphenyl oxygen positively charged ion, three (4-tolyl) oxygen positively charged ion and 4-tert-butyl-phenyl diphenyloxide positively charged ion.
As having that the cationic object lesson of iodine can be mentioned: phenylbenzene iodine positively charged ion, two (4-aminomethyl phenyl) iodine positively charged ion and two (4-tert-butyl-phenyl) iodine positively charged ion.
As having that the example of organic boron salt compound of formula (7) expression can be mentioned: normal-butyl triphenyl boric acid tetramethyl-ammonium, isobutyl-triphenyl boric acid tetraethyl ammonium, normal-butyl three (4-tert-butyl-phenyl) boric acid tetra-n-butyl ammonium, normal-butyl three naphthyl boric acid tetra-n-butyl ammoniums, methyl three (4-methyl naphthyl) boric acid tetra-n-butyl ammonium, normal-butyl triphenyl-boron triphenyl phosphate base sulfonium, normal-butyl triphenyl-boron triphenyl phosphate base oxo sulfonium, normal-butyl triphenyl-boron triphenyl phosphate base oxygen, normal-butyl triphenyl boric acid N-picoline, normal-butyl triphenyl boric acid tetraphenylphosphoniphenolate and normal-butyl triphenyl boric acid phenylbenzene iodine.
Because organic boron salt compound of formula (7) representative common absorbing wavelength 300nm or longer light hardly, so when using separately, it almost is insensitive to common UV-lamp light source, but through making up with sensitizing agent, can reach very high sensitivity.
When organic boron salt compound and Hexaarylbiimidazole compound of the present invention used together, the Hexaarylbiimidazole compound in photopolymerizable composition and the total amount of organic boron salt compound preferably accounted for whole 20-60 weight % and more preferably 30-50 weight %.If the ratio of Hexaarylbiimidazole compound and organic boron salt compound is too low, the generation of free radical may be insufficient, cause low photosensitivity or solidify inadequate shortcoming, and if too high, the relative content of sensitizing agent or hydrogen donor reduces, the rough sledding that causes photosensitivity to reduce.
3. photopolymerizable composition
Being characterized as of photopolymerizable composition of the present invention: comprise (A) above-mentioned photopolymerization initiator composition of the present invention and (B) have the compound of ethylenically unsaturated group.It can also comprise adhesive resin or tinting pigment.
3-(1) has the compound of ethylenically unsaturated group
The compound with ethylenically unsaturated group in the photopolymerizable composition of the present invention is to carry out polymerization and crosslinked compound by the free radical that the optical free radical polymerization starter produces under rayed, and can be in monomer or the polymkeric substance any.
3-(1)-[1] monomer
Preferred (methyl) acrylate that uses is as monomer.Particularly, that can mention has (methyl) alkyl acrylate, (methyl) methyl acrylate for example, (methyl) vinylformic acid ethyl ester, (methyl) vinylformic acid propyl diester, (methyl) butyl acrylate cores, (methyl) vinylformic acid isobutyl, (methyl) vinylformic acid sec-butyl ester, (methyl) vinylformic acid tertiary butyl ester, (methyl) vinylformic acid polyhexamethylene, (methyl) vinylformic acid octyl group ester, (methyl) isooctyl acrylate ester, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid decyl ester, (methyl) vinylformic acid Lauryl Ester and (methyl) vinylformic acid stearyl;
Alicyclic (methyl) acrylate is (methyl) vinylformic acid cyclohexyl ester for example, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclopentenyl ester and (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester;
Aromatics (methyl) acrylate is (methyl) vinylformic acid benzyl ester for example, (methyl) phenyl acrylate, (methyl) vinylformic acid phenyl carbitol ester, (methyl) vinylformic acid nonyl phenylester, (methyl) vinylformic acid nonyl phenyl carbitol ester and (methyl) vinylformic acid Nonylphenoxy ester;
(methyl) acrylate that contains hydroxyl, (methyl) vinylformic acid 2-hydroxyethyl ester for example, (methyl) vinylformic acid hydroxypropyl ester, (methyl) vinylformic acid hydroxybutyl ester, butyleneglycol list (methyl) acrylate, glycerine (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate and glycerine two (methyl) acrylate;
Contain amino (methyl) acrylate, (methyl) vinylformic acid 2-dimethylaminoethyl ester for example, (methyl) vinylformic acid 2-diethyl aminoethyl ester and (methyl) vinylformic acid 2-tertiary butyl aminoethyl ester;
The methacrylic ester that contains phosphorus, phosphoric acid methacryloyl oxygen base ethyl ester for example, di(2-ethylhexyl)phosphate methacryloyl oxygen base ethyl ester and methacryloyl oxygen base ethylphenyl phosphate ester acid (phenyl P);
Diacrylate, ethylene glycol bisthioglycolate (methyl) acrylate for example, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate and diglycidyl (methyl) acrylate;
Polyacrylic ester, trimethylolpropane tris (methyl) acrylate for example, tetramethylolmethane three (methyl) acrylate and Dipentaerythritol six (methyl) acrylate; The polyvalent alcohol polyacrylic ester of modification is the diacrylate of the bisphenol S of oxyethane 4-mole addition for example, the diacrylate of the dihydroxyphenyl propane of oxyethane 4-mole addition, the pentaerythritol diacrylate of aliphatic acid modification, the triacrylate of the TriMethylolPropane(TMP) of the triacrylate of the TriMethylolPropane(TMP) of propylene oxide 3-mole addition and the addition of propylene oxide 6-mole.
The polyacrylic ester that contains the isocyanuric acid skeleton, two (acryl oxygen base ethyl) monohydroxy ethyl chlorinated isocyanurates for example, three (acryl oxygen base ethyl) isocyanuric acid ester of three (acryl oxygen base ethyl) isocyanuric acid esters and 6-caprolactone addition; Polyester acrylate is α for example, ω-two acryl (Diethylene Glycol) phthalic ester and α, ω-tetrapropylene acyl group (ditrimethylolpropane) tetrahydrophthalic acid ester; With
Glycidyl (methyl) acrylate; Allyl group (methyl) acrylate; ω-hydroxyl hexylyloxy ethyl (methyl) acrylate; Polycaprolactone (methyl) acrylate; Phthalic acid (methyl) acryloxy ethyl ester; Succsinic acid (methyl) acryl oxygen base ethyl ester; Vinylformic acid 2-hydroxyl-3-phenoxy propyl ester; Vinylformic acid phenoxy ethyl or the like.
N-vinyl compound (for example N-vinyl pyrrolidone, N-vinyl formamide and N-vinyl acetamide) also is suitable as monomer.
At these compounds that are used for improving photosensitivity, the preferred compound that can mention has: polyacrylic ester is trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate and Dipentaerythritol six (methyl) acrylate for example.
3-(1)-[2] polymkeric substance
The polymkeric substance that can mention has: (methyl) acrylic acid epoxy base ester, urethane (methyl) acrylate and the acrylic copolymer that contains ethylenically unsaturated group, but because for purposes as resist and colored filter, development is carried out in alkali aqueous solution, preferably contains the polymkeric substance of carboxyl.Here, term " polymer " " comprise low molecular " prepolymer " and " oligopolymer " equally.
＜contain epoxy group(ing) (methyl) acrylate (EA) of carboxyl 〉
Do not have concrete restriction for being used for epoxy group(ing) (methyl) acrylate that contains carboxyl of the present invention, suitable epoxy group(ing) (methyl) acrylate comprises: with epoxy compounds with contain the monocarboxylic reaction product of unsaturated group and the spawn that anhydride reaction obtains.
Do not have special restriction for epoxy compounds, the epoxy compounds that can mention is bisphenol-A epoxy compound, Bisphenol F epoxy compounds, bisphenol S epoxy compounds, phenol-phenolic resin varnish compound, cresols-phenolic varnish epoxy compounds and aliphatic epoxy compound for example.These compounds can use separately or two or more mix use.
As having that the example of the monocarboxylic acid that contains unsaturated group can be mentioned: (methyl) vinylformic acid; 2-(methyl) acryl oxygen base ethyl succinic acid; 2-(methyl) acryl oxygen base ethyl phthalic acid; (methyl) acryl oxygen base ethyl hexahydrophthalic acid, (methyl) acrylic acid dimer, β-furfuryl group vinylformic acid; β-styrene acrylic; styracin, Ba Dousuan, alpha-cyano styracin or the like.That can mention equally has: as the half ester of the reaction product of the acrylate that contains hydroxyl and saturated or undersaturated dibasic acid anhydride with as the half ester of the reaction product of the monoglycidyl ether that contains unsaturated group and saturated or undersaturated dibasic acid anhydride.These monocarboxylic acids that contain unsaturated group can use separately or two or more mix use.
As having that acid anhydrides can be mentioned: dibasic acid anhydride is maleic anhydride for example, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, the methyl carbic anhydride, chlorendic anhydride and methyl tetrahydrophthalic anhydride, aromatic series polyvalent carboxylic acid acid anhydride, for example trimellitic acid 1,2-anhydride, PMA and benzophenone tetracarboxylic dianhydride, or polyvalent carboxylic acid anhydride derivative, for example 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride and bridge two rings [2,2,1]-heptan-5-alkene-2, the 3-dicarboxylic anhydride.These compounds can use separately equally or two or more mix use.
Molecular weight for the epoxy group(ing) that contains carboxyl (methyl) acrylate that obtains by this way has no particular limits, but according to GPC based on the preferred 1000-40 of the weight-average molecular weight of polystyrene, 000, and more preferably 2000-5000.
In order between the alkali resistance of alkaline development performance (caustic solubility) and cured film, to obtain satisfactory balance, the acid number of above-mentioned epoxy group(ing) (methyl) acrylic compound (is measured the solid acid number according to JIS K0070, following content is identical) preferred 10mg KOH/g at least, more preferably in 45-160mg KOH/g scope and most preferably in 50-140mg KOH/g scope.If acid number is lower than 10mgKOH/g, caustic solubility reduces, yet too high acid number can cause other performance of lower alkali resistance or cured film, and this depends on the combined situation of the component of the curable resin composition that is used for resist.
＜contain urethane (methyl) acrylate (UA) of carboxyl 〉
Be used for urethane (methyl) acrylic compound that contains carboxyl of the present invention and can therefore be suitable for the purpose of requirement snappiness and flex resistance as than acrylic copolymer or the more flexible adhesive resin of epoxy group(ing) (methyl) acrylate.
Urethane (methyl) acrylic compound that contains carboxyl is a kind of comprising derived from the unit that contains hydroxyl (methyl) acrylate, derived from the unit of polyvalent alcohol with derived from the unit of the polymeric polyisocyanate compound as structural unit.More particularly, it comprises following repeating unit, wherein two ends are made up of (methyl) acrylate deutero-unit of hydroxyl, the zone of while between two ends is by forming derived from the unit of polyvalent alcohol with derived from the unit of polymeric polyisocyanate that the urethane bonding connects, and carboxyl is present in the repeating unit.
In other words, carboxylic urethane (methyl) acrylic compound is by-(OR
bO-OCNHR
cNHCO)
n-expression, (OR wherein
bO is the dehydrogenation residue of polyvalent alcohol, and R
cBe polymeric polyisocyanate take off the isocyanic ester residue).
Urethane (methyl) acrylic compound that contains carboxyl can prepare by following method: with (methyl) acrylate (a) and the polyvalent alcohol (b) and polyisocyanates (c) reaction of at least a hydroxyl, but for one of in polyvalent alcohol and the polyisocyanates or both must use the compound that comprises carboxyl, the carboxylic polyvalent alcohol of preferred package.By like this, use carboxylic compound as polyvalent alcohol and/or polyisocyanates, can prepare at R
bOr R
cThe place has urethane (methyl) acrylic compound of carboxyl.In following formula, preferably about 1-200 of n and more preferably 2-30.The outstanding snappiness that will cause cured film in the n of this scope value.
In using polyvalent alcohol and polyisocyanates the two one of or during among both two or more, repeating unit will be many types, and the regularity of plurality of cells can according to purposes from all irregular, block, the localization etc. suitably selected.
As having that (methyl) acrylate (a) that comprises hydroxyl can be mentioned: (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid hydroxy-propyl ester, (methyl) vinylformic acid hydroxybutyl ester, the oxyalkylene affixture of caprolactone or above-mentioned (methyl) acrylate, glycerine list (methyl) acrylate, glycerine two (methyl) acrylate, glycidyl methacrylate-vinylformic acid affixture, TriMethylolPropane(TMP) list (methyl) acrylate, trishydroxymethyl two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, TriMethylolPropane(TMP)-oxyalkylene affixture-two (methyl) acrylate or the like.
These contain, and hydroxyl (methyl) acrylate (a) can use separately or two or more dissimilar mixing are used.Preferred (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) acrylate hydroxypropyl and (methyl) vinylformic acid hydroxybutyl ester, more preferably (methyl) vinylformic acid 2-hydroxyethyl ester among these.Use (methyl) vinylformic acid 2-hydroxyethyl ester to promote to comprise urethane (methyl) acrylic compound (UA) synthetic of carboxyl.
Being used for polyvalent alcohol of the present invention (b) can be polyvalent alcohol and/or dihydroxy compound.As having that polyvalent alcohol can be mentioned: polyether diols is polyoxyethylene glycol for example, polypropylene glycol and polytetramethylene glycol, polyester glycol by polyvalent alcohol and polybasic ester acquisition, comprise unit such as coming from hexamethylene carbonic ether, pentamethylene carbonic ether as the polycarbonate diol of structural unit and polylactone glycol for example polycaprolactone glycol and poly-butyrolactone glycol.
When use comprises the polyvalent alcohol of carboxyl, for example can between the synthesis phase of polyvalent alcohol, add ternary or, obtain the synthetic compound to keep carboxyl greater than ternary polyprotonic acid trimellitic acid (or acid anhydrides) for example.
Polyvalent alcohol can be a kind of in those as mentioned above, or two or more mixture.Polyvalent alcohol with 200-2000 number-average molecular weight will cause the outstanding snappiness of cured film.
Employed dihydroxy compound can be the straight-chain or branched-chain compound with two alcoholic extract hydroxyl groups, but the special carboxylic dihydroxyl aliphatic carboxylic acid of preferred package.What such dihydroxy compound can be mentioned has: dimethylol propionic acid and dimethylolpropionic acid.Comprise the dihydroxyl aliphatic carboxylic acid of carboxyl by use, can easily in urethane (methyl) acrylic compound, comprise carboxyl.
Can use the mixture of a kind of dihydroxy compound or two or more dihydroxy compound, choose wantonly and use with polyvalent alcohol.
When comprising the polyvalent alcohol of carboxyl, maybe when using the compound that comprises carboxyl as described below, can use the dihydroxy compound that does not have carboxyl as polyisocyanates with mutual blended form use, ethylene glycol for example, Diethylene Glycol, propylene glycol, 1,4-butyleneglycol, 1, the 3-butyleneglycol, 1, the 5-pentanediol, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol or 1,4 cyclohexane dimethanol.
As being used for concrete polyisocyanates of the present invention, that can mention has: vulcabond for example 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, the diphenylmethylene vulcabond, (o, m or p)-Xylene Diisocyanate, methylene radical two (cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, hexanaphthene-1,3-dimethylene diisocyanate, hexanaphthene-1,4-dimethylene diisocyanate and 1, the 5-naphthalene diisocyanate.These polyisocyanates can use separately or two or more mix use.Also can use the polyisocyanates that comprises carboxyl.
Have no particular limits for being used for the molecular weight that contains urethane (methyl) acrylate of carboxyl of the present invention, but according to GPC based on the preferred 1000-40 of the weight-average molecular weight of polystyrene, 000 and more preferably 8000-30,000.Equally, the preferred 5-150 milligram KOH/ gram of acid number (UA) and the more preferably 30-120 milligram KOH/ gram that comprise urethane (methyl) acrylic compound of carboxyl.
If the weight-average molecular weight of urethane (methyl) acrylic compound (UA) that comprises carboxyl can weaken the elongation and the intensity of cured film less than 1000, if greater than 40,000, film may become hard and snappiness less.Acid number can weaken the caustic solubility (developing performance) of the curable resin composition that is used for resist less than 5 milligrams of KOH/ grams, if restrain greater than 150 milligrams of KOH/, can weaken the alkali resistance of cured film.
＜comprise the acrylic copolymer (AP-A) of carboxyl and ethylenically unsaturated group 〉
The acrylic copolymer that comprises carboxyl and ethylenically unsaturated group can obtain by following method: will a) comprise the ethylenically unsaturated monomer and the b of carboxyl) ethylenically unsaturated monomer copolymerization except that a); the epoxy reaction that has the compound (for example glycidyl (methyl) acrylate or glycidyl allyl ether) of epoxy group(ing) and ethylenically unsaturated group then on some carboxyls on acrylic copolymer (AP-B) side chain that will obtain by monomeric interpolymerization and each molecule; or, introduce ethylenically unsaturated group at side chain with this with some or all hydroxyls of acrylic copolymer and the isocyanic ester radical reaction that on each molecule, has the compound (for example isocyanic acid 2-methacryloyl oxygen base ethyl ester) of isocyanate group and ethylenically unsaturated group.
Can use the ethylenically unsaturated monomer that comprises carboxyl a) so that give acrylic copolymer alkaline development character.The object lesson that contains the ethylenically unsaturated monomer of carboxyl comprises: (methyl) vinylformic acid; 2-(methyl) acryl oxygen base ethyl succinic acid; 2-(methyl) acryl oxygen base ethyl phthalic acid; (methyl) acryl oxygen base ethyl hexahydrophthalic acid; (methyl) acrylic acid dimer, toxilic acid, Ba Dousuan; methylene-succinic acid, fumaric acid or the like.
For control coating (resist, colored filter) intensity and pigment-dispersing can use except above-mentioned ethylenically unsaturated monomer b a)).As having that object lesson can be mentioned: vinyl compound, vinylbenzene for example, alpha-methyl styrene, (o, m, p-) hydroxy styrenes and vinyl acetate; (methyl) acrylate, (methyl) methyl acrylate for example, (methyl) vinylformic acid ethyl ester, (methyl) vinylformic acid n-propyl ester, (methyl) isopropyl acrylate, (methyl) n-butylacrylate, (methyl) vinylformic acid tertiary butyl ester, (methyl) vinylformic acid n-hexyl ester, (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid phenoxy group ethyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinyl cyanide, (methyl) vinylformic acid glycidyl esters, glycidyl allyl ether, (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, vinylformic acid trifluoroethyl ester, (methyl) vinylformic acid 2,2,3,3-tetrafluoro propyl diester and (methyl) vinylformic acid perfluoro octyl group ethyl ester; With acid amides (methyl) acrylamide for example; N; N-dimethyl (methyl) acrylamide; N, N-diethyl (methyl) acrylamide, N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-sec.-propyl (methyl) acrylamide, N-vinyl pyrrolidone, N-caprolactam and N-(methyl) acryloyl morpholine.
A) and b) be preferably 5: 95 to 40: 60 and more preferably 10: 90 to 35: 65 based on the copolymerization ratio of weight.If copolymerization ratio a) is less than 5, the alkaline development performance reduces, and becomes and be difficult to form pattern.If copolymerization ratio a) is greater than 40, then alkaline development will trend towards partly carrying out in phototype setting, make to be difficult to keep the constant line width.
The molecular weight that comprises the acrylic copolymer of carboxyl and ethylenically unsaturated group is to represent with the weight-average molecular weight based on polystyrene according to gel permeation chromatography (GPC), preferably at 1000-500, and within 000 scope, and 3000-200 more preferably, 000.Less than 1000 o'clock, film toughness is considerably reduced.Greater than 500,000 o'clock, caustic solubility (developing performance) reduced widely.
Above-mentioned monomer and the polymkeric substance that comprises ethylenically unsaturated group can use with two or more dissimilar hybrid modes equally.
3-(2) adhesive resin
Photopolymerizable composition of the present invention can also comprise the adhesive resin that does not contain ethylenically unsaturated group.What such adhesive resin can be mentioned has: Resins, epoxy, and vibrin and urethane resin, but when being used for resist, the special carboxylic acrylic copolymer of preferred package.Such acrylic copolymer can be mentioned an acrylic copolymer (AP-B) that comprises carboxyl, preferred AP-B multipolymer can be mentioned be those with the side chain of AP-A as mentioned above on multipolymer before having the compound reaction of ethylenically unsaturated group.
3-(3) tinting pigment
When photopolymerizable composition of the present invention is used for colored filter, will comprise tinting pigment.The tone commonly used that is used for colored filter is: red, green and blue additive mixture, cyan, red-purple and xanchromatic subtractive mixing of colors, and the black that is used for the black matix part.When dyestuff and pigment can be as tinting materials,, preferably use pigment according to thermotolerance and sunproof viewpoint.Use the mixture of two or more different pigment usually can obtain suitable wave spectrum, for example, can obtain suitable wave spectrum by following method: mix green pigment and violet pigment and obtain blueness, mix veridian and yellow ultramarine and obtain green, mix red pigment and yellow or orange pigments and obtain redness.
Following what mention is to be used for tinting pigment of the present invention, is shown by their chromaticity index.C.I. pigment Yellow 12,13,14,17,20,24,55,83,86,93,109,110,117,125,137,139,147,148,153,154,166,168, C.I. pigment orange 36,43,51,55,59,61, C.I. Pigment Red 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228,240, C.I. pigment violet 19,23,29,30,37,40,50, C.I. pigment Blue 15,15:1,15:4,15:6,22,60,64, C.I. pigment Green 7,36, C.I. pigment brown 23,25,26.
What black pigment can be mentioned has: carbon black, and titanium is black or the like, as the Special Black 4 of having that the object lesson of carbon black can be mentioned: Degussa, Special Black 100, Special Black 250, Special Black 350 and Special Black 550, the Raven 1040 of Colombia Carbon, Raven 1060, the MA7 of Raven 1080 and Raven 1255 and Mitsubishi Chemical, MA8, MA11, MA100, MA220 and MA230.
Other component of 3-(4)
Solvent is preferred for being more suitable for adjusting in the photopolymerizable composition of the present invention the viscosity of coating.As having that the example of solvent can be mentioned: methyl alcohol, ethanol, toluene, hexanaphthene, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethylbenzene, ethylbenzene, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, Glycol Monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetic ester, Isoamyl Acetate FCC, ethyl lactate, methyl ethyl ketone, acetone, hexanaphthene or the like, wherein any can use separately or two or more mix use.
The photopolymerizable preparation of compositions of 3-(5)
When photopolymerizable composition of the present invention comprises pigment, can prepare by utilizing for example triple pulverators of diverting device, dual pulverator, sand mill, masher, ball mill, stirrer, paint shaker etc. to mix each of said components.The gelation of stopper be can add, or monomer or photoinitiator after colo(u)rant dispersion, added to prevent to produce owing to polymerization during dispersion.In order to obtain more satisfactory pigment dispersion, also can add suitable dispersing auxiliary.Dispersing auxiliary has the effect that promotes colo(u)rant dispersion and prevent to disperse the back reflocculation.
Embodiment
By embodiment the present invention is described now, should understands embodiment without limits for the present invention.
Synthetic
Synthesizing of diimidazole compound
Synthetic embodiment 1:2,2 '-two (2-chloro-phenyl-)-4,4 '-5,5 '-four (4-aminomethyl phenyls)-1,2 '-diimidazole
(below's be abbreviated as MHABI) is synthetic
With 27.50 gram (115mmol) 4,4 '-dimethyl benzil (4,4 '-dimethylbenzil) (TokyoKasei Kogyo Co., Ltd.), 16.25 gram (116mmol) o-chlorobenzaldehyde (Tokyo KaseiKogyo Co., Ltd.), 69.45 the gram (901mmol) ammonium acetates (Junsei Chemicals Co., Ltd.) and 450 the gram acetate (Junsei Chemicals Co., Ltd.) put into the flask of volume 1L after, mixture was reacted 5 hours down at 117 ℃, stir simultaneously.Make the reaction mixture cooling, be poured at leisure then in the deionized water of 2L stirring, make 2-chloro-phenyl--4,5-two (4-aminomethyl phenyl) imidazoles precipitation.With 2-chloro-phenyl--4,5-two (4-aminomethyl phenyl) imidazoles filter and washing after, it is dissolved in the 500 gram methylene dichloride (Junsei Chemicals Co. Ltd.), and joins solution in the 4 neck flasks of volume 2L and is cooled to 5-10 ℃.Then to wherein adding 117.6 gram (357mmol) Tripotassium iron hexacyanide (JunseiChemicals Co., Ltd.), 44.7 gram sodium hydroxide (Junsei Chemicals Co., Ltd.) and 600 the gram deionized waters mixture, stirred simultaneously one hour, the reaction at room temperature carried out 18 hours.With reaction mixture deionized water wash three times, (JunseiChemicals Co., Ltd.) dehydration then under reduced pressure steams methylene dichloride, the crystal of preparation MHABI with about 50 anhydrous magnesium sulfates that restrain then.(Junsei Chemicals Co. Ltd.) with the MHABI recrystallization, filters and drying then, obtains the pale yellow crystals products (88.7% productive rate) of 36.5 grams with ethanol.
The chemical formula of the MHABI that obtains is C
46H
36C
L2N
4, and molecular weight is 715.70.
Structural analysis
(1)
1H-NMR
MHABI's
1The H-NMR chart is seen Fig. 1.
1H-NMR utilizes the JNM-AL400 of JEOL to measure in heavy chloroform.
(2)
13C NMR
MHABI's
13The C-NMR chart is seen Fig. 2 and Fig. 3.
13C-NMR utilizes the AMX400 of Bruker to measure in heavy chloroform.The characterization displacement study is belonged to.
21.0,21.2,21.5,21.6ppm: 24,25,24 ', the methine carbon atom 110.7ppm:2 ' carbon atom of 25 ' position
(3) mass spectrum
Utilize the mass spectrum of the JMS-SX102A mensuration MHABI of JEOL.Chart is seen Fig. 4.The molecular weight of MHABI is 715.69, detects molecular ion peak at 714 places.This value is complementary with the molecular weight that does not contain the MHABI of atom isotope.
(4) fusing point
Utilize the 510 type melting point apparatuss of Buchi to measure fusing point.The fusing point of MHABI is 211 ℃.
Synthesizing of adhesive resin
Synthetic embodiment 2: comprise the acrylic copolymer (AP-B) of carboxyl, AP-1:25 weight %
The acrylic copolymer solution that comprises carboxyl (solvent: propylene glycol methyl ether acetate, below be abbreviated as
PGMEA, Tokyo Kasei Kogyo Co., the product of Ltd)
With the methacrylic acid of 11.25 weight parts (below be abbreviated as MAA, Kyoeisha ChemicalCo., Ltd. product), 15.00 the methyl methacrylate of weight part (below be abbreviated as MMA, the product of Kyoeisha Chemical), 41.25 the methacrylic acid n-butyl of weight part (below be abbreviated as BMA), 7.50 the methacrylic acid 2-hydroxyl ethyl ester of weight part (below be abbreviated as HEMA, the product of Kyoeisha Chemical) and the PGMEA of 210.0 weight parts join dropping funnel be housed, thermometer, prolong, after in the 4 neck flasks of agitator and nitrogen inlet tube, 4 neck flasks were replaced one hour with nitrogen.After being heated to 90 ℃, be added dropwise to 2 of the PGMEA of HEMA, 210.0 weight parts of BMA, 7.50 weight parts (0.0776 mole) of MMA, 41.25 weight parts of MAA, 15.00 weight parts of 11.25 weight parts and 3.20 weight parts in during one hour, 2 '-Diisopropyl azodicarboxylate (is abbreviated as AIBN, Wako Pure Chemical Industries, the product of Ltd.) mixture.Behind the polyase 13 hour, be heated to 100 ℃, add the mixture of the PGMEA of the AIBN of 1.0 weight parts and 30.0 weight parts, extra again polymerization 1.5 hours obtains comprising the acrylic copolymer (AP-1) of carboxyl.The weight-average molecular weight of AP-1 (measuring by GPC, based on polystyrene) is 26,000.
Compound synthetic that comprises ethylenically unsaturated group
Synthetic embodiment 3: the acrylic copolymer that comprises carboxyl and ethylenically unsaturated group
(AP-A), the acrylic acid series copolymerization that comprises carboxyl and ethylenically unsaturated group of AP-2:26 weight %
Solution (the solvent: PGMEA) of thing
The propylene-based copolymer AP-1 that comprises carboxyl, 8.8 gram isocyanic acid 2-methacryloyl oxygen base ethyl ester (Karenz MOI with 600 weight parts; the product of Showa Denko K.K.) and 0.36 the gram dibutyl tin dilaurate (Tokyo Kasei Kogyo Co.; Ltd. after product) joining in the 4 neck flasks that thermometer, prolong, agitator and nitrogen inlet tube are housed; be reflected at and carried out under 60 ℃ 3 hours; blast air simultaneously; with the reaction mixture cooling, obtain AP-2 then.
Synthetic embodiment 4: comprise epoxy acrylate (EA) synthetic of carboxyl, EA-1:60 is heavy
Solution (the solvent: the diethylene glycol monoethyl ether acetic ester) of the epoxy acrylate that comprises carboxyl of amount %
Cresols-phenolic resin varnish (the EPOTOTO YDCN-704 that adds 210 weight parts, epoxy equivalent (weight): 210, softening temperature: 90 ℃, Toto chemical Co., Ltd. product), 72 parts by weight of acrylic (Tokyo Kasei Kogyo Co., Ltd. product), 0.28 the Resorcinol of weight part (Tokyo Kasei Kogyo Co., product) and the diethylene glycol monoethyl ether acetic ester of 232.6 weight parts (Tokyo Kasei Kogyo Co. Ltd., Ltd. product), with mixture heating up to 95 ℃, after confirming uniform dissolution, the triphenylphosphine (Tokyo Kasei Kogyo Co., the product of Ltd.) that adds 1.4 weight parts is with mixture heating up to 100 ℃, reaction was carried out about 30 hours, obtained having the reaction mixture of 0.5mgKOH/ gram acid number.To the Tetra Hydro Phthalic Anhydride that wherein adds 66.9 weight parts, with mixture heating up to 90 ℃, reaction is carried out by about 6 hours, confirm to have lost the absorption of acid anhydrides by IR (infrared absorption spectrum), obtained having the Epocryl EA-1 that comprises carboxyl of 70 milligrams of KOH/ grams of solid acid number and solid concentration 60.0%.
The evaluation of photopolymerizable composition
Reagent
The compound (monomer) that comprises ethylenically unsaturated group
Dipentaerythritol acrylate: Toa Gosei Co., the product of Ltd.
Photo-induced polymerization initiator
1) EMK (4,4 '-two (N, N-diethylamino) benzophenone): Hodogaya ChemicalCo., the product of Ltd..
2) HABI (2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-tetraphenyl-1,2 ' diimidazole): HodogayaChemical Co., the product of Ltd.
3) MN
3M (methyl three (4-methyl naphthyl) boric acid tetra-n-butyl ammonium): synthetic by the method for in Japanese unexamined patent publication HEI No.11-222489, describing
4) TPMP (trimethylolpropane tris (3-mercaptopropionic acid ester)): Yodo Kagaku Co., the product of Ltd..
5) methone: Tokyo Kasei Kogyo Co., the product of Ltd.
Pigment
1) carbon black: Special Black 4, the product of Degussa
Other component
1) PGMEA (propylene glycol methyl ether acetate): Tokyo Kasei Kogyo Co., the product of Ltd.
2) hexanaphthene: Wako Pure Chemical Industries, the product of Ltd..
3) FLOWLEN DOPA-33: dispersion agent comprises amino acrylic copolymer, solid concentration: 30 weight %, main solvent: pimelinketone, Kyoeisha Chemical Co., the product of Ltd..
Photopolymerizable preparation of compositions
Embodiment 1
The acryl copolymer A P-1 (solid part of 49.0 weight parts with 196.0 weight parts; the solvent part of 147 weight parts), the FLOWLEN DOPA-33 (dispersion agent: Kyoeisha Chemical Co. of Special Black 4,21.7 weight parts of 65.0 weight parts; Ltd. (the solid part of 6.5 weight parts product); 15.2 the solvent part of weight part) and after the pimelinketone of 200.0 weight parts mixes; use coating conditioning agent (Asada Iron Works Co., the product of Ltd.) to disperse 3 hours.
In this dispersion, the compd E A-1 (solid part of 21.0 weight parts that comprises ethylenically unsaturated group with 35.0 weight parts, 14.0 the solvent part of weight part), 4 of the dipentaerythritol acrylate of 38.5 weight parts, 5.0 weight parts, the pimelinketone of the MHABI of 4 '-two (N, N-diethylamino) benzophenone (below be abbreviated as " EMK "), 15.0 weight parts, the TPMP of 15.0 weight parts and 600.0 weight parts mixes and dissolving.Then composition is filtered with 0.8 μ m pore filter paper (the Kiriyama filter paper that is used for GFP), obtain photopolymerizable composition of the present invention.The physicals of the photopolymerizable composition that obtains is assessed by following method.The results are shown in Table 1.
Embodiment 2, and the comparative example 1,2
Except consumption in the table 1 is listed in use, with and embodiment 1 same method carry out embodiment 2 and comparative example 1 and 2.The physicals of the photopolymerizable composition that obtains is according to the method assessment of embodiment 1.The results are shown in Table 1.
Assessment method
(1) residual film photosensitivity
The photopolymerizable composition that obtains is spin-coated on substrate of glass, and (100 * 100mm) go up to about 1.5 microns build, and at room temperature dry 30 minutes, vacuum-drying at room temperature was 10 minutes then.With film thickness surveying instrument (SURFCOM130A, Tokyo Seimitsu Co., Ltd. product) accurately measure the film thickness of exsiccant coating, then with having ultrahigh pressure mercury lamp (Ushio, Inc. exposure apparatus " Multilight ML-251A/B ") is exposed in the light photopolymerizable composition, change exposure by quartzy photomask simultaneously, be used for phototype setting.Utilize ultraviolet integrating photometer (Ushio Inc. " UIT-150 " that have " UVD-S365 " receptor) to measure exposure.In employed quartzy photomask, formed 5,10,30,50,70,100 microns straight line/space diagrams.Gap between photomask and coating is set to 100 microns.The coating of will exposing is at 0.1% aqueous sodium carbonate neutral and alkali develop the specified time (25 ℃).Development time is set to 1.5 times of time cycle (tD), and tD dissolves the needed time by the alkaline development of coating with coating before the exposure fully.Time cycle tD dissolves the needed time fully by the coating that repeated experiments is measured, and wherein observes the solubleness of the coating with different alkaline development times.After the alkaline development,, measure the film thickness of remaining coating (resist), calculate the remaining ratio of film according to following equation by spraying into air with substrate of glass washing and dry:
The remaining ratio (%) of film=100x (film thickness after the alkaline development)/(film thickness before the alkaline development) carries out identical phototype setting method, change exposure simultaneously, on the chart relation between exposure and the remaining ratio of film is being mapped then, wherein the remaining ratio of recording film reaches the exposure (mJ/cm of fullness of shade
2), with it as the remaining light sensitivity of film.Less value shows to have higher light sensitivity.
(2) sublimate during the oven dry of back
The photopolymerizable composition that obtains is spin-coated on substrate of glass, and (100 * 100 * 1mm) go up to about 1.5 microns build, and at room temperature dry 30 minutes, vacuum-drying at room temperature was 10 minutes then.With above-mentioned exposure apparatus irradiation 100mJ/cm
2Light, carry out phototype setting.The substrate that obtains is placed in the dish, dish is placed on makes its heating on the hot-plate then.(200 * 200 * 1mm) are placed in the dish, and will wrap aqueous dish and be placed on it, to cool off the stainless steel-based end with the stainless steel-based end.Use hot-plate after heating 30 minutes under 230 ℃ substrate of glass, with opticmicroscope (VH-Z250, the product of Keyence Corporation) observes the sublimate that is derived from cured film and stick at stainless steel-based the end, and visually judge existence or do not have crystal.The results are shown in Figure 5 (embodiment 1) and Fig. 6 (comparative example 1).When using HABI,, there is not tangible crystal when using MHABI although produced crystal (in Fig. 6 and the similar mark of bird footprint).
Table 1
| Embodiment 1 | Embodiment 2 | The comparative example 1 | The comparative example 2 | ||
| Photopolymerizable composition | (weight part numerical value) | ||||
| Adhesive resin | AP-1 *1 (25.0 weight % solid part) | 196.0 | 140.0 | 196.0 | 140.0 |
| The compound polymer monomer that comprises ethylenically unsaturated group | AP-2 *2(26.0 weight % solid part) EA-1 *3(60.0 weight % solid part) dipentaerythritol acrylate | 35.0 38.5 | 130.0 38.5 | 35.0 38.5 | 130.0 38.5 |
| Dispersion agent | FLOWLEN DOPA-33 *4(30.0 weight % solid part) | 21.7 | 21.7 | 21.7 | 21.7 |
| Coloured material | Carbon black *5 | 65.0 | 65.0 | 65.0 | 65.0 |
| Photoepolymerizationinitiater initiater | |||||
| Sensitizing agent | EMK *6 | 5.0 | 5.0 | 5.0 | 5.0 |
| Optical free radical produces agent | MHABI *7HABI *8MN3M *9 | 15.0 | 10.0 5.0 | 15.0 | 10.0 5.0 |
| Hydrogen donor | TPMP *10Methone | 15.0 | 15.0 | 15.0 | 15.0 |
| Organic solvent | Pimelinketone | 800.0 | 760.0 | 800.0 | 760.0 |
| Evaluation result | |||||
| Remaining light sensitivity (the mJ/cm of film 2) | 20 | 20 | 40 | 40 | |
| Exist/there is not crystal | Do not exist | Do not exist | Exist | Exist |
*1: methacrylic acid/methyl methacrylate/methacrylic acid n-butyl/methacrylic acid 2-hydroxyl ethyl ester=15/20/55/10 (weight ratio) multipolymer, Mw=26,000, solids concn: 25 weight %, solvent; PGMEA.
*2: comprise the acrylic copolymer of the 2-isocyanic ester Jia Jibingxisuanyizhi that adds on the AP-1, solids concn: 26 weight %, solvent: PGMEA.
*3: comprise the cresols-phenolic varnish epoxy acrylate of carboxyl, solids concn: 60 weight %, acid number: 70 milligrams of KOH/ grams.
*4:FLOWLEN DOPA-33
* 4: dispersion agent comprises amino acrylic copolymer, solids concn: 30 weight %, main solvent: pimelinketone.
*5：Special Black 4
*6:4,4 '-two (N, N-diethylamino) benzophenone
*7:2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four (4-aminomethyl phenyls)-1,2 '-diimidazole
*8:2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole
*9: methyl three (4-methyl naphthyl) boric acid tetra-n-butyl ammonium
*10: trimethylolpropane tris (3-mercaptopropionic acid ester)
The new Hexaarylbiimidazole compound of the present invention has low heat of sublimation hydrolysis products, and when in photosensitive composition during used as the component of photopolymerization initiator composition, they in addition during the back oven dry of the resist production of colored filter etc., do not produce sublimate.Can prevent the trouble that usually occurs when utilizing the photosensitive composition comprise conventional Photoepolymerizationinitiater initiater like this, for example the sublimate of Chan Shenging adheres on the vapor pipe or the like and such adhesion is fallen on the resist.
The photopolymerization initiator composition of the present invention that uses above-mentioned Hexaarylbiimidazole compound for as various resists for example the photopolymerizable composition of solder resist, anti-etching dose, photoresist etc. be effective especially, and can be used in particular for photopolymerizable composition, the latter is used for the colored filter of color liquid crystal display device, photographic camera etc. compatibly as the colored filter resist in production.
Claims (4)
1. photopolymerization initiator composition, it contains as the defined Hexaarylbiimidazole compound of following formula (2):
And contain the hydrogen donor of the defined dicarbonyl compound of following formula (3) as the Hexaarylbiimidazole compound:
R wherein
3And R
4Each represents the straight or branched alkyl of 1-8 carbon independently, and it is unsubstituted or is selected from the substituting group replacement of alkoxyl group and halogen; The straight or branched alkoxyl group of 1-8 carbon, it is unsubstituted or is selected from the substituting group replacement of alkoxyl group and halogen; Amino, it is unsubstituted or their the hydrogen atom substituting group that is selected from alkyl, aralkyl and aryl replaces; Aralkyl, it is unsubstituted or is selected from the substituting group replacement of alkyl, alkoxyl group, aryl and halogen; Aryl, it is unsubstituted or is selected from the substituting group replacement of alkyl, alkoxyl group, aryl and halogen; Aryloxy, it is unsubstituted or is selected from the substituting group replacement of alkyl, alkoxyl group, aryl and halogen; Organic group with polymerisable unsaturated group, it is selected from vinyl, vinylidene, acryl and methacryloyl; The organic group that has polymer residue, it is selected from the multipolymer that 2-acetoacetoxy groups Jia Jibingxisuanyizhi, 2-acetoacetoxy groups ethyl propenoate or 2-acetoacetoxy groups butenoic acid ethyl and methacrylic acid or methyl methacrylate form; Or R
3And R
4Can be combined together to form 5-to 7-unit ring texture,
R
5Represent hydrogen; The straight or branched alkyl of 1-8 carbon, it is unsubstituted or is selected from the substituting group replacement of alkyl, aryl, alkoxyl group and halogen; Aralkyl, it is unsubstituted or is selected from selected substituting group replacement from alkyl, aryl, alkoxyl group and halogen; Or aryl, it is unsubstituted or is selected from the substituting group replacement of alkyl, aryl, alkoxyl group and halogen.
2. according to the photopolymerization initiator composition of claim 1, it is characterized in that comprising one or more be selected from compound based on benzophenone, based on the compound of thioxanthone with based on the compound in the compound of ketone group tonka bean camphor.
3. photopolymerizable composition is characterized in that its component below comprising at least:
(A) according to the photopolymerization initiator composition of claim 1; With
(B) have the compound of ethylenically unsaturated group.
4. according to the photopolymerizable composition of claim 3, it is characterized in that it is used for the colored filter resist.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002300446A JP4393051B2 (en) | 2002-10-15 | 2002-10-15 | Hexaarylbiimidazole compound and photopolymerization initiator composition containing the same |
| JP300446/2002 | 2002-10-15 | ||
| US60/419,093 | 2002-10-18 |
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| CN1705646A CN1705646A (en) | 2005-12-07 |
| CN1325477C true CN1325477C (en) | 2007-07-11 |
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| CNB2003801014251A Expired - Fee Related CN1325477C (en) | 2002-10-15 | 2003-10-01 | Hexaarylbiimidazole compounds and photopolymerization initiator compositions containing the same |
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| JP (1) | JP4393051B2 (en) |
| KR (1) | KR100768863B1 (en) |
| CN (1) | CN1325477C (en) |
| TW (1) | TW200413326A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004264728A (en) * | 2003-03-04 | 2004-09-24 | Sumitomo Chem Co Ltd | Photosensitive resin composition |
| JP4674048B2 (en) * | 2004-02-23 | 2011-04-20 | 東洋インキ製造株式会社 | Coloring composition for forming color filter and color filter |
| WO2005111674A1 (en) * | 2004-05-13 | 2005-11-24 | Showa Denko K.K. | Black resist composition for color filter |
| JP4547308B2 (en) * | 2005-06-30 | 2010-09-22 | 富士フイルム株式会社 | Photosensitive composition, image recording material, and image recording method |
| JP2007127818A (en) * | 2005-11-02 | 2007-05-24 | Fujifilm Corp | Photosensitive composition for color filter, color filter, method for producing color filter, and liquid crystal display device |
| JP4835210B2 (en) | 2006-03-10 | 2011-12-14 | 東洋インキＳｃホールディングス株式会社 | Coloring composition for color filter, color filter, and method for producing color filter |
| JP2007256477A (en) * | 2006-03-22 | 2007-10-04 | Fujifilm Corp | Method for manufacturing optical compensation sheet, polarizing plate including optical compensation sheet manufactured by same manufacturing method, and liquid crystal display device |
| CN100369955C (en) * | 2006-04-13 | 2008-02-20 | 上海交通大学 | Polymer type hexaryl diimidazole photoinitiator and its prepn process |
| JP5128838B2 (en) * | 2007-03-28 | 2013-01-23 | 富士フイルム株式会社 | Novel photoactive biimidazole compound, photosensitive composition containing the same, and method of using the same |
| JP5513711B2 (en) * | 2007-10-01 | 2014-06-04 | 太陽ホールディングス株式会社 | Photosensitive resin composition and cured product thereof |
| JP2009265515A (en) * | 2008-04-28 | 2009-11-12 | The Inctec Inc | Colored photosensitive composition for color filter |
| CN101441416B (en) * | 2008-12-18 | 2012-07-25 | 番禺南沙殷田化工有限公司 | Dry film photoresist and preparing method thereof |
| JP6238516B2 (en) * | 2011-11-07 | 2017-11-29 | 住友化学株式会社 | Colored curable resin composition |
| JP6095104B2 (en) * | 2012-12-26 | 2017-03-15 | 日本化薬株式会社 | Active energy ray-curable resin composition, colored spacer for display element, and black matrix |
| CN111258181B (en) * | 2018-11-30 | 2024-02-27 | 常州正洁智造科技有限公司 | Hexaarylbisimidazole hybrid photoinitiators |
| CN111258180B (en) * | 2018-11-30 | 2024-03-08 | 常州正洁智造科技有限公司 | Hexaarylbisimidazoles mixed photoinitiator and application thereof |
| CN111747897A (en) * | 2019-03-29 | 2020-10-09 | 常州格林感光新材料有限公司 | Hexaarylbisimidazole photoinitiator and application thereof |
| CN112062721B (en) * | 2019-05-23 | 2023-06-30 | 常州正洁智造科技有限公司 | HABI photoinitiator capable of improving system stability and application thereof |
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2002
- 2002-10-15 JP JP2002300446A patent/JP4393051B2/en not_active Expired - Fee Related
-
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- 2003-09-18 TW TW092125780A patent/TW200413326A/en unknown
- 2003-10-01 CN CNB2003801014251A patent/CN1325477C/en not_active Expired - Fee Related
- 2003-10-01 KR KR1020057006528A patent/KR100768863B1/en not_active IP Right Cessation
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| US3533797A (en) * | 1967-03-13 | 1970-10-13 | Du Pont | Hexaarylbiimidazole-coumarin compositions |
| JPH10253815A (en) * | 1997-03-12 | 1998-09-25 | Mitsubishi Chem Corp | Photopolymerization composition for color filter, and the color filter |
| EP0902327A2 (en) * | 1997-09-09 | 1999-03-17 | JSR Corporation | Radiation sensitive composition |
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| WO2003072614A2 (en) * | 2002-02-28 | 2003-09-04 | Showa Denko K.K. | Thiol compound, photopolymerization initiator composition and photosensitive composition |
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| JP2004137152A (en) | 2004-05-13 |
| KR100768863B1 (en) | 2007-10-19 |
| KR20050072439A (en) | 2005-07-11 |
| CN1705646A (en) | 2005-12-07 |
| JP4393051B2 (en) | 2010-01-06 |
| TW200413326A (en) | 2004-08-01 |
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