Source: http://www.docstoc.com/docs/43496604/Photosensitive-Resin-Composition-And-Color-Filter-Comprising-A-Polymer-Dyeable-With-An-Anionic-Dye-An-Azide-Compound-And-A-Compound-With-At-Least-Two-Acrylol-Groups---Patent-5190845
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Photosensitive Resin Composition And Color Filter Comprising A Polymer Dyeable With An Anionic Dye, An Azide Compound And A Compound With At Least Two Acrylol Groups - Patent 5190845 by Patents-38
43496604
The present invention relates to a photosensitive resin composition for dyeing easily a transparent substrate such as glass with an anionic dye into a desired tone, and to a color filter obtained by using the resin composition.In recent years, color filters obtained by coloring transparent substrates such as glass have been used in various display devices and the like. Particularly, there has been an increasing demand for filters for color resolution which areobtained by coloring transparent substrates such as glass and are used for liquid-crystal color TV sets or color TV cameras.The present invention, made for meeting the demand, relates to a photosensitive resin composition for dyeing a transparent substrate such as glass, and to a color filter obtained by using the resin composition.BACKGROUND ARTIn this industrial field, protein-based natural high molecular substances such as casein, gelatin, etc. have hitherto been mainly used. In use of such a material, ammonium or potassium dichromate is added as a photo-curing agent to a liquidobtained by dissolving casein, gelatin or the like in warm water, and the resultant liquid is applied to a glass plate by a spin coating method. Next, irradiation with active rays is conducted through a mask to form a latent image of a dyeable layer onthe glass plate, followed by development to develop the dyeable layer. Then, the layer is dyed with a dye. Thus, a natural high molecular substances have been used.In the case of using casein, gelatin or the like, there are problems that such a natural material is putrescible, the quality thereof is not constant but varies widely depending on the origin thereof, resulting in its extremely poor colorreproduction, the material is liable to peel off in hot water, the physical properties of the material are greatly deteriorated by heat, working conditions are restricted, and so on. Further, there are problems in dyeing, that the temperature of a dyebath for dyeing or the like is restri
United States Patent: 5190845
5,190,845
Photosensitive resin composition and color filter comprising a polymer
dyeable with an anionic dye, an azide compound and a compound with at
least two acrylol groups
(c) a compound having at least two acryloyl and/or methacryloyl groups in
the same molecule thereof, and a color filter obtained by using the resin
Hashimoto; Matsuo (Tano, JP), Futamura; Nobuyuki (Maebashi, JP), Yoda; Sumio (Takasaki, JP), Saiki; Yoshifumi (Maebashi, JP)
07/345,543
PCT/JP88/00700
WO89/01186
62-186561
62-245900
63-88993
430/196  ; 430/145; 430/167; 430/197; 430/288.1; 430/7
G03F 7/012&amp;nbsp(20060101); G03F 7/008&amp;nbsp(20060101); G03F 007/021&amp;nbsp(); G03C 001/695&amp;nbsp()
430/196,197,7,195,288,281
4614701
4675252
Nagono et al.
4820619
4943512
49-41685
50-108003
54-161402
57-117689
60-221755
61-210344
62-115402
62-127735
62-138802
62-149988
62-194203
62-209504
62-275042
62-283339
63-10152
Patent Abstracts of Japan, vol. 9, No. 1.
Patent Abstracts of Japan, vol. 8, No. 86..
Assistant Examiner:  Chu; John S.
1.  A photosensitive resin composition comprising
2.  A resin composition according to claim 1, wherein 0.1 to 20 arts of the azide photosensitive compound and 0.1 to 20 parts of the compound having at least two acryloyl groups int eh same molecule thereof are used per 100 parts of the polymer
dyeable with an anionic dye.
3.  A resin composition according to claim 1 or 2, wherein the azide photosensitive compound is at least one compound selected from the group consisting of
4,4&#39;-diazidochalcone,
2,6-bis(4&#39;-azidobenzal)cyclohexanone,
2,6-bis(4&#39;-azidobenzal)- 4-methylcyclohexanone,
1,3-bis(4&#39;-azidobenzal)- 2-propanone,
1,3-bis(4&#39;-azidobenzal)- 2-propanone-2&#39;-sulfonic acid,
4,4&#39;-diazidostilbene-2,2&#39;-disulfonic acid,
sodium 4,4&#39;-diazidostilbene-2,2&#39;-disulfonate,
1.  3-bis(4&#39;-azido-2&#39;-sulfobenzal)-2-propanone,
1,3-bis(4&#39;-azido-2&#39;-sodiumsulfonatobenzal)-2-propanone,
2,6-bis(4&#39;-azido-2&#39;-sulfobenzal)cyclohexanone,
2,6-bis(4&#39;-azido-2&#39;-sulfobenzal)methylcyclohexanone,
2,6-bis(4&#39;-azido-2&#39;-sodiumsulfonatobenzal)methylcyclohexanone, and
N,N&#39;-diethyl-2,2&#39;-disulfonamido-4,4&#39;-diazidostilbene.
4.  A color filter obtained by using a resin composition according to claim 1 or 2.
5.  A color filter obtained by using a resin composition according to claim 3.
6.  A resin composition according to claim 1, wherein said polymer dyeable with an anionic dye is a polymer prepared by polymerizing:
b. a hydrophilic monomer;  and
7.  A resin according to claim 6, wherein the dyeable monomer is selected from the group consisting of (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)ethyl methacrylate, (N,N-diethylamino)ethyl acrylate, (N,N-diethylamino)ethyl
methacrylate, (N,N-dimethylamino)propyl acrylamide, (N,N-dimethylamino)propyl methacrylamide, (N,N-dimethylamino)ethyl vinyl ether, (N,N-dimethylamino)propyl acrylate, (N,N-dimethylamino)propyl methacrylate, 4-vinylpyridine,
2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, and methacryloyloxyethyltrimethylammonium chloride.
8.  A resin composition according to claim 6, wherein the hydrophilic monomer is selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylamide, methacrylamide, vinylpyrrolidone, dimethylaminoacrylamide, and
9.  A resin composition according to claim 6, wherein the hydrophobic monomer is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, styrene, p-methylstyrene, butyl acrylate, butyl methacrylate,
2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate.  Description
In recent years, color filters obtained by coloring transparent substrates such as glass have been used in various display devices and the like.  Particularly, there has been an increasing demand for filters for color resolution which are
obtained by coloring transparent substrates such as glass and are used for liquid-crystal color TV sets or color TV cameras.
In this industrial field, protein-based natural high molecular substances such as casein, gelatin, etc. have hitherto been mainly used.  In use of such a material, ammonium or potassium dichromate is added as a photo-curing agent to a liquid
obtained by dissolving casein, gelatin or the like in warm water, and the resultant liquid is applied to a glass plate by a spin coating method.  Next, irradiation with active rays is conducted through a mask to form a latent image of a dyeable layer on
the glass plate, followed by development to develop the dyeable layer.  Then, the layer is dyed with a dye.  Thus, a natural high molecular substances have been used.
In the case of using casein, gelatin or the like, there are problems that such a natural material is putrescible, the quality thereof is not constant but varies widely depending on the origin thereof, resulting in its extremely poor color
reproduction, the material is liable to peel off in hot water, the physical properties of the material are greatly deteriorated by heat, working conditions are restricted, and so on.  Further, there are problems in dyeing, that the temperature of a dye
bath for dyeing or the like is restricted and, therefore, it is difficult to obtain a deep color.
Moreover, the use of casein, gelatin or the like is accompanied by the use of ammonium or potassium dichromate as the photo curing agent and, therefore, there are problems that it is necessary to solve the pollution problem associated with the
working process or disposal of the materials, and chromium contained in the gelatin would not be completely removed but would cause bad effects.
The present inventors have studied synthetic high molecular weight materials in order to solve the above-mentioned problems.  First, an attempt was made to dye the surface of a substrate by use of a polymer having a basic group or quaternary
ammonium salt group having affinity for anionic dyes.  The polymer itself is dyeable because of its affinity for the anionic dyes, but the polymer is soluble in water.  Therefore, when the polymer was applied to a glass substrate or the like and dyeing
was conducted after drying the applied polymer, the coating peeled off from the surface of the substrate into the dye bath in the dyeing process, and it was impossible to accomplish the purpose of the dyeing or to obtain a dyed substrate.  Besides, the
present inventors have found out that when a photosensitive resin composition obtained by adding an azide compound to a dyeable polymer as a crosslinking agent is applied to the surface of a substrate such as a glass plate and is irradiated with light,
it is possible to form a favorably dyeable resin coating free of peeling.  This finding is now being put into practical use.  However, with the recent requirements for higher resolution quality, speedup of process, energy saving and the like, there has
been a request for a further reduction in the quantity of light used for curing a photosensitive resin composition.  In general, when the quantity of light used for curing a photosensitive resin composition is insufficient, the resin film obtained is
weak, and a film roughening phenomenon takes place at the time of dyeing of the film, resulting in an opaque dyed film.  In such a case, dyeability and resolution are also poor.  Furthermore, there arise the problems of poor dimensional stability of
images, etc. In order to meet the above-mentioned requirements through increasing the photo-reaction rate of the azide compound in the photosensitive resin composition, the effect of addition of various known sensitizers on the increase of the
photo-reaction rate was studied, but none of the sensitizers gave a satisfactory effect.
Namely, the photosensitive resin composition (D) used in the invention can be cured, to accomplish the purpose, by a quantity of light which is a fraction of the quantity of light required for curing a resin composition using only the azide
photosensitive compound (B).  In general, the compound (C), when used singly, requires a quantity of light equal to several times that required for the azide photosensitive compound (B).  When the azide photosensitive compound (B) and the compound (C)
are used together, it is possible to accomplish the purpose by using a small quantity of light.  This is presumed to be due to some favorable interaction between the azide photosensitive compound (B) and the compound (C).
The polymer dyeable with an anionic dye (A) used in this invention preferably comprises a dyeable monomer (a), a hydrophilic monomer (b) and a hydrophobic monomer (c) as constituents.  The polymer (A) can be prepared by using a conventional
method of polymerization.
The dyeable monomer (a), the hydrophilic monomer (b) and the hydrophobic monomer (c) are preferably used in respective proportions of 10 to 80% by weight, 2 to 60% by weight, and 5 to 50% by weight.  The molecular weight of the polymer (A) thus
prepared is preferably 5,000 to 200,000, particularly 10,000 to 100,000.
1,3-bis(4&#39;-azido-2&#39;-sulfobenzal)-2-propanone,
The photosensitive resin composition having the above-mentioned composition is ordinarily used after diluted with an organic solvent or the like.  As the organic solvent, there may be mentioned, for example, methyl cellosolve, ethyl cellosolve,
toluene, xylene, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, methyl isobutyl ketone, methyl ethyl ketone, etc. At least one of such solvents may be used either singly or in combination.  The proportion of the organic
solvent in the dyeable photosensitive resin liquid depends on the composition of the photosensitive resin composition and cannot be specifically prescribed.  It is preferable, however, to select the proportion of the organic solvent to obtain such a
viscosity that the resin liquid is applicable to the surface of a substrate.
Furthermore, in order to ensure favorable adhesion of the dyeable resin coating to a glass plate, a silane coupling agent is ordinarily added to the photosensitive resin composition.  The amount of the silane coupling agent added is preferably
0.1 to 20 parts, particularly 0.5 to 10 parts, per 100 parts of the dyeable polymer (A).
The substrate, such as glass, thus coated with the dyeable resin liquid is ordinarily exposed to rays such as UV rays through a mask.  Unexposed portions are then developed by an aqueous solution.
The development is preferably carried out in the range from normal temperature to 60.degree.  C. (for instance, 10 to 60.degree.  C.).  The thickness of the resin coating thus developed can be set to an arbitrary value, for instance, 0.2 to 10
.mu..  The substrate, such as glass and plastic, having a predetermined pattern thus developed is dyed with an anionic dye.
As the anionic dye, there may be mentioned acid dyes described as &quot;C.I.  Acid&quot; in Colour Index (published by the Society of Dyers and Colourists), direct dyes described as &quot;C.I.  Direct&quot; in the same, reactive dyes described as &quot;C.I.  Reactive&quot; in
the same, etc., among which the acid dyes are particularly preferable.  As the acid dyes, there may be mentioned C.I.  Acid Yellows 17, 49, 67, 72, 127, 110, 135 and 161, C.I.  Acid Reds 37, 50, 111, 114, 257, 266 and 317, C.I.  Acid Blues 41, 83, 90,
113, 129 182 and 125, C.I.  Acid Oranges 7 and 56, C.I.  Acid Greens 25 and 41, C.I.  Acid Violets 97, 27, 28 and 48, etc.
To perform dyeing by use of the dye, 0.01 to 200 parts by weight of the dye is dissolved in 1000 parts by weight of water.  The pH of the liquid thus prepared may be in a weak basic to acidic range.  Dyeing by use of the dye solution is carried
out at a temperature ranging from room temperature to 100.degree.  C. It is preferable to carry out dyeing at a high temperature in the range, because a dyed product is thereby obtainable in a short time.  After the dyeing, the dyed product is taken out
and dried, whereby the substrate with a dyed surface coating (color filter) is obtainable.
______________________________________ Dimethylaminopropylacrylamide  31 parts  2-Hydroxyethyl methacrylate  14 parts  Vinylpyrrolidone 15 parts  Methyl methacrylate 15 parts  Methyl acrylate 13 parts  Dimethylaminoacrylamide  10 parts  Dioxane
200 parts  .alpha.,.alpha.&#39;-azobis(isobutyronitrile)  1 part  ______________________________________
A liquid of the above formulation was brought into polymerization reaction in a nitrogen atmosphere at 80.degree.  C. for 5 hours.  The polymerization liquid was put into a large amount of isopropyl ether, and after precipitation of a polymeric
component, the polymer was taken out and dried.  A solution comprising a mixture of 15 parts of the dried polymer with 0.63 part of 4,4&#39;-diazidochalcone, 0.57 part of spiroglycol diacrylate, 88 parts of ethyl cellosolve, 27 parts of diethylene glycol
dimethyl ether and 0.6 part of a silane coupling agent KBM 603 (a product by Shinetsu Chemical Co., Ltd.) was used as a dyeable photosensitive resin liquid.
Next, the dyeable photosensitive resin liquid was applied to a glass plate by a spin coating method, and after drying at 80.degree.  C for 30 minutes, the dried resin coating was irradiated with UV rays at a surface illuminance of 8 mW/cm.sup.2
through a mask having a resolution test pattern for 5 seconds.  The UV-irradiated resin coating was developed for 5 minutes by immersion in a developing liquid containing 2 parts of Emulgen 913 (a polyoxyethylene nonylphenylene ether type nonionic
surface active agent, produced by Kao Soap Co., Ltd.) in 1000 parts of water at 60.degree.  C. under stirring, whereby a glass substrate having a dyeable coating in only the irradiated areas was obtained.  The glass plate was subjected further to
post-baking at 160.degree.  C. for 30 minutes, after which the thickness of the coating was 0.5 .mu..  The glass plate thus treated was dyed by using a 0.2% aqueous solution of Blue 43P (a dye for color filter, produced by Nippon Kayaku Co., Ltd.) at
60.degree.  C. for 10 minutes, to obtain a glass plate dyed pattern-wise in deep blue.  The resolving power of the pattern of the glass plate was 5 .mu., and both the transparency of the dyed coating and the dimensional stability of the image were
The same operation as in Example 1 was repeated except that 0.57 part of spiroglycol diacrylate used in Example 1 was replaced by 0.59 part of SU.4100 (a polyacrylate oligomer, produced by Mitsubishi Yuka Fine Chemicals Co., Ltd.).  The UV
irradiation time required for obtaining the same resolving power, transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 7 seconds.
The same operation in Example 1 was carried out except that 0.57 part of spiroglycol diacrylate used in Example 1 was replaced by 0.67 part of cyclohexanedimethylol diacrylate.  The UV irradiation time required for obtaining the same resolving
power, transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 5 seconds.
The same operation in Example 1 was carried out except that 0.63 part of 4,4&#39;-diazidochalcone used in Example 1 was replaced by 0.2 part of 1,3-bis(4&#39;-azidobenzal)-2-propanone and 0.4 part of 4,4&#39;-diazidochalcone.  The UV irradiation time
required for obtaining the same resolving power, transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 5 seconds.
The same operation in Example 1 was carried out except that 0.57 part of spiroglycol diacrylate used in Example 1 was replaced by 0.3 part of ethylene glycol dimethacrylate and 0.3 part of spiroglycol diacrylate.  The UV irradiation time required
for obtaining the same resolving power, transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 5 seconds.
The same operation in Example 1 was carried out except that 0.63 part of 4,4&#39;-diazidochalcone used in Example 1 was replaced by 0.65 part of p-azidobenzalacetophenone.  The UV irradiation time required for obtaining the same resolving power,
transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 5 seconds.
The same operation as in Example 1 was carried out except that 0.57 part of spiroglycol diacrylate used in Example 1 was not added.  The UV irradiation time required for obtaining the same resolving power, transparency of the dyed coating and
dimensional stability of the image as those in Example 1 was 40 seconds.
The same operation as in Example 4 was carried out except that 0.57 part of spiroglycol diacrylate used in Example 4 was not added.  The UV irradiation time required for obtaining the same resolving power, transparency of the dyed coating and
dimensional stability of the image as those in Example 4 was 35 seconds.
The same operation as in Example 6 was carried out except that 0.57 part of spiroglycol diacrylate used in Example 6 was not added.  The UV irradiation time required for obtaining the same resolving power, transparency of the dyed coating and
dimensional stability of the image as those in Example 1 was 43 seconds.
The same operation as in Example 1 was carried out except that 0.63 part of 4,4&#39;-diazidochalcone used in Example 1 was replaced by 0.68 part of sodium 4,4&#39;-diazidostilbene-2,2-disulfonate, 0.57 part of spiroglycol diacrylate used in Example 1 was
replaced by 0.67 part of cyclohexanedimethylol diacrylate, and that the 5-minute development in the stirred developing liquid at 60.degree.  C carried out in Example 1 was replaced by 1-minute development in the stirred developing liquid at 25.degree.
C. The UV irradiation time required for obtaining the same resolving power, transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 5 seconds.
The same operation as in Example 1 was carried out except that 0.63 part of 4,4&#39;-diazidochalcone used in Example 1 was replaced by 0.67 part of 1,3-bis(4&#39;-azidobenzal)-2-propanone-2&#39;-sulfonic acid, 0.57 part of spiroglycol diacrylate used in
Example 1 was replaced by 0.67 part of cyclohexanedimethylol diacrylate, and that the 5-minute development in the stirred developing liquid at 60.degree.  C. carried out in Example 1 was replaced by 2-minute development in the stirred developing liquid
at 25.degree.  C. The UV irradiation time required for obtaining the same resolving power, transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 20 seconds.
The same operation as in Example 7 was carried out except that 0.67 part of cyclohexanedimethylol diacrylate used in Example 7 was not added.  Image formation was unsatisfactory even with UV irradiation for 30 seconds, and a satisfactory result
The same operation as in Example 8 was carried out except that 0.67 part of cyclohexanedimethylol diacrylate used in Example 8 was not added.  Image formation was unsatisfactory even with UV irradiation for 60 seconds, and a satisfactory result
The same operation as in Example 1 was carried out except that 0.63 part of 4,4&#39;-diazidochalcone used in Example 1 was replaced by 0.15 part of sodium 4,4&#39;-diazidostilbene-2,2&#39;-disulfonate and 0.48 part of 4,4&#39;-diazidochalcone, that 0.57 part of
spiroglycol diacrylate used in Example 1 was replaced by 0.67 part of cyclohexanedimethylol diacrylate, and that the 5-minute development in the stirred developing liquid at 60.degree.  C. carried out in Example 1 was replaced by 5-minute development in
the stirred developing liquid at 40.degree.  C. The UV irradiation time required for obtaining the same resolving power, transparency of the dyed coating and dimensional stability of the image as those in Example 1 was 8 seconds.
The same operation as in Example 9 was carried out except that 0.67 part of cyclohexanedimethylol diacrylate used in Example 9 was not added.  The UV irradiation time required for obtaining the same results as in Example 9 was 50 seconds.
______________________________________ Example  10 11 12  ______________________________________ Dimethylaminopropyl  30 parts 28 parts  31 parts  acrylamide  2-Hydroxyethyl 18 parts 19 parts  17 parts  methacrylate  Methyl methacrylate  33 parts
15 parts  15 parts  Methyl acrylate  0 part 20 parts  19 parts  Vinylpyrrolidone  15 parts 0 part 21 parts  Dimethylaminoacrylamide  10 parts 20 parts  0 part  Dioxane 210 parts 218 parts  220 parts  .alpha.,.alpha.&#39;-azobis  2 parts 1.9 parts  2.3 part
(isobutyronitrile)  Total 318 parts 321.8  parts  325.3  parts  ______________________________________
Liquids of the above formulations were subjected to polymerization and the polymer obtained was dried by the same operation as in Example 1.  Dyeable photosensitive resin liquids were prepared in the same manner as in Example 1 except for using
the respective polymers thus obtained, and the resin liquids were processed in the same manner as in Example 1.  The UV irradiation times required for obtaining the same resolving power, transparency of the dyed coating and dimensional stability of the
image as those in Example 1 were equal to that in Example 1.
The same operations as in Examples 10 to 12 were repeated except that 0.57 part of spiroglycol diacrylate used in Examples 10 to 12 was not added.  The UV irradiation times required for obtaining the same resolving power, transparency of the dyed
coating and dimensional stability of the image as those in Examples 10 to 12 were 35 seconds.
This invention solves the problems of putrescibility of natural materials and wide variations in the product quality depending on the origin of the raw materials, associated with the conventional photosensitive resins obtained by use of natural
matter such as gelatine, casein, etc. and a dichromate.  Besides, the invention is free of the hexavalent chromium pollution problem arising from a waste liquid.
Furthermore, the dyeable photosensitive resin composition (D) according to this invention ensures curing of the resin by a quantity of light which is a fraction of the quantity of light required for curing a resin composition not using the
compound (C).  Thus, the invention contributes to energy saving, rationalization of process and a reduction of cost.
"Photosensitive Resin Composition And Color Filter Comprising A Polymer Dyeable With An Anionic Dye, An Azide Compound And A Compound With At Least Two Acrylol Groups - Patent 5190845"
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