CN106019846A - Colored photosensitive resin composition, color filter and image display device - Google Patents
Colored photosensitive resin composition, color filter and image display device Download PDFInfo
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- CN106019846A CN106019846A CN201610182804.7A CN201610182804A CN106019846A CN 106019846 A CN106019846 A CN 106019846A CN 201610182804 A CN201610182804 A CN 201610182804A CN 106019846 A CN106019846 A CN 106019846A
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- methyl
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- photosensitive resin
- resin composition
- colored photosensitive
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
The invention relates to a colored photosensitive resin composition, which comprises a colorant (A), an adhesive resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E). The colorant (A) contains C.I. pigment green 59 and one or more of pigment and dye. The invention further relates to a color filter made from the composition and an image display device of the color filter.
Description
Technical field
The present invention relates to colored photosensitive resin composition, the coloring formed with this resin combination
Pattern, comprises the colored filter of this colored pattern, and has the image of this colored filter
Display device.
Background technology
Colored filter is widely used in various display device such as imaging device and liquid crystal display dress
Put (LCD), and range of application increases rapidly.For imaging device, liquid crystal
Colored filter in showing device etc. or formed with the colored pattern of 3 kinds of colors of red, green and blue,
Or formed with the colored pattern of yellow, fuchsin and blue or green 3 kinds of colors.
Each colored pattern of described colored filter generally utilizes colored photosensitive resin composition
Being formed, described compositions includes coloring agent such as pigment or dyestuff, adhesive resin, light can
Polymerizable compound, Photoepolymerizationinitiater initiater and solvent.Described colored photosensitive resin is utilized to combine
The colored pattern processing of thing generally utilizes photoetching process to carry out.
Recently, in order to improve machinability and product quality, it is desirable to for various display devices
(including solid-state image device such as digital camera and liquid crystal indicator (LCD))
Colored filter there is high brightness and high coloring character.
Meanwhile, Korean patent application publication No.2013-0134494 discloses and utilizes C.I. pigment
Green 7 and the resin combination of C.I. pigment yellow 185, but have a problem in that can not meet simultaneously highlighted
Degree and high coloring character.
[prior art literature]
[patent documentation]
Korean patent application publication No.10-2013-0134494
Summary of the invention
In view of above-mentioned, it is made that the present invention, it is an object of the present invention to provide colored photosensitive
Resin combination, it has outstanding brightness, coloring property and adhesion, and can be formed
There is the pixel of high transmission rate and high-contrast.
Another object of the present invention provides the coloured silk including described colored photosensitive resin composition
Colo(u)r filter, and include the image display device of described colored filter.
One aspect of the present invention provides colored photosensitive resin composition, and it includes coloring agent
(A), adhesive resin (B), photopolymerizable compound (C), photopolymerization cause
Agent (D) and solvent (E), wherein coloring agent (A) include C.I. naphthol green 59 and
One or more types in pigment and dyestuff.
Another aspect of the present invention provides and includes by described colored photosensitive resin composition shape
The colored filter of the pattern become.
It is yet another aspect of the present invention to provide the image display device including colored filter.
Accompanying drawing explanation
Fig. 1 is the figure of absorbance spectrum in the case of the coloring agent being shown with including each pigment.
Detailed description of the invention
The present invention includes coloring agent (A), adhesive resin (B), photopolymerizable chemical combination
Thing (C), Photoepolymerizationinitiater initiater (D) and solvent (E), wherein coloring agent (A) includes
The compound represented by chemical formula 1 below and the one or many in pigment and dyestuff
Type.
[chemical formula 1]
In chemical formula 1, A1To A16It is Cl, Br or H independently of one another, and A1To A16
In 1 to 6 be H, its 0 to 5 is Cl, and its 5 to 13 is Br.
Hereinafter, the various components of the colored photosensitive resin composition forming the present invention will be described.
But, the invention is not restricted to these components.
(A) coloring agent
Coloring agent (A) according to the present invention is that can to represent color the most red, green or blue
So that preparation has the component of the pattern of color of object.
Pigment (a1)
The coloring agent (A) that the colored photosensitive resin composition of the present invention includes includes by followingization
The compound that formula 1 represents is as pigment (a1).The compound tool represented by chemical formula 1 below
There is ZnPc (ZnPc) structure.The present invention including the compound represented by chemical formula 1 below
The advantage that toner (A) has height color rendering.
[chemical formula 1]
In chemical formula 1, A1To A16It is Cl, Br or H independently of one another, and A1To A16
In 1 to 6 be H, its 0 to 5 is Cl, and its 5 to 13 is Br.
The preferred example of the described compound represented by chemical formula 1 can include C.I. naphthol green 59
(hereinafter, also referred to as ' G59 ').This situation is in terms of maximizing the effect of the present invention
Preferably.
C.I. naphthol green 58 (G58) has the advantage of high brightness, but, in order to reach high coloring
Character, pigment content increases, and when compositions includes the most substantial amounts of described pigment, may
The pattern that generation problem, such as developability reduce, is formed by described compositions have stripping risk,
And sensitivity reduces.
But, the present invention by utilize represented by chemical formula 1 pigment, particularly G59 as
Toner, even if can be designed that the resist remaining to height color rendering under little pigment content.
Meanwhile, include that C.I. pigment Green 7 (G7) is conducive to using at described resin combination,
Even if because still be able to obtain high coloring character under low pigment content, but it has asking of low-light level
Topic.But, the chemical combination of the described chemical formula 1 that the colored photosensitive resin composition of the present invention includes
Thing, particularly G59, function is when being included in described colored photosensitive resin composition to represent
Outstanding brightness shows with C.I. pigment Green 7 as transmitted spectrum and color as pigment phase simultaneously
Coordinate.As Fig. 1 identifies, saturating under 400nm to 610nm wavelength of C.I. naphthol green 59
Penetrate spectrum similar to C.I. pigment Green 7.
In the present invention, Tmax refers to the wavelength at the point with maximum pigment transmittance, and
T50%Refer to that pigment transmittance is the wavelength at the point of the 50% or above of maximum.
In one embodiment of the invention, described C.I. naphthol green 59 can have 500nm
To the Tmax of 530nm, and it is preferred in terms of having outstanding coloring property.
In another embodiment of the invention, described C.I. naphthol green 59 can have 445nm
T to 580nm50%, and it is preferred in terms of having outstanding coloring property.
Relative to the gross weight of the colored photosensitive resin composition of the present invention, the change of described chemical formula 1
Compound preferably comprises 0.05 weight % to 50 weight %, and more preferably 0.1 weight % to 25 weight % is also
More preferably 0.5 weight % is to 20 weight %.Due to transmittance height, high and outstanding the showing of contrast
Shadow, the compound of described chemical formula 1 accounts for 0.05 weight % to 50 weight % based on above-mentioned standard
In the range of be preferred.
Coloring agent (A) according to the present invention is in addition to the compound represented by chemical formula 1, also
Including one or more types in pigment and dyestuff, described pigment and dyestuff are generally in ability
In territory, as representing, color is such as red, green or blueness is so that preparation has color of object
The component of pattern uses, and these can be prepared as the form of mill base.
In the present compositions, preferably with weight ratio 1:0.050 to 1:18.0, more preferably 1:0.1
The described compound represented by chemical formula 1 and institute is included to 1:9 and more preferably 1:0.2 to 1:4
State one or more types in pigment and dyestuff.Due to high coloring character and high brightness, with
And improve fininsh allowance and the advantage of outstanding sensitivity, the most above-mentioned weight ratio is preferred.
In this case, include described in that chemical formula 1 compound according to the present invention is as pigment
Coloring agent can have the x=0.1 to 0.35 as y=0.6 or higher in XYZ colorimeter system
Chromaticity coordinates.
Meanwhile, when with G58 as an example, it is possible to obtain when in XYZ colorimeter system
The chromaticity coordinates of substantially x=0.2 to 0.35 during y=0.6 or higher.Here, in order to utilize G58 to have
Close to the value of x=0.1, need to include and blue secondary colour, and the problem declined due to brightness,
This is not preferred.
When with G7 as another example, it is possible to the region representing color may be big, but has bright
Spend low problem.
Described pigment (a1) includes organic pigment and inorganic pigment, and these can individually or make
Mixture for two or more types uses.Organic pigment is used to have outstanding thermostability
Form aspect of performance with color and be probably preferred.Described organic pigment can be synthetic dyestuff or
Natural pigment.
Described organic pigment is as required it may be that resin treatment；Utilize introduce acidic-group or
The pigment derivative surface of basic group processes；Utilize polymer compound etc. on the surface of the pigment
Grafting processes；The atomizations such as sulphuric acid atomization method are utilized to process；Or remove with organic solvent or water
Impurity and carrying out washing treatment.
As described inorganic pigment, metallic compound such as metal-oxide or metal network can be included
Adduct salt, inorganic salt such as barium sulfate (body pigment), the more style of described metallic compound
Son can include metal such as ferrum, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and
The oxide of white carbon black, or metal composite oxide, etc..
The object lesson of described pigment (a1) can be more preferably included in " colour index " (Color Index)
(being published by dyeing association of man (Society of Dyers and Colourists)) classifies as pigment
Compound, and more specifically include by following colour index (C.I.) numbering illustrate face
Material.But, described pigment is not limited to this, and one or more types therefrom selected can be in order to
With the common distribution such as adhesive resin, dispersant in case using, thus obtain target colorimetric.
C.I. the object lesson of pigment yellow can include C.I. pigment yellow 1,3,12,13,14,15,
16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,
129,137,138,139,147,148,150,153,154,166,173,180,185,
194,214 etc.；
C.I. the object lesson of pigment orange can include C.I. pigment orange 13,31,38,40,42,
43,51,55,59,61,64,65,71,73 etc.；
C.I. the object lesson of paratonere can include C.I. Pigment Red 9,97,105,122,123,
144,149,166,168,176,177,180,192,209,215,216,224,242,
254,255,264,265 etc.；
C.I. the object lesson of alizarol saphirol can include C.I. pigment blue 15: 3,15:4,15:6,16,
22,28,60 etc.；
C.I. the object lesson of pigment violet can include C.I. pigment violet 14,19,23,29,32,
177 etc., and
C.I. the object lesson of naphthol green can include C.I. pigment Green 7,36,58 etc..
Among pigment illustrated above, including selected from C.I. pigment yellow 13 8, C.I. pigment yellow
129, one or more types in the group that C.I. pigment yellow 150 and C.I. pigment yellow 185 is formed
It is probably preferred.
Dyestuff (a2)
The dyestuff (a2) that can include in the coloring agent (A) of the present invention can make without limitation
With, maybe can disperse in organic solvent as long as it has dissolubility in organic solvent.Excellent
Selection of land, it can be advantageous to use be able to ensure that reliability such as to the dissolubility of alkali developing solution,
Thermostability and solvent resistance have the deliquescent dyestuff to organic solvent simultaneously.Do not have organic
The deliquescent dyestuff of solvent can disperse in case using.
As dyestuff (a2), it is possible to use selected from the acid with acidic-group such as sulfonic acid or carboxylic acid
Property dyestuff, nitrogen-containing compound and the salt of acid stain, the sulfonamide etc. of acid stain and derivative
One or more types in thing.In addition, described dyestuff can also be selected from azo,
Oxa anthracenes and phthalocyanines acid stain, and derivant.
Described dyestuff (a2) can be preferably included in " colour index " (being published by association of dyeing man)
In classify as the compound of dyestuff or at " dyeing explanation " (Dyeing Note) (Color and Dye
Corporation) known dye described in.
The object lesson of described dyestuff (a2) can include,
C.I. solvent yellow 2, C.I. solvent yellow 14, C.I. solvent yellow 16, C.I. solvent yellow 33, C.I. is molten
Agent Huang 34, C.I. solvent yellow 44, C.I. solvent yellow 56, C.I. solvent yellow 82, C.I. solvent yellow 93,
C.I. solvent yellow 94, C.I. solvent yellow 98, C.I. solvent yellow 116 and C.I. solvent yellow 135；
C.I. solvent orange 1, C.I. solvent orange 3, C.I. solvent orange 7 and C.I. solvent orange 63；
C.I. solvent red 1, C.I. solvent red 2, C.I. solvent red 3, C.I. solvent red 8, C.I. solvent
Red 18, C.I. solvent red 23, C.I. solvent red 24, C.I. solvent red 27, C.I. solvent red 35,
C.I. solvent red 43, C.I. solvent red 45, C.I. solvent red 48, C.I. solvent red 49, C.I. solvent
Red 91:1, C.I. solvent red 119, C.I. solvent of red 135, C.I. solvent red 140, C.I. solvent red
196 and C.I. solvent red 197；
C.I. solvent purple 8, C.I. solvent violet 9, C.I. solvent violet 13, C.I. solvent violet 26, C.I. is molten
Agent purple 28, C.I. solvent purple 31 and C.I. solvent violet 59；
C.I. solvent blue 4, C.I. solvent blue 5, C.I. solvent blue 25, C.I. solvent blue 35, C.I. is molten
Agent indigo plant 36, C.I. solvent blue 38 and C.I. solvent blue 70；
C.I. solvent green 3, C.I. solvent green 5 and C.I. solvent green 7, etc., but it is not limited to this.
Relative to the solid in colored photosensitive resin composition, described coloring agent (A) divides in weight
Number can preferably comprise 5 weight % to 85 weight % more preferably 10 weight % to 50 weight %.
When described coloring agent (A) content is less than 5 weight %, the pattern formed is likely to be of decline
Color separating power, and when described content more than 85 weight % time, photoetching efficiency may decline,
Cause residue residual or the problem of such as not development etc.
Solids content in the colored photosensitive resin composition of the present invention refers at described colored photosensitive
In resin combination, the total content of the component in addition to solvent.
(B) adhesive resin
The adhesive resin (B) that the colored photosensitive resin composition of the present invention includes is to development
During use alkali developing solution provide deliquescent component.It addition, described adhesive resin
Serve as pigment binder, and when forming dyed layer, be molten to the development in process color
Liquid (particularly preferred alkali developing solution) has deliquescent component.
In the present invention, described adhesive resin (B) preferably include selected from following copolymer (B1),
One or more types in following polymer (B2) and following copolymer (B3).
Described copolymer (B1) includes that (methyl) acrylic acid copolymer (is hereinafter also referred to as " altogether
Polymers (B1) ") (b1)；N-substituted maleimide amine (b2)；With selected from following one
Or polytype unsaturated compound (b3) (is hereinafter also referred to as " unsaturated compound (b3) "
Or " (b3) "): styrene, α-methyl styrene, to hydroxy-alpha-methyl styrene, (methyl)
Acrylic acid methyl ester., (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl)
Acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl)
Glycerol acrylate, single [2-(methyl) acryloyl-oxyethyl] succinate, the many caprolactones of ω-carboxyl
Single (methyl) acrylate, Group-capped Polystyrene Macromer and polymethyl methacrylate macromole list
Body.
Described Group-capped Polystyrene Macromer and polymethyl methacrylate macromonomer can be
Refer to the monomer of the polymer of each polystyrene or polymethyl methacrylate.
The example of N-substituted maleimide amine (b2) can include N-phenylmaleimide, N-
O-hydroxy-phenyl maleimide, hydroxyphenyl-maleimides between N-, N-p-hydroxybenzene Malaysia
Acid imide, N-benzyl maleimide, N-N-cyclohexylmaleimide, N-succinimido-3-
Maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinum
Imide-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid ester,
N-(acridinyl) maleimide etc..
Among these N-substituted maleimide amine, preferably N-phenylmaleimide, N-hexamethylene
Base maleimide etc., and more preferably N-phenylmaleimide, N-benzyl maleimide etc..
Described N-substituted maleimide amine can make individually or as the mixture of two or more types
With.
The example of described unsaturated compound (b3) preferably includes selected from one of the following or multiple
Type: styrene, (methyl) n-butyl acrylate, 2-(methyl) EHA, (methyl)
Acrylic acid 2-hydroxy methacrylate, (methyl) benzyl acrylate, single (methyl) glycerol acrylate, single [2-(first
Base) acryloyl-oxyethyl] succinate and ω-carboxyl many caprolactones list (methyl) acrylate.More
Preferably, (methyl) 2-EHA and/or ω-carboxyl can be selected and use how own interior
Ester list (methyl) acrylate.
Except described (methyl) acrylic acid (b1), N-substituted maleimide amine (b2) and unsaturationization
Outside compound (b3), the adhesive resin (B) of the present invention can also include copolymerizable with these
The copolymer of other unsaturated monomers (b4) copolymerization separately.
Here, described unsaturated monomer (b4) does not include described (b1), (b2) and (b3) component.
The preferred object lesson of the copolymer (B1) as above obtained can include,
(methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) benzyl acrylate copolymer,
Hydroxyphenyl-maleimides/styrene/(methyl) benzyl acrylate copolymerization between (methyl) acrylic acid/N-
Thing, (methyl) acrylic acid/N-p-hydroxybenzene maleimide/styrene/(methyl) benzyl acrylate is common
Polymers, (methyl) acrylic acid/N-N-cyclohexylmaleimide/styrene/(methyl) benzyl acrylate copolymerization
Thing, (methyl) acrylic acid/N-phenylmaleimide/α-methyl styrene/(methyl) benzyl acrylate is common
Polymers, (methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) n-butyl acrylate copolymerization
Thing, (methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) 2-EHA
Copolymer, (methyl) acrylic acid/N-phenylmaleimide/to hydroxy-alpha-methyl styrene/(methyl)
Benzyl acrylate copolymer, (methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) propylene
Acid N-butyl copolymer, (methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) acrylic acid
2-Octyl Nitrite copolymer, (methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) propylene
Acid 2-hydroxy methacrylate/(methyl) benzyl acrylate copolymer, (methyl) acrylic acid/N-benzyl maleimide
Amine/styrene/(methyl) benzyl acrylate/mono-(methyl) glycerol acrylate copolymer, (methyl) propylene
Acid/N-p-hydroxybenzene maleimide/styrene/(methyl) benzyl acrylate/mono-(methyl) acrylic acid
Glyceride copolymer, (methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) acrylic acid benzene
Ester/(methyl) acrylic acid 2-hydroxy methacrylate/Group-capped Polystyrene Macromer copolymer, (methyl) acrylic acid
/ N-phenylmaleimide/styrene/(methyl) phenyl acrylate/(methyl) acrylic acid 2-hydroxy methacrylate/
Polymethyl methacrylate macromonomer copolymer, (methyl) acrylic acid/N-phenylmaleimide
/ styrene/(methyl) benzyl acrylate/(methyl) n-butyl acrylate/(methyl) acrylic acid 2-hydroxyl second
Ester copolymer, (methyl) acrylic acid/N-phenylmaleimide/styrene/(methyl) benzyl acrylate
/ (methyl) n-butyl acrylate/mono-(methyl) glycerol acrylate copolymer, (methyl) acrylic acid/N-benzene
Base maleimide/styrene/(methyl) benzyl acrylate/(methyl) 2-EHA/(methyl)
Acrylic acid 2-hydroxy methacrylate copolymer, (methyl) acrylic acid/N-phenylmaleimide/styrene/(first
Base) benzyl acrylate/(methyl) 2-EHA/mono-(methyl) glycerol acrylate copolymer,
(methyl) acrylic acid/mono-[2-(methyl) acryloyl-oxyethyl] succinate/N-phenylmaleimide/
Styrene/(methyl) benzyl acrylate copolymer, (methyl) acrylic acid/mono-[2-(methyl) acryloxy
Ethyl] succinate/N-p-hydroxybenzene maleimide/styrene/(methyl) benzyl acrylate is common
Polymers, (methyl) acrylic acid/mono-[2-(methyl) acryloyl-oxyethyl] succinate/N-phenyl Malaysia
Acid imide/styrene/(methyl) allyl acrylate copolymer, (methyl) acrylic acid/mono-[2-(methyl)
Acryloyl-oxyethyl] succinate/N-N-cyclohexylmaleimide/styrene/(methyl) acrylic acid
Allyl ester copolymer, (methyl) acrylic acid/mono-[2-(methyl) acryloyl-oxyethyl] succinate/N-
N-cyclohexylmaleimide/styrene/(methyl) benzyl acrylate copolymer, (methyl) acrylic acid/mono-
[2-(methyl) acryloyl-oxyethyl] succinate/N-phenylmaleimide/styrene/(methyl) third
Olefin(e) acid N-butyl/(methyl) acrylic acid 2-hydroxy methacrylate copolymer, (methyl) acrylic acid/mono-[2-(methyl)
Acryloyl-oxyethyl] succinate/N-phenylmaleimide/styrene/(methyl) acrylic acid is just
Butyl ester/mono-(methyl) glycerol acrylate copolymer, (methyl) acrylic acid/mono-[2-(methyl) acryloyl-oxy
Base ethyl] succinate/N-phenylmaleimide/styrene/(methyl) 2-EHA
/ (methyl) acrylic acid 2-hydroxy methacrylate copolymer, (methyl) acrylic acid/mono-[2-(methyl) acryloxy
Ethyl] succinate/N-phenylmaleimide/styrene/(methyl) 2-EHA/mono-
(methyl) glycerol acrylate copolymer, (methyl) acrylic acid/ω-carboxyl many caprolactones list (methyl) third
Hydroxyphenyl-maleimides/styrene/(methyl) benzyl acrylate copolymer, (first between olefin(e) acid ester/N-
Base) acrylic acid/ω-carboxyl many caprolactones list (methyl) acrylate/N-p-hydroxybenzene maleimide
/ styrene/(methyl) benzyl acrylate copolymer, (methyl) acrylic acid/ω-carboxyl many caprolactones list (first
Base) acrylate/N-phenylmaleimide/styrene/(methyl) benzyl acrylate/mono-(methyl) third
Olefin(e) acid glyceride copolymer, (methyl) acrylic acid/ω-carboxyl many caprolactones list (methyl) acrylate/N-
P-hydroxybenzene maleimide/styrene/(methyl) benzyl acrylate/mono-(methyl) acrylic acid glycerol
Ester copolymer, (methyl) acrylic acid/ω-carboxyl many caprolactones list (methyl) acrylate/N-phenyl Malaysia
Acid imide/styrene/(methyl) n-butyl acrylate/(methyl) acrylic acid 2-hydroxy methacrylate copolymer,
(methyl) acrylic acid/ω-carboxyl many caprolactones list (methyl) acrylate/N-phenylmaleimide/benzene
Ethylene/(methyl) n-butyl acrylate/mono-(methyl) glycerol acrylate copolymer, (methyl) acrylic acid
/ ω-carboxyl many caprolactones list (methyl) acrylate/N-phenylmaleimide/styrene/(methyl) third
Olefin(e) acid 2-Octyl Nitrite/(methyl) acrylic acid 2-hydroxy methacrylate copolymer, (methyl) acrylic acid/ω-carboxyl
Many caprolactones list (methyl) acrylate/N-phenylmaleimide/styrene/(methyl) acrylic acid 2-
Octyl Nitrite/mono-(methyl) glycerol acrylate copolymer etc., but it is not limited to this.
In other words, the copolymer that described adhesive resin (B) includes can pass through combined polymerization (first
Base) acrylic acid (b1), N-substituted maleimide amine (b2) and unsaturated compound (b3) system
Standby, furthermore it is also possible to include and other unsaturated monomers of combined polymerization (b4).
Here, the ratio deriving from the composition of (b1), (b2), (b3) and (b4) is preferred
In the scope below relative to the gross weight of described copolymer composition.
Derive from the composition of (b1): 5 weight % to 40 weight % more preferably 10 weight % are extremely
30 weight %；
Derive from the composition of (b2): 5 weight % to 40 weight % more preferably 10 weight % are extremely
30 weight %；
Derive from the composition of (b3): 30 weight % to 80 weight % more preferably 30 weight % are extremely
75 weight %；With
Derive from the composition of (b4): 0 weight % to 30 weight % more preferably 0 weight % are extremely
20 weight %.
In the present invention, the component ratio of described adhesive resin is preferred within the above range,
Because can obtain that there is high transmission rate and high-contrast and the colored photosensitive of outstanding developability
Resin combination.
Polymer (B2) is one or more the type weights selected from chemical formula 2 below and chemical formula 3
Multiple unit.
[chemical formula 2]
In chemical formula 2, R1、R2、R3And R4It is that to have 1 to 20 carbon former independently of one another
Son also can contain the organic residue of hydrogen atom, halogen atom or oxygen atom.
[chemical formula 3]
In chemical formula 3, R5、R6、R7And R8It is that to have 1 to 20 carbon former independently of one another
Son also can contain the organic residue of hydrogen atom, halogen atom or oxygen atom.
In the description of chemical formula 2 and chemical formula 3, described organic residue can include that aromatics is organic
Residue, aliphatic series organic residue, alicyclic organic residue, heterocyclic type organic residue or tool in chain
There are the aliphatic organic residue of aromatic ring, alicyclic organic residue or heterocyclic type organic residue.
Relative to the gross weight of adhesive resin (B), polymer (B2) preferably comprises 1 weight %
To 99 weight %, more preferably 1 weight % to 50 weight % more preferably 1 weight % are to 30 weights
Amount %.It is preferably as state of cure improves in accounting for above-mentioned scope, and therefore, when showing
Pattern it is formed accurately, even if in the case of compositions pigment content height during shadow.
It addition, in addition to the repetitive of chemical formula 2 or chemical formula 3, the present invention can be additionally
Copolymer including carboxylic monomer with other monomers having with described monomers copolymerizable.
The example of described carboxylic monomer can include unsaturated carboxylic acid such as unsaturated monocarboxylic,
Unsaturated dicarboxylic or there is the unsaturated polyvalent carboxylic acid of one or more carboxyl in the molecule such as
Unsaturated tricarboxylic acids.
The object lesson of described unsaturated monocarboxylic can include acrylic acid, methacrylic acid, Fructus Crotonis
Acid, α-chloro-acrylicacid, cinnamic acid etc..
The object lesson of described unsaturated dicarboxylic can include maleic acid, fumaric acid, itaconic acid,
Citraconic acid, mesaconic acid etc..
Described unsaturated polyvalent carboxylic acid can be anhydride, and its specific example can include maleic acid
Acid anhydride, itaconic anhydride, citraconic anhydride etc..It addition, described unsaturated polyvalent carboxylic acid can be its single (2-
Methacryloxyalkyl) ester, its object lesson can include list (2-acryloyl-oxyethyl) amber
Amber acid esters, single (2-methacryloxyethyl) succinate, list (2-acryloyl-oxyethyl)
Phthalic acid ester, list (2-methacryloxyethyl) phthalic acid ester etc..Described insatiable hunger
Can be list (methyl) acrylate of dicarboxyl polymer with the two ends of polyvalent carboxylic acid, its concrete example
Son can include ω-carboxyl many caprolactones mono acrylic ester, ω-carboxyl many caprolactones monomethacrylate
Ester etc..
Described carboxylic monomer can make individually or as the mixture of two or more types
With.
Described copolymer (B3) is by combined polymerization aromatic vinyl compound (B ' 1), at one
Molecule has compound (B ' 2) and the change of chemical formula 4 below of unsaturated bond and epoxide group
Compound (B ' 3) and obtain.
More specifically, described copolymer (B3) includes the copolymer containing unsaturated group, its
By the compound represented by chemical formula 4 below (B ' 3) is reacted to by aromatic vinyl
Compound (B ' 1) and there is in a molecule compound (B ' 2) of unsaturated bond and epoxide group
Obtain on the copolymer that combined polymerization obtains.
[chemical formula 4]
In chemical formula 4,
R1And R2It is unsubstituted independently of one another or is selected from halogen, ketone group, ester group and mercapto
In one or more types substituted C1 to C6 alkyl,
A is unsubstituted or one or more types of being selected from halogen, methoxyl group and ethyoxyl take
The aliphatic polycyclic moiety in generation；With unsubstituted or be selected from pi-allyl, halogen, methoxyl group, ethyoxyl
With one or more types substituted aromatics polycyclic moiety in C1 to C8 alkoxyl；With
N and m is individually 0 or 1.
The concrete example of described aromatic vinyl compound (B ' 1, be hereinafter also referred to as ' B ' 1 ')
Son can include vinyltoluene, styrene, α-methyl styrene, α-chlorostyrene, vinyl
Ketopyrrolidine, divinylbenzene etc., but it is not limited to this, and these can be individually or as two kinds
Or more types of be applied in combination.When considering preparation availability, reliability etc., use ethylene
Base toluene is preferred as described aromatic vinyl compound (B ' 1).Particularly, contain
The adhesive resin (B) prepared as aromatic vinyl compound including vinyltoluene
Color Photosensitve resin composition, has and effectively reduces the advantage producing outgassing.
Described there is in a molecule unsaturated bond and epoxide group compound (B ' 2, under
Also referred to as ' B ' 2 ' in literary composition) object lesson can include (methyl) glycidyl acrylate, (first
Base) acrylic acid 3,4-ethyoxyl cyclohexyl, (methyl) acrylic acid 3,4-ethoxycyclohexyl methyl ester, (first
Base) acrylic acid methylglycidyl esters etc., but it is not limited to this, and these can be individually or as
Being applied in combination of two or more types.Especially (methyl) glycidyl acrylate can in preparation
Obtain property and reliability aspect is outstanding, can more preferably use.
In the present invention, (methyl) acrylate refers to acrylate and/or methacrylate.
It addition, the compound of described chemical formula 4 (B ' 3, be hereinafter also referred to as ' B ' 3 ') does not has
There is particularly restriction, but, use the chemical combination selecting free chemical formula 5 below to represent to chemical formula 9
One or more types in thing are preferred.
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
According to the present invention, described adhesive resin (B) preferably use gel permeation chromatography (GPC,
Use oxolane as eluting solvent) measure have polystyrene conversion weight average molecular weight (
Hereinafter be also referred to as ' weight average molecular weight ') be 2000 to 100000 resin, and more preferably have
There is the resin that weight average molecular weight is 3000 to 50000 of polystyrene conversion.Described Weight-average molecular
Amount is preferably as improve hardness of film within the above range, causes film retention rate height, storage
Deposit the dissolubility that stability is outstanding and non-exposed unit is in developing solution outstanding, and improve point
Resolution.
It addition, the molecular weight distribution of adhesive resin (B), that is, weight average molecular weight compares number
Average molecular weight (weight average molecular weight (Mw)/number-average molecular weight (Mn)), with regard to developability and storage
Deposit for stability preferably from 1.5 to 6.0 and more preferably from 1.8 to 4.0.
Adhesive resin (B) is preferably based on solid and has 30mgKOH/g to 170mgKOH/g
And the acid number of more preferably 50mgKOH/g to 150mgKOH/g.Acid number is less than 30mgKOH/g
Adhesive resin (B) because colored photosensitive resin composition be difficult to ensure that enough developing rates
Rather than preferably, and acid number is undesirable more than 170mgKOH/g because pattern due to
The adhesion of substrate reduces and is susceptible to short circuit, and owing to the problem with colorant compatible can
The problem of colorant precipitation in colored photosensitive resin composition can occur, or due to colored photosensitive tree
The storage stability of oil/fat composition reduces, it may occur however that the problem that viscosity increases.
Relative to the solid in colored photosensitive resin composition of the present invention, adhesive resin (B) exists
Weight fraction preferably comprises 1 weight % to 85 weight % more preferably 10 weight % to 70 weight %.
It is preferred based on above-mentioned standard from adhesive resin (B) content of 1 weight % to 85 weight %,
Because due to abundant to the dissolubility of developing solution, it is difficult in the non-pixel portion of substrate to occur aobvious
Shadow residue, and by preventing the film of the pixel portion of exposing unit during developing from reducing, non-
The depigmentation of pixel portion is intended to good.
(C) photopolymerizable compound
The photopolymerizable compound (C) that the colored photosensitive resin composition of the present invention includes is
By by Photoepolymerizationinitiater initiater (D) from the description below through light irradiate and produce active group,
The polymerisable compounds such as acid, and have no particular limits, as long as it is can be gathered by described light
Close the compound of the effect polymerization of initiator.Preferably, it is possible to use monofunctional monomer, double
Functional monomer or trifunctional or higher polyfunctional monomer, and can use and select from which
One or more type monomers.
The object lesson of described monofunctional monomer can include nonylphenol acrylate phenyl carbitol ester, third
Olefin(e) acid 2-hydroxyl-3-phenoxy-propyl, acrylic acid 2-ethylhexyl carbitol ester, acrylic acid 2-hydroxyl
Base ethyl ester, NVP etc., and its commodity can include Aronix M-101
(Toagosei Co., Ltd.), KAYARAD TC-110S (Nippon Kayaku Co., Ltd.),
Biscoat 158 (Osaka Yuki Kagaku Kogyo Co., Ltd.) etc., but it is not limited to this.
The object lesson of described bifunctional monomer can include 1,4-butanediol two (methyl) acrylate,
1,6-HD two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (first
Base) acrylate, triethylene glycol two (methyl) acrylate, double (acryloxy second of bisphenol-A
Base) ether, 3-methyl pentanediol two (methyl) acrylate, dimethacrylate, amino
Formic acid esters (methyl) acrylate etc., and its commodity can include Aronix M-210, M-1100
Or 1200 (Toagosei Co., Ltd.), KAYARAD HDDA (Nippon Kayaku Co.,
Ltd.), Biscoat 260 (Osaka Yuki Kagaku Kogyo Co., Ltd.), AH-600,
AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.) etc., but it is not limited to this.
The object lesson of described trifunctional or higher polyfunctional monomer can include trihydroxy methyl third
Alkane three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, the third oxygen
Base trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, season
Penta tetrol four (methyl) acrylate, dipentaerythritol diacrylate, dipentaerythritol three propylene
Acid esters, dipentaerythritol five (methyl) acrylate, ethoxylated dipentaerythritol six (methyl) third
Olefin(e) acid ester, propoxylated dipentaerythritol six (methyl) acrylate, dipentaerythritol six (methyl)
Acrylate etc., and its commodity can include Aronix M-309, TO-1382 (Toagosei
Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD
DPHA-40H (Nippon Kayaku Co., Ltd.) etc., but it is not limited to this.
Among photopolymerizable compound illustrated above, use trifunctional or higher many
Functional monomer is it is furthermore preferred that and have outstanding polymerizability with regard to them and can improve strong
For degree, (methyl) acrylate and carbamate (methyl) acrylate are more preferably.
Relative to the solid in colored photosensitive resin composition of the present invention, photopolymerizable compound
(C) in weight fraction, 1 weight % to 50 weight % more preferably 10 weight % are preferably comprised extremely
35 weight %.The photopolymerizable chemical combination of 1 weight % to 50 weight % scopes is accounted for based on above-mentioned standard
Thing (C), because the intensity of pixel cell or flatness become favourable, thus is preferred.
(D) Photoepolymerizationinitiater initiater
The Photoepolymerizationinitiater initiater (D) that the colored photosensitive resin composition of the present invention includes is to pass through
Be exposed to visual ray, ultraviolet, far ultraviolet rays, electron beam and radiation such as X-ray and
Generation can cause the chemical combination of the group etc. that photopolymerizable compound (C) described above is polymerized
Thing.
The type of Photoepolymerizationinitiater initiater (D) has no particular limits, as long as it is not damage this
Compound commonly used in the art and described binding agent tree can be polymerized in the range of the purpose of invention
Fat and photopolymerizable compound.Its exemplary can include oxime compound, 1-Phenylethanone.
Compounds, benzoin compounds, benzophenone compound, bisglyoxaline compounds, three
Piperazine compounds, thiaxanthone compounds, anthracene compounds etc., but it is not limited to this, and permissible
Therefrom select one or more types and use.Among those, when considering aggregation property, initiation
When efficiency, absorbing wavelength etc., it is preferred for using oxime compound.
The example of described oxime compound can include adjacent carbethoxyl group-α-oxyimino group-1-phenyl third
-1-ketone, (Z)-2-((benzoyloxy) imino group)-1-(4-(thiophenyl) phenyl) octyl-1-ketone (refers to followingization
Formula 10), (E)-1-(((1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base) ethylidine)
Amino) oxygen) ethyl ketone (referring to chemical formula 1 below 1), (E)-1-(((1-(6-(4-((2,2-dimethyl-1,3-dioxy
Penta ring-4-base) methoxyl group)-2-methyl benzoyl)-9-ethyl-9H-carbazole-3-base) ethylidine) amino)
Oxygen) ethyl ketone (referring to chemical formula 1 below 2) etc., and its commodity can include BASF Corporation
OXE-01 and OXE-02 etc., but be not limited to this.
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
The content of Photoepolymerizationinitiater initiater (D) has no particular limits, but, relative to color sensation
Total solid weight in photopolymer resin compositions, described Photoepolymerizationinitiater initiater preferably comprises 0.1 weight % extremely
40 weight % more preferably 1 weight % are to 30 weight %.Photoepolymerizationinitiater initiater within the above range
Content is preferably as described colored photosensitive resin composition becomes extremely sensitive, shortens exposure
The light time, this improves productivity ratio and maintain high-resolution.It addition, utilize the present invention's
The intensity of the pixel cell that colored photosensitive resin composition is formed and putting down of described pixel cell surface
Whole degree can become favourable.
Meanwhile, according to one embodiment of the present invention, described Photoepolymerizationinitiater initiater (D) also may be used
To include that photopolymerization causes auxiliary agent (d1), to improve the colored photosensitive resin composition of the present invention
Sensitivity.The colored photosensitive resin composition of the present invention by containing described photopolymerization cause auxiliary agent,
Productivity ratio can be improved because increasing sensitivity further.
Described photopolymerization causes the example of auxiliary agent (d1) can preferably include selected from amines, carboxylic
In the group that acid compound, the organosulfur compound with mercapto and alkoxy anthracene compound are formed
One or more type compounds, but be not limited to this.
(E) solvent
Solvent (E) according to the present invention can use solvent commonly used in the art, the most especially
Restriction, as long as it effectively dissolves other components that described colored photosensitive resin composition includes i.e.
Can.Object lesson as described solvent, it is possible to use selected from ethers, acetate esters, aromatic hydrocarbons,
One or more types in ketone, alcohols, esters, amide-type etc., but, described solvent is not
It is limited to this.
The object lesson of described ether solvent can include ethylene glycol monoalkyl ether such as ethylene glycol list
Methyl ether, ethylene glycol monoethyl ether, ethylene glycol ether and ethylene glycol monobutyl ether；Diethylene glycol dialkyl group
Ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol
Butyl oxide；Deng.
The object lesson of described acetate esters solvent can include aklylene glycol alkylether acetates
Such as methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, third
2-ethoxyethanol acetas and propylene glycol monopropyl ether acetas；Alkoxyalkyl acetas such as acetic acid
Methoxybutyl and acetic acid methoxyl group pentyl ester；Deng.
The object lesson of described aromatic hydrocarbon solvent can include benzene,toluene,xylene, sym-trimethylbenzene.
Deng.
The object lesson of described ketones solvent can include methyl ethyl ketone, acetone, methyl amyl ketone,
Methyl iso-butyl ketone (MIBK), Ketohexamethylene etc..
The object lesson of described alcohols solvent can include ethanol, propanol, butanol, hexanol, hexamethylene
Alcohol, ethylene glycol, glycerol etc..
The object lesson of described esters solvent can include cyclic ester such as gamma-butyrolacton；3-ethoxy-c
Acetoacetic ester, 3-methoxy methyl propionate, etc..
The object lesson of described amide solvent can include N,N-dimethylformamide, N, N-diformazan
Yl acetamide, N-Methyl pyrrolidone etc..
According to coating performance and dry property, described solvent (E) be preferably boiling point be 100 DEG C extremely
The organic solvent of 200 DEG C, can more preferably include aklylene glycol alkylether acetates class；Ketone；
Esters such as 3-ethoxyl ethyl propionate and 3-methoxy methyl propionate, and can more preferably wrap
Include propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, Ketohexamethylene, 3-ethoxy-propionic acid
3-ethyl ester, 3-methoxy methyl propionate etc..These solvents can be individually or as two or more
The mixture of type uses.
Relative to the gross weight of colored photosensitive resin composition of the present invention, the colored photosensitive tree of the present invention
The content of the solvent (E) that oil/fat composition includes is preferably from 30 weight % to 95 weight % more excellent
Select from 70 weight % to 85 weight %.When solvent (E) accounts for above-mentioned scope, when with coating apparatus
Such as roll coater, spin coater, slit spin coater, slit type coater (are sometimes referred to as die coating cloth
Machine) and ink jet printer coating time, it is provided that the effect of favourable coating performance.
(F) additive
Within the scope without prejudice to the object of the present invention, the colored photosensitive resin composition of the present invention also may be used
Additive (F) in addition to the above components, example is included with the needs according to those skilled in the art
As filler, other polymer compounds, firming agent, surfactant, adhesion promoter, antioxidant,
Solve coalescent, pigment dispersing agent and ultraviolet absorber.
Described surfactant may be used for improving further the film forming of described Photosensitve resin composition
Character, and the object lesson of described surfactant can preferably include fluorine class surfactant,
Organosilicone surfactants etc..
As commodity, the example of described fluorine class surfactant includes, by DIC Corporation
Megafac F-470, F-471, F-475, F-482, the F-489 etc. manufactured.
As commodity, the example of described organosilicone surfactants includes, by Dow Corning
DC3PA that Toray Silicone Co., Ltd. manufactures, DC7PA, SH11PA, SH21PA,
SH-8400 etc., and by GE Toshiba Silicone Co., Ltd manufacture TSF-4440,
TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 etc..
Surfactant exemplified above can be individually or as two or more types
Mixture uses.
Described pigment dispersing agent is can be in order to pigment (a1) solves coalescence and keeps stability to add
Component.One example of the method for dispersed pigment (a1) particle includes by adding pigment
Dispersant carries out dispersion process, it is possible to obtain the dispersed dispersible pigment dispersion in the solution of pigment.
As described pigment dispersing agent, it is possible to use be generally used for those in this area, not limit
System.
The example of the method for the colored photosensitive resin composition of the preparation present invention can be described as follows.
First, ball mill etc. is utilized to be mixed with solvent (E) by the pigment (a1) in coloring agent (A)
Merge dispersion, until the mean diameter of described pigment becomes about 0.2 μm or less.Here, root
According to needs, described pigment dispersing agent, some or all of adhesive resin (B) or dyestuff
(a2) can mix with solvent (E), and dissolve or dispersion.
To described mixed dispersion liquid add further dyestuff (a2), remaining adhesive resin (B),
Photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D), additive (F) as required
With solvent (E) so that have specific concentration, it is possible to prepare according to the present invention color sensation
Photopolymer resin compositions.
It addition, the present invention includes the colored pattern prepared with described colored photosensitive resin composition.Institute
Stating colored pattern can be by applying colored photosensitive resin composition the light of the present invention on substrate
Solidification and develop described product and prepare.The thickness of described colored pattern has no particular limits,
And for example, it is possible to from 1 μm to 6 μm.
<colored filter>
It addition, the invention provides the color-patch map including preparing with described colored photosensitive resin composition
The colored filter of case.The colored filter of the present invention includes substrate and on the substrate with this
Colored pattern prepared by the colored photosensitive resin composition of invention.Described substrate is transparent material, and
And for the stability of described colored filter, it is possible to use there is enough intensity and supporting force
Material.Preferably, it is possible to use there is the glass of outstanding chemical stability and high intensity.
As the method manufacturing described colored filter, it is possible to use general side as known in the art
Method.
<image display device>
Present invention also offers the image display device including described colored filter.Described image shows
The object lesson of showing device can include display device such as liquid crystal display (liquid crystal indicator；
LCD), organic el display (organic EL display), liquid crystal projection apparatus, game machine
The display device of display device, portable terminal such as portable phone, the display of digital camera
Device and the display device etc. of auto navigation, and colour display device is specially suitable.
In addition to providing described colored filter, described image display device includes art technology
Structure known to personnel, in other words, the present invention includes the colored filter that can use the present invention
Image display device.
Hereinafter, reference example and comparative example are more fully described the present invention.But, with
Lower embodiment, only for illustrative purpose, the invention is not restricted to following example, it is possible at this
Diversely modifications and changes in the range of invention.The scope of the present invention is wanted by the right described below
The technical concept asked determines.
It addition, represent " % " and " part " of content in following preparation example, embodiment and comparative example
It is based on weight, unless otherwise expressly specified.
<synthesis example>
<synthesis example 1 to 6>
To be equipped with agitator, thermostat, reflux cooling pipe, Dropping funnel (dropping lot) and
The flask of nitrogen introducing tube introduces the propylene glycol methyl ether acetate of 150 weight portions, and in flask
Atmosphere after air is converted to nitrogen, temperature is increased to 100 DEG C.Afterwards, according to synthesis example
1 to 6 respective composite adhesives resin.
Synthesis example 1. adhesive resin B-1
Add the methacrylic acid of 15 weight portions, the N-phenylmaleimide of 25 weight portions, 35
The benzyl methacrylate of weight portion, the glycerol monomethacrylate of 10 weight portions, 15 weight
After the styrene of part and the α-methyl styrene dimer (chain-transferring agent) of 2.5 weight portions, with 2
Hour instill double for 1 weight portion 2,2 '-azo (2,4-methyl pentane nitrile) to flask from described Dropping funnel
Add the solution in 50 parts by weight of propylene glycol methyl ether acetates to, and by product at 100 DEG C
Under be further continued for stirring 5 hours.
Obtain the resin solution (solid concentration=30 weight %) that solid acid value is 97mgKOH/g
B-1.It is 24000 by the weight average molecular weight of the polystyrene conversion of gpc measurement, molecular weight distribution
(Mw/Mn) it is 2.3.
Synthesis example 2. adhesive resin B-2
Add the methacrylic acid of 15 weight portions, the N-benzyl maleimide of 25 weight portions, 35
The benzyl methacrylate of weight portion, the glycerol monomethacrylate of 10 weight portions, 15 weight
After the styrene of part and the α-methyl styrene dimer (chain-transferring agent) of 2.5 weight portions, with 2
Hour instill double for 1 weight portion 2,2 '-azo (2,4-methyl pentane nitrile) to flask from described Dropping funnel
Add the solution in 50 parts by weight of propylene glycol methyl ether acetates to, and by product at 100 DEG C
Under be further continued for stirring 5 hours.
Obtain the resin solution (solid concentration=30 weight %) that solid acid value is 95mgKOH/g
B-2.It is 25000 by the weight average molecular weight of the polystyrene conversion of gpc measurement, molecular weight distribution
(Mw/Mn) it is 2.2.
Synthesis example 3. adhesive resin B-3
Add ω-carboxyl two caprolactone list propylene of the methacrylic acid of 15 weight portions, 10 weight portions
Acid esters, the N-phenylmaleimide of 25 weight portions, the benzyl methacrylate of 35 weight portions,
The glycerol monomethacrylate of 10 weight portions, the styrene of 15 weight portions and 2.5 weight portions
After α-methyl styrene dimer (chain-transferring agent), with 2 hours from described Dropping funnel to flask
Instill and add 1 weight portion 2,2 '-azo double (2,4-methyl pentane nitrile) to 50 parts by weight of propylene glycol lists
Solution in methyl ether acetate, and be further continued for product at 100 DEG C stirring 5 hours.
Obtain the resin solution (solid concentration=30 weight %) that solid acid value is 100mgKOH/g
B-3.It is 22000 by the weight average molecular weight of the polystyrene conversion of gpc measurement, molecular weight distribution
(Mw/Mn) it is 2.2.
Synthesis example 4. adhesive resin B-4
Add the list ((2-methylacryoyloxyethyl) of the methacrylic acid of 15 weight portions, 10 weight portions
Succinate, the N-phenylmaleimide of 25 weight portions, the methacrylic acid benzyl of 25 weight portions
The α-methyl styrene dimer (chain-transferring agent) of ester, the styrene of 25 weight portions and 2.5 weight portions
After, instilled 1 weight portion 2,2 '-azo double (2,4-to flask from described Dropping funnel with 2 hours
Methyl pentane nitrile) add the solution in 50 parts by weight of propylene glycol methyl ether acetates to, and will generate
Thing is further continued for stirring 3 hours at 100 DEG C.
Obtain the resin solution (solid concentration=30 weight %) that solid acid value is 105mgKOH/g
B-4.It is 15000 by the weight average molecular weight of the polystyrene conversion of gpc measurement, molecular weight distribution
(Mw/Mn) it is 2.5.
Synthesis example 5. adhesive resin B-5
Add the methacrylic acid of 15 weight portions, the N-phenylmaleimide of 25 weight portions, 10
The benzyl methacrylate of weight portion, the n-BMA of 20 weight portions, 15 weight portions
The Alpha-Methyl benzene of styrene, the 2-hydroxyethyl methacrylate of 15 weight portions and 2.5 weight portions
After ethylene dimerization body (chain-transferring agent), instilled 1 to flask from described Dropping funnel with 2 hours
Weight portion 2,2 '-azo double (2,4-methyl pentane nitrile) adds 50 parts by weight of propylene glycol monomethyl ether acetic acid to
Solution in ester, and be further continued for product at 100 DEG C stirring 3 hours.
Obtain the resin solution (solid concentration=30 weight %) that solid acid value is 94mgKOH/g
B-5.It is 12000 by the weight average molecular weight of the polystyrene conversion of gpc measurement, molecular weight distribution
(Mw/Mn) it is 2.4.
Synthesis example 6. adhesive resin B-6
Add ω-carboxyl two caprolactone list propylene of the methacrylic acid of 15 weight portions, 10 weight portions
Acid esters, the N-phenylmaleimide of 15 weight portions, the methacrylic acid 2-ethyl of 33 weight portions
Own ester, the styrene of 12 weight portions, the glycerol monomethacrylate of 15 weight portions and 2.5 weight
Part α-methyl styrene dimer (chain-transferring agent) after, with 2 hours from described Dropping funnel to
Flask instills and double for 1 weight portion 2,2 '-azo (2,4-methyl pentane nitrile) adds to 50 weight portions the third two
Solution in alcohol methyl ether acetate, and be further continued for product at 100 DEG C stirring 3 hours.
Obtain the resin solution (solid concentration=30 weight %) that solid acid value is 103mgKOH/g
B-6.It is 15300 by the weight average molecular weight of the polystyrene conversion of gpc measurement, molecular weight distribution
(Mw/Mn) it is 2.3.
Synthesis example 7. adhesive resin B-7
23.3g is added to the 4-neck flask being equipped with Dropping funnel, thermostat, cooling tube and agitator
Methyl-2-(bromomethyl) acrylate (product of Sigma-Aldrich Co.LLC.), 15.8g
Triethylamine (product of Sigma-Aldrich Co.LLC.) and the propylene glycol monomethyl ether of 115.0g
(product of TCI Co., Ltd.), and the inside of described 4-neck flask is replaced with nitrogen.It follows that
Described flask was heated to 90 DEG C, and was added dropwise over methyl-2-(the hydroxyl first of 15.1g to it with 1 hour
Base)-acrylate (product of Sigma-Aldrich Co.LLC.), 3.2g 2,2 '-azo double different
Butyronitrile (Wako Pure Chemical Industries, the product of Ltd.) and the propylene glycol of 110.0g
The mixed solution of monomethyl ether (product of TCI Co., Ltd.), and carry out 30 minutes polyreactions
To produce the polymer containing pyrans.Then, it was slowly added drop wise 37.5g's with 1 hour to it
Methacrylic acid, the methyl methacrylate of 19.0g, the propylene glycol monomethyl ether of 225.0g and 3.2g
2,2 '-azobis isobutyronitrile (Wako Pure Chemical Industries, the product of Ltd.)
Mixed solution, carries out 8 hours polyreactions, and then product is put and is cooled to room temperature.
After replacing described 4-neck flask interior with nitrogen, add the methyl-prop of 61.5g to described flask
Olefin(e) acid ethylene oxidic ester (product of Mitsubishi Rayon), the tetra-n-butyl ammonium bromide of 3.6g
First quinone (methoquinone) (the Junsei Chemical of (product of TCI Co., Ltd.) and 0.15g
The product of Co., Ltd.), and product is reacted at 80 DEG C 12 hours with to described copolymer
Carboxyl plus glycidyl methacrylate (GMA), then, obtain adhesive resin
B-7。
It is 23000 by the weight average molecular weight of the adhesive resin B-7 of gpc measurement.
Synthesis example 8. adhesive resin B-8
Add 37.5g's to the 4-neck flask being equipped with Dropping funnel, thermostat, cooling tube and agitator
The methacrylic acid product of Co., Ltd. (Kyoeisha Chemical), the metering system of 19.0g
The acid methyl ester product of Co., Ltd. (Kyoeisha Chemical), the DHF (TCI of 9.1g
The product of Co., Ltd.) and the propylene glycol monomethyl ether (product of TCI Co., Ltd.) of 225.0g,
And the inside of described 4-neck flask is replaced with nitrogen.It follows that described flask is heated to 70 DEG C,
And it was slowly added drop wise the metering system of the methacrylic acid of 37.5g, 19.0g to it with 1 hour
Acid methyl ester, the DHF of 9.1g, the propylene glycol monomethyl ether of 225.0g and the 2 of 3.2g, 2 '-
The mixing of azobis isobutyronitrile (Wako Pure Chemical Industries, the product of Ltd.) is molten
Liquid.After being polymerized 8 hours, product is placed and is cooled to room temperature, replace described 4-neck with nitrogen and burn
Bottle is internal, then adds the glycidyl methacrylate of 61.5g to described flask
Tetra-n-butyl ammonium bromide (the TCI Co., Ltd. of (product of Mitsubishi Rayon), 3.6g
Product) and the first quinone product of Co., Ltd. (Junsei Chemical) of 0.15g, and will be raw
Thing is become to react 12 hours at 80 DEG C to add Glycidyl methacrylate to the carboxyl of described copolymer
Glyceride (GMA), then, obtains adhesive resin B-8.
It is 17000 by the weight average molecular weight of the adhesive resin B-8 of gpc measurement.
Synthesis example 9. adhesive resin B-9
To being equipped with agitator, thermostat, reflux cooling pipe, Dropping funnel and the burning of nitrogen introducing tube
Bottle introduces the propylene glycol methyl ether acetate of 182g, and the atmosphere in flask is converted to from air
After nitrogen, temperature is increased to 80 DEG C.The azobis isobutyronitrile of 3.6g is added to and includes 85.2g
(0.6mol) glycidyl methacrylate, the vinyltoluene of 23.6g (0.2mol) and
Solution in the mixture of the propylene glycol methyl ether acetate of 136g leaked from described dropping liquid with 2 hours
Bucket instills described flask, and continues product at 80 DEG C to be stirred for 5 hours.Then, institute
The atmosphere stated in flask is transformed into air from nitrogen, and by 29.6g, [0.6mol is (relative to for described
The epoxide group of the glycidyl methacrylate in reaction is 33.33mol%)] chemical formula
The hydroquinone of the compound of 6, the three dimethylaminomethyl phenol of 0.9g and 0.145g introduces described flask,
And product is continued at 110 DEG C reaction 4 hours, it is thus achieved that adhesive resin B-9.Use GPC
The weight average molecular weight of the polystyrene conversion measured is 17000, and molecular weight distribution (Mw/Mn) is
2.3。
Synthesis example 10 to 13. adhesive resin B-10 to B-13
In addition to the variation listed during its respective component and content are by table 1 below, binding agent tree
Fat is prepared in the way of identical with synthesis example 9.
[table 1]
The weight average molecular weight (Mw) of described binder polymer and the measurement of number-average molecular weight (Mn)
GPC method is utilized to carry out under the following conditions:
Device: HLC-8120GPC (Tosoh Corporation manufacture)
Post: TSK-GELG4000HXL+TSK-GELG2000HXL (connects)
Column temperature: 40 DEG C
Mobile solvent: oxolane
Flow velocity: 1.0ml/min
Sample size: 50 μ l
Detector: RI
The concentration of measuring samples: 0.6 weight % (solvent=oxolane)
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4,
F-1, A-2500, A-500 (Tosoh Corporation manufacture)
The ratio of weight average molecular weight obtained above and number-average molecular weight is with molecular weight distribution
(Mw/Mn) use.
The preparation of colored photosensitive resin composition
Preparation has example 1 below to the composition described in 18 and comparative example 1 to 5 and content
Colored photosensitive resin composition.
<embodiment 1 to 9 and comparative example 1 to 2>
Embodiment 1.
The preparation of fluid composition (G1)
Using 40 weight portions as the C.I. naphthol green 59 (manufacturer: DIC Corporation) of pigment
(convert with solid with 60/40 (weight ratio) mixture, 24 weight portions of C.I. pigment yellow 185
About 10.8 weight portions) as BYK 2001 (the DISPER BYK:BYK Chemie of dispersant
Manufacture, solid concentration 45.1 weight %) and include 136 parts by weight of propylene glycol lists as solvent
The mixed liquor of methyl ether acetate utilizes ball mill to mix/disperse 12 hours, prepares dispersible pigment dispersion.
Subsequently, using the dispersible pigment dispersion obtained by 400 weight portions, 200 weight portions as binding agent
The resin solution (B-1) of resin, 60 weight portions are as two seasons penta 4 of photopolymerizable compound
Alcohol six acrylate, 40 weight portions are as the 2-benzyl-2-dimethylamino of Photoepolymerizationinitiater initiater
-1-(4-morpholino phenyl) butanone-1 and 1000 weight portions are as the propylene glycol monomethyl ether acetic acid of solvent
Ester mixes, and prepares fluid composition (G1).
Embodiment 2 to 6.
The preparation of fluid composition (G2 to G6)
Except using 200 parts by weight resin solution (B-2) (embodiment 2), 200 weight portion trees
Lipoprotein solution (B-3) (embodiment 3), 200 parts by weight resin solution (B-4) (embodiment 4),
200 parts by weight resin solution (B-6) (embodiment 5) or 200 parts by weight resin solution (B-5)
Outside (embodiment 6) replaces 200 parts by weight resin solution (B-1) as adhesive resin, liquid
Body compositions (G2 to G6) is prepared in the same manner as example 1.
Embodiment 7.
The preparation of fluid composition (G7)
In addition to using C.I. pigment yellow 150 to replace C.I. pigment yellow 185, fluid composition (G7)
Prepare in the same manner as example 1.
Embodiment 8.
The preparation of fluid composition (G8)
Except using 200 parts by weight resin solution (B-4) to replace 200 parts by weight resin solution (B-1)
Outside adhesive resin, fluid composition (G8) is prepared in the way of same as in Example 7.
Embodiment 9.
The preparation of fluid composition (G9)
Except using 200 parts by weight resin solution (B-6) to replace 200 parts by weight resin solution (B-1)
Outside adhesive resin, fluid composition (G9) is prepared in the way of same as in Example 7.
Comparative example 1.
The preparation of fluid composition (g1)
Mixture (the weight of C.I. pigment Green 7 and C.I. pigment yellow 185 except using 40 weight portions
Amount is than 56:44) replace described C.I. naphthol green 59 (manufacturer: the DIC of 40 weight portions
Corporation) and 60/40 (weight ratio) mixture of C.I. pigment yellow 185 as pigment outside,
Fluid composition (g1) is prepared in the same manner as example 1.
Comparative example 2.
The preparation of fluid composition (g2)
Mixture (the weight of C.I. pigment Green 7 and C.I. pigment yellow 150 except using 40 weight portions
Amount is than 55:45) replace described C.I. the naphthol green 59 and C.I. pigment yellow 150 of 40 weight portions
Outside 60/40 (weight ratio) mixture is as pigment, fluid composition (g2) with embodiment 7
Prepared by identical mode.
<embodiment 10 to 18 and comparative example 3 to 5>
[table 2]
(weight portion)
<test example>colored photosensitive resin composition evaluation
<test example 1 to 3>
The formation of pattern of pixels
The glass substrate (Corning Incorporated manufactures, #1737) of 2 square inches is used in succession
Mild detergent, water and alcohol washing, be then dried.Embodiment 1 to 9 and comparative example 1 and 2
Each compositions is spin-coated on this glass substrate so that when with 100mJ/cm2Light exposure (365nm)
When exposing and skip process color, the film thickness after rear baking becomes 2.0 μm, then described
Product preliminarily dried 3 minutes at 100 DEG C in the baking oven of cleaning.After cooling, by this coloring
Photosensitve resin composition coated substrates and the photomask being made up of quartz glass (have absorbance with step
Enter mode from 1 to 100% pattern changed and the lines/void pattern of 1 μm to 50 μm) between
Distance be maintained at 100 μm, under air atmosphere, utilize the supertension manufactured by USHIO Inc.
Finsen lamp (name of product USH-250D) is with 100mJ/cm2The light of light exposure (365nm)
Irradiate.
Afterwards, described film is including 0.12% nonionic surfactant and 0.06% potassium hydroxide
Developing aqueous solution at 26 DEG C soak regular time develop, then rinse product,
Then it is dried 30 minutes at 220 DEG C.
Test example 1. brightness measurement
Brightness utilizes microspectrograph OSP-SP2000 to measure, and the brightness value at identical chromaticity coordinates exists
Table 3 below is listed.
Test example 2. chromaticity coordinates evaluation
The chromaticity coordinates of described dyed layer utilizes microspectrograph OSP-SP2000 to measure, result under
Face table 3 is listed.
Test example 3. contrast evaluation
Substrate obtained above is placed on two and rises between Polarizer, is utilizing Topcon Korea
The BM-5A type contrast that Corporation manufactures is measured equipment and is irradiated fluorescence (wavelength model from rear side
Enclose 380nm to 780nm) while the maximum of measured light intensity and minima, contrast with
Described maximum is divided by the value evaluation of described minima.Measurement standard be based on glass substrate (
Chromatograph formed before) contrast 1/30000.
It addition, store after one month at 23 DEG C, utilize various fluid composition (G1 to G9,
G1 and g2) evaluate contrast in the same fashion, result shows in the following Table 3.
[table 3]
<test example 4 to 7>
Each light curing resin composition of preparation in embodiment 10 to 13 and comparative example 3 and 4
Spin coater is utilized to be coated on 50mm × 50mm glass substrate while controlling revolution,
Making dried film thickness become 2.5 μm, product is dried 3 minutes at 100 DEG C in an oven.
Described dry base plate exposure so that the comprehensive light exposure merging lamp (fusion lamp) exists
Distance photomask 300 μm distance becomes 40mJ, and manufactures colored filter.
Afterwards, each method described in test example 4 to 7 is utilized to test.
Test example 4. sensitivity assessment
Afterwards, described colored filter utilizes the KOH aqueous solution of spray development device pH 10.5 to show
Shadow 1 minute, rinses and dries.Afterwards, product solidifies 20 minutes at 230 DEG C in an oven,
Measure the pattern line-width in colored filter and pattern extent of exfoliation.
Identify described pattern line-width (X1) and the difference of photomask live width (X2) sensitivity of measurement.
Result shows in the following Table 4.
<live width evaluation criterion>
+ 5 or higher: suitable
More than or equal to-5 and less than+5: good
Less than-5: be not suitable for
<pattern stripping evaluation criterion>
Zero: do not have pattern to peel off
△: 1 to 3 place's pattern is peeled off
X:4 or more many places pattern are peeled off
Test example 5. solvent resistance evaluation
Afterwards, described colored filter utilizes the KOH aqueous solution of spray development device pH 10.5 to show
Shadow 1 minute, rinses and dries.Afterwards, product solidifies 20 minutes at 230 DEG C in an oven.
Described colored filter at room temperature immersion 30 minutes in nmp solution, with milli-Q water also
The hot plate be heated to 120 DEG C is dried 2 minutes, measures the colourity before and after soaking.Use at this
Formula calculated by following mathematical expression 1, described mathematical expression 1 illustrate by L*, a* and b* limit
The fixed variable color in 3-dimension colorimeter, and because variable color is less, it is possible to manufacture high reliability
Colored filter.Result shows in the following Table 4.
[mathematical expression 1]
△ Eab*=[(△ L*) 2+ (△ a*) 2+ (△ b*) 2] ^0.5
<solvent resistance evaluation criterion>
△ Eab* is 3 or less: be suitable for
△ Eab* is more than 3: be not suitable for
Test example 6. produces the evaluation of inverted cone degree
Afterwards, described colored filter utilizes the KOH aqueous solution of spray development device pH 10.5 to show
Shadow 1 minute, rinses and dries.Afterwards, by scanning electron microscopy (HITACHI S4300)
Measure the end of manufactured pattern to measure the degree of inverted cone.As described measurement, measure from
End is internally formed the length of the part of groove and compares to pattern.Result shows table 4 below
In.
Test example 7. brightness evaluation
Afterwards, described colored filter utilizes the KOH aqueous solution of spray development device pH 10.5 to show
Shadow 1 minute, rinses and dries.Afterwards, product solidifies 20 minutes at 230 DEG C in an oven.
Brightness utilizes microspectrograph OSP-SP2000 to measure, list identical chromaticity coordinates (x=0.260,
Y=0.640) brightness value at place.Result shows in the following Table 4.
[table 4]
<test example 8 to 11>
The colored photosensitive resin composition profit of preparation in each comfortable embodiment 14 to 18 and comparative example 5
It is coated on glass substrate (#1737, Corning Incorporated manufacture) with spin-coating method, and
Product is placed on hot plate and at a temperature of 100 DEG C, keeps 3 minutes to form thin film.
Subsequently, use the 1KW high pressure mercury vapour lamp containing whole g, h and i rays as ultraviolet
Light source, makes light with 100mJ/cm2Intensity illumination on the membrane.Here, do not use spy
Different optical filter.The illuminated thin film of ultraviolet is molten in the development of the KOH aqueous solution of pH 10.5
Liquid soaks and within 2 minutes, develops.
The glass substrate distilled water wash of described film coated, then nitrogen blowing is dried, and is adding
Hot stove heats 30 minutes at 220 DEG C, to manufacture dyed layer.The thickness of the dyed layer of above-mentioned manufacture
Degree is that 1 μm is to 5 μm.
Test example 8. Evaluation of Heat Tolerance
After ultimately forming pattern, relatively and evaluate the variable color (thermostability) before and after 230 DEG C/2hr.
Being defined as outstanding here, change into 1 or less in the Eab calculated, 3 or less be well, greatly
In 3 for poor.
Formula as used herein is calculated by following<mathematical expression 1>, described mathematical expression 1 illustrate by
The variable color in 3-dimension colorimeter that L*, a* and b* limit, and because variable color is less, it is possible to
Manufacture the colored filter of high reliability.Result shows in the following Table 5.
<mathematical expression 1>
△ Eab*=[(△ L*) 2+ (△ a*) 2+ (△ b*) 2] 1/2
Test example 9. developability evaluation
The colored photosensitive resin composition profit of preparation in each comfortable embodiment 14 to 18 and comparative example 5
It is coated on glass substrate (#1737, Corning Incorporated manufacture) with spin-coating method, and
Product is placed on hot plate and at a temperature of 100 DEG C, keeps 3 minutes to form thin film.
The substrate being dried has pH 10.5 and propylene glycol methyl ether acetate (PGMEA) solvent
KOH aqueous solution soaking, measuring until dissolving institute's time spent.Result shows table 5 below
In.
<developability evaluation criterion>
Zero: 2 minute or shorter
△: be longer than 2 minutes and be shorter than or equal to 4 minutes
X: be longer than 4 minutes and peel off
Test example 10. is developed the evaluation of residue
The residue that do not develops on substrate is classified as ' zero ', occurs being classified as of development residue on substrate
‘×’.Result shows in the following Table 5.
Test example 11. brightness measurement
Brightness utilizes microspectrograph OSP-SP2000 to measure, and lists identical chromaticity coordinates
The brightness value at (x=0.262, y=0.642) place.Result shows in the following Table 5.
[table 5]
| Thermostability | Developability | Development residue | Brightness | |
| Embodiment 14 | Outstanding (0.7) | △ | ○ | 48.2 |
| Embodiment 15 | Well (1.3) | ○ | ○ | 48.4 |
| Embodiment 16 | Outstanding (0.9) | △ | ○ | 48.1 |
| Embodiment 17 | Well (1.6) | ○ | ○ | 48.0 |
| Embodiment 18 | Well (2.3) | ○ | ○ | 48.2 |
| Comparative example 5 | Outstanding (0.8) | ○ | X | 45.7 |
As shown in table 3, it can be seen that based on identical chromaticity coordinates, when using G59, with
The situation using C.I. pigment Green 7 (G7) is compared, the index of transmittance, brightness Y, increases
7.0% to 8.0%.
It addition, when compared with the comparative example with identical chromaticity coordinates, contrast also improves
300 to 3000, even and if after storing one month at 23 DEG C, the rate of descent of contrast
The least, this shows to maintain high-contrast, it is thus identified that have stability in time.
Find out from the result of table 4, the embodiment 10 that it includes in confirming the scope of the invention to
The colored photosensitive resin composition of 13 has outstanding in sensitivity, solvent resistance and brightness
Evaluation result, and also show the inverted cone degree outstanding result less than 1.5 μm.Meanwhile,
The colored photosensitive resin composition of comparative example 3 and 4 is at sensitivity, solvent resistance, inverted cone
With there is on brightness evaluation poor result.
In table 5, the embodiment 14 to 18 that it confirms to include in the scope of the invention
The colored filter that colored photosensitive resin composition is formed has outstanding thermostability and development
Property, and development residue does not occur.Meanwhile, it confirms particularly brightness and development
Residue evaluation result is the most outstanding in comparative example 5.
In other words, the colored photosensitive resin composition of the present invention be have high brightness character,
High coloring character and high sensitive have target color coordinates value simultaneously and have outstanding thermostability
Compositions with solvent resistance.
The colored photosensitive resin composition of the present invention has high brightness, high chroma and high sensitive,
And can have outstanding thermostability and developability.
Additionally, it is possible to provide formed have outstanding light transmittance and the pixel of outstanding contrast,
Improve reliability by improving curing degree and reduce the effect of inverted cone.
In addition, it is possible to provide use colored filter prepared by described colored photosensitive resin composition
And image display device.
Claims (15)
1. colored photosensitive resin composition, it comprises:
Coloring agent (A)；
Adhesive resin (B)；
Photopolymerizable compound (C)；
Photoepolymerizationinitiater initiater (D)；With
Solvent (E),
Wherein said coloring agent (A) includes C.I. naphthol green 59 and selected from pigment and dyestuff
In one or more types.
Colored photosensitive resin composition the most according to claim 1, wherein said binding agent
Resin (B) includes in copolymer (B1), polymer (B2) and copolymer (B3)
One or more types, and
Described copolymer (B1) includes (methyl) acrylic acid copolymer (b1)；N-replaces Malaysia
Acid imide (b2)；With selected from one of the following or polytype unsaturated compound (b3):
Styrene, α-methyl styrene, to hydroxy-alpha-methyl styrene, (methyl) acrylic acid methyl ester., (first
Base) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate,
(methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) glycerol acrylate, single
[2-(methyl) acryloyl-oxyethyl] succinate, ω-carboxyl many caprolactones list (methyl) acrylic acid
Ester, Group-capped Polystyrene Macromer and polymethyl methacrylate macromonomer；
Described polymer (B2) is one or more classes selected from chemical formula 2 below and chemical formula 3
Type repetitive；And
Described copolymer (B3) is by combined polymerization aromatic vinyl compound (B ' 1), one
Individual molecule has compound (B ' 2) and the chemical formula 4 below of unsaturated bond and epoxide group
Compound (B ' 3) and the copolymer that obtains:
[chemical formula 2]
Wherein, in chemical formula 2, R1、R2、R3And R4It is to have 1 to 20 independently of one another
Individual carbon atom also can contain the organic residue of hydrogen atom, halogen atom or oxygen atom,
[chemical formula 3]
In chemical formula 3, R5、R6、R7And R8It is that to have 1 to 20 carbon former independently of one another
Son also can contain the organic residue of hydrogen atom, halogen atom or oxygen atom,
[chemical formula 4]
In chemical formula 4,
R1And R2It is unsubstituted independently of one another or is selected from halogen, ketone group, ester group and mercapto
In one or more types substituted C1 to C6 alkyl,
A is unsubstituted or one or more types of being selected from halogen, methoxyl group and ethyoxyl take
The aliphatic polycyclic moiety in generation；With unsubstituted or be selected from pi-allyl, halogen, methoxyl group, ethyoxyl
With one or more types substituted aromatics polycyclic moiety in C1 to C8 alkoxyl；And
N and m is individually 0 or 1.
Colored photosensitive resin composition the most according to claim 2, wherein said binding agent
Resin (B) includes copolymer (B1), and the gross weight relative to copolymer (B1), bag
Include:
The composition deriving from described (b1) of 5 weight % to 40 weight %；
The composition deriving from described (b2) of 5 weight % to 40 weight %；With
The composition deriving from described (b3) of 30 weight % to 80 weight %.
Colored photosensitive resin composition the most according to claim 2, wherein said binding agent tree
Fat (B) includes polymer (B2), and described polymer (B2) is relative to described binding agent
The gross weight of resin accounts for 1 weight % to 99 weight %.
Colored photosensitive resin composition the most according to claim 2, wherein said binding agent tree
Fat (B) includes copolymer (B3), and total relative to copolymer (B3) component units
Mol number,
The ratio of the component units deriving from described (B ' 1) is 20mol% to 60mol%；And
The ratio of the component units deriving from described (B ' 2) is 20mol% to 60mol%.
Colored photosensitive resin composition the most according to claim 2, wherein relative to described
The 100mol epoxide group of (B ' 2), the ratio of the component units deriving from described (B ' 3) is
20mol to 120mol..
Colored photosensitive resin composition the most according to claim 1, wherein said binding agent tree
Fat (B) has the weight average molecular weight of 2000 to 100000.
Colored photosensitive resin composition the most according to claim 1, wherein relative to described
The gross weight of color Photosensitve resin composition, described C.I. naphthol green 59 accounts for 0.05 weight % to 50 weights
Amount %.
Colored photosensitive resin composition the most according to claim 1, wherein, with 1:0.050
Weight ratio to 1:18.0 include described C.I. naphthol green 59 and described in pigment and dyestuff one
Plant or polytype.
Colored photosensitive resin composition the most according to claim 1,
Relative to the solid in described colored photosensitive resin composition, on weight fraction, comprise:
The described coloring agent (A) of 5 weight % to 85 weight %；With
The adhesive resin (B) of 1 weight % to 85 weight %.
11. colored photosensitive resin compositions according to claim 1, wherein said C.I. face
Expect green 59 Tmax with 500nm to 530nm.
12. colored photosensitive resin compositions according to claim 1, wherein said C.I. face
Expect green 59 T with 445nm to 580nm50%。
13. colored photosensitive resin compositions according to claim 1, it is in XYZ colourity system
System has the chromaticity coordinates of x=0.1 to 0.35 as y=0.6 or higher.
14. 1 kinds of colored filters, comprise with according to described in any one of claim 1 to 13
Colored pattern prepared by color Photosensitve resin composition.
15. 1 kinds of image display devices, comprise colored filter according to claim 14.
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| KR10-2015-0042373 | 2015-03-26 | ||
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| KR20150042373 | 2015-03-26 | ||
| KR20150045402 | 2015-03-31 | ||
| KR10-2015-0045402 | 2015-03-31 | ||
| KR10-2016-0033800 | 2016-03-22 | ||
| KR1020160033800A KR101995097B1 (en) | 2015-03-26 | 2016-03-22 | Colored photosensitive resin composition, color filter and image display device using the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109814192A (en) * | 2017-11-21 | 2019-05-28 | 阪田油墨股份有限公司 | Colored filter Blue pigment dispersion composition |
| CN109870877A (en) * | 2017-11-03 | 2019-06-11 | 东友精细化工有限公司 | Photosensitive composition, colored filter and image display device |
| CN110007561A (en) * | 2018-01-04 | 2019-07-12 | 东友精细化工有限公司 | Green photonasty resin composition, colored filter and image display device |
| CN110018615A (en) * | 2018-01-10 | 2019-07-16 | 东友精细化工有限公司 | Green photonasty resin composition, colored filter and image display device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008122478A (en) * | 2006-11-08 | 2008-05-29 | Fujifilm Corp | Green photosensitive resin composition, photosensitive transfer material, color filter substrate, and display device |
| CN101598897A (en) * | 2008-06-03 | 2009-12-09 | 住友化学株式会社 | Cured composition for color |
| JP2010102277A (en) * | 2007-11-22 | 2010-05-06 | Toyo Ink Mfg Co Ltd | Green colored composition for color filter, and color filter |
| KR20110024070A (en) * | 2009-09-01 | 2011-03-09 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| CN104423150A (en) * | 2013-09-02 | 2015-03-18 | 东友精细化工有限公司 | Photosensitive resin composition, color filter and liquid crystal display device using the same |
| CN105388705A (en) * | 2014-09-01 | 2016-03-09 | 东友精细化工有限公司 | Coloured photosensitive resin composition |
-
2016
- 2016-03-28 CN CN201610182804.7A patent/CN106019846B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008122478A (en) * | 2006-11-08 | 2008-05-29 | Fujifilm Corp | Green photosensitive resin composition, photosensitive transfer material, color filter substrate, and display device |
| JP2010102277A (en) * | 2007-11-22 | 2010-05-06 | Toyo Ink Mfg Co Ltd | Green colored composition for color filter, and color filter |
| CN101598897A (en) * | 2008-06-03 | 2009-12-09 | 住友化学株式会社 | Cured composition for color |
| CN103869613A (en) * | 2008-06-03 | 2014-06-18 | 住友化学株式会社 | Colored hardening composite, pattern hardeninig colored layer using same, colored filter and liquid crystal display device |
| KR20110024070A (en) * | 2009-09-01 | 2011-03-09 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| CN104423150A (en) * | 2013-09-02 | 2015-03-18 | 东友精细化工有限公司 | Photosensitive resin composition, color filter and liquid crystal display device using the same |
| CN105388705A (en) * | 2014-09-01 | 2016-03-09 | 东友精细化工有限公司 | Coloured photosensitive resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109870877A (en) * | 2017-11-03 | 2019-06-11 | 东友精细化工有限公司 | Photosensitive composition, colored filter and image display device |
| CN109814192A (en) * | 2017-11-21 | 2019-05-28 | 阪田油墨股份有限公司 | Colored filter Blue pigment dispersion composition |
| CN110007561A (en) * | 2018-01-04 | 2019-07-12 | 东友精细化工有限公司 | Green photonasty resin composition, colored filter and image display device |
| CN110018615A (en) * | 2018-01-10 | 2019-07-16 | 东友精细化工有限公司 | Green photonasty resin composition, colored filter and image display device |
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