CN1424624A - Photosensitive composition - Google Patents
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- CN1424624A CN1424624A CN 02155958 CN02155958A CN1424624A CN 1424624 A CN1424624 A CN 1424624A CN 02155958 CN02155958 CN 02155958 CN 02155958 A CN02155958 A CN 02155958A CN 1424624 A CN1424624 A CN 1424624A
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Abstract
The invention provides a photosensitive composition, a color filter obtained using the composition, a manufacturing methof thereof and a colored image forming method using the photosensitive composition. The photosensitive compositions comprise [A] a pigment having 0.01-0.10 [mu]m average particle diameter, [B] a binder resin, [C] an addition- polymerizable compound having at least one ethylenically unsaturated bond, [D] a photopolymerization initiator and [E] a solvent. When a film formed from each of the photosensitive compositions is immersed in >=10 times (by weight) as much said solvent as the film, dissolution time is within 5 min.
Description
Technical field
The present invention relates to photosensitive composite, more particularly the present invention relates to the photosensitive composite of formation coloured image (the being also referred to as pixel) usefulness that can in color liquid crystal display arrangement and imaging apparatus etc., use and the formation method of using the color filter and the rendered image of this photosensitive composite.
Background technology
Color filter in color liquid crystal display arrangement and the imaging apparatus etc., what normally the method for formation red, green and blue three primary colors image was made on substrates such as glass substrate, film substrate, silicon single crystal flake.And the black matrix that light is used between these rendered images is blocked in setting usually.So the method that adopts when forming these rendered images of all kinds is, form at light shield layer on the substrate of pattern, after being dispersed with the sensitization liquid of the corresponding pigment of shades of colour with the evenly even coating of spinner, heat drying (prebake) is made dry coating, and this is filmed according to making its heat curing (back roasting) after pattern exposure, the development.By being repeated these operations, every kind of required color of color filter obtains the shades of colour image.And when forming, black matrix also often adopts the sensitization liquid contain black pigment.
As making the apparatus for coating that color filter uses, bringing into use with slit spin-coating method (Slit And Spin) is province's liquid spreader of representative in recent years.This province liquid spreader is compared with existing spinner, and the coating weight on base material is few, has the low advantage of cost.But because the dry thing of sensitization liquid is easily attached on the color filter, so the problem that exists color filter throughput rate to reduce as its countermeasure, whenever need be removed attached to the painted attachment on the slit part with solvent through certain hour.Even remain inadequate yet so frequently wash, thereby people are desirably on the productivity and can improve.
Summary of the invention
The object of the invention does not produce painted attachment when being to provide a kind of use, and the yet high photosensitive composite of throughput rate, and the color filter that uses said composition to form.And the object of the invention also is to provide a kind of and can forms transmitance, contrast, sensitivity, resolution, solvent resistance and structure cell the reliability evenly photosensitive composite of good rendered image and the color filter that uses said composition to make.
Disclosure of an invention
The present invention's 1 relates to a kind of photosensitive composite 1, be that to contain (A) on average even particle diameter be 0.01～0.10 micron pigment, (B) resin glue, (C) has the compound of an ethylenic unsaturated double bond and energy addition polymerization at least, the photosensitive composite of (D) Photoepolymerizationinitiater initiater and (E) solvent, the film immersion that described photosensitive composite is formed in 10 times of above-described solvents of weight the time dissolution time be within 5 minutes.
In addition, the present invention's 2 also relates to a kind of photosensitive composite 2, relates in the present invention's the 1 described photosensitive composite and also contains the photosensitive composite that (F) has two above epoxy compounds.
And the present invention's 3 relates to the color filter 3 that a kind of the present invention's of use 1 or 2 described photosensitive composites are made in addition.
And the present invention's 4 also relates to the method 4 of a kind of the present invention's of use 1 or 2 described photosensitive composites manufacturing color filters.
At last, the present invention's the 51 or 2 described photosensitive composites that relate to a kind of the present invention of use form the method 5 of rendered image.
Description of drawings
Fig. 1 is the synoptic diagram of a color filter example of expression.
Fig. 2 is the synoptic diagram that the expression colored pattern forms operation.
Fig. 3 is the synoptic diagram that the expression colored pattern forms operation.
Fig. 4 is the synoptic diagram that the expression colored pattern forms operation.
The explanation of symbol:
1: color filter
2: colored pattern 2R: red pixel
2 ': colored pattern 2G: green pixel
2 ": colored pattern 2B: blue pixel
3: substrate
4: painted photographic layer
4 ': painted photographic layer
4 ": painted photographic layer
5: sensitization mask 51: glass plate
52: light shield layer
53: the light transmission part
6: light
Embodiment
Below specify the present invention.
Photosensitive composite of the present invention, it is characterized in that it being that to contain (A) on average even particle diameter be 0.01～0.10 micron pigment, (B) resin glue, (C) has the compound of the energy addition polymerization of an ethylenic unsaturated double bond at least, the photosensitive composite of (D) Photoepolymerizationinitiater initiater and (E) solvent, when described photosensitive composite was immersed in 10 times of above-described solvents of weight, the film dissolution time that described photosensitive composite forms was within 5 minutes.
By the film that photosensitive composite of the present invention forms, the dissolution time in 10 times of above solvents of weight be in 5 minutes as follows with interior confirmation method.
After being coated on photosensitive composite on the glass baseplate surface with spin-coating method, made the fugitive constituent volatilization form film (1.6 microns of thickness) down in dry 3 minutes at 100 ℃.This film immersion was placed 5 minutes in 10 times of above solvents of weight (solvent that uses with photosensitive composite is identical).The state of visualization dissolving back solvent.
For example use the glass substrate (#7059) of Corning Incorporated's manufacturing as this substrate.
In order to form the film of 1.6 microns of thickness, rotational speed in the time of for example can suitably selecting to dilute the photosensitive composite use amount of solvent, employing spin-coating method coating photosensitive composite and temperature etc., for example after increasing film, spend, can reduce solvent load or reduce revolution, reduce temperature, can increase solvent load or improve revolution in order to reduce film thickness, perhaps improve temperature.
Contained pigment (A) in the photosensitive composite that the present invention uses can be inorganic pigment or organic pigment.As inorganic pigment, can enumerate metal oxide or the such metallic compound of metal complex salt, inorganic pigment can specifically be enumerated the oxide or the composite metal oxide of metals such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony.And organic pigment can specifically be enumerated the compound that is sorted in the color index (Colour Index) that dyes and dyestuffs association (The Society of Dyes and Colourists) publishes in the pigment.
In order to form black matrix, use and contain the photosensitive composite that black pigment is colored as black.In order to form versicolor pixels such as red pixel, green pixel and blue pixel, use contains with purpose colored pixels corresponding color pigment and is colored as versicolor photosensitive composite.
As black pigment, for example can use for example carbon black, graphite described in the flat 6-11613 communique of Te Kaiping 5-311109 communique and Te Kai, the above black inorganic pigment of the flat 3-274503 communique of Te Kaiping 4-322219 communique and Te Kai, the above azo class black pigment such as Te Kaiping 2-216102 communique, black pigments such as C.I. pigment black 1, C.I. pigment black 7 etc.
Be colored as in the photosensitive composite of black, also can contain red pigment, viridine green, blue pigment, yellow uitramarine, cyano group look (シ ア Application look) pigment, magenta pigment etc.
Be painted to versicolor photosensitive composite and contain versicolor pigment.The pigment of various pigment both can contain a kind of pigment, also can contain two or more pigment.Described pigment for example can be enumerated C.I. pigment yellow 1, C.I. pigment yellow 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 60, C.I. pigment yellow 61, C.I. pigment yellow 65, C.I. pigment yellow 71, C.I. pigment yellow 73, C.I. pigment yellow 74, C.I. pigment yellow 81, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 95, C.I. pigment yellow 97, C.I. pigment yellow 98, C.I. pigment yellow 100, C.I. pigment yellow 101, C.I. pigment yellow 104, C.I. pigment yellow 106, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 113, C.I. pigment yellow 114, C.I. pigment yellow 116, C.I. pigment yellow 117, C.I. pigment yellow 119, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 6, C.I. pigment Yellow 12 7, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 152, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 156, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 17 5
C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73
C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38,
C.I. paratonere 1, C.I. paratonere 2, C.I. pigment red 3, C.I. pigment red 4, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. pigment Red 8, C.I. Pigment Red 9, C.I. paratonere 10, C.I. paratonere 11, C.I. paratonere 12, C.I. paratonere 14, C.I. paratonere 15, C.I. paratonere 16, C.I. paratonere 17, C.I. paratonere 18, C.I. paratonere 19, C.I. pigment red 21, C.I. paratonere 22, C.I. paratonere 23, C.I. pigment red 30, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 37, C.I. pigment red 38, C.I. pigment red 40, C.I. pigment red 41, C.I. pigment red 42, C.I. pigment red 4 8:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. pigment red 4 9:1, C.I. pigment red 4 9:2, C.I. paratonere 50:1, C.I. paratonere 52:1, C.I. paratonere 53:1, C.I. paratonere 57, C.I. paratonere 57:1, C.I. paratonere 58:2, C.I. paratonere 58:4, C.I. paratonere 60:1, C.I. paratonere 63:1, C.I. paratonere 63:2, C.I. paratonere 64:1, C.I. pigment red 81: 1, C.I. pigment Red 83, C.I. pigment Red 88, C.I. Pigment Red 9 0:1, C.I. Pigment Red 97, C.I. paratonere 101, C.I. paratonere 102, C.I. paratonere 104, C.I. paratonere 105, C.I. paratonere 106, C.I. paratonere 108, C.I. pigment red 112, C.I. paratonere 113, C.I. paratonere 114, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 146, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 151, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 172, C.I. paratonere 174, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 188, C.I. paratonere 190, C.I. paratonere 193, C.I. paratonere 194, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 208, C.I. paratonere 209, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 226, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 245, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 265
C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60,
C.I. pigment Green 7, C.I. pigment green 36 and
C.I. pigment brown 23 and C.I. pigment brown 25 etc.
The preferred pigment of conduct in these pigment, can enumerate C.I. pigment yellow 117, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 150, C.I. pigment yellow 155, C.I. pigment yellow 185, C.I. paratonere 209, C.I. paratonere 242, C.I. paratonere 254, C.I. pigment black 1, C.I. pigment black 7 etc., preferred especially C.I. pigment yellow 150, C.I. paratonere 254, C.I. pigment black 1 and C.I. pigment black 7.
The average even particle diameter of pigment is 0.01～0.10 micron among the present invention, preferred 0.02～0.08 micron.
The average even particle diameter of pigment is directly measured the primary granule size with electron micrograph, gets its on average even value.Specifically measure the major diameter and the minor axis diameter of each particle, with the diameter of its on average even value as this particle.After the such mensuration of 50 above particles, be decided to be average even particle diameter.
There is no particular restriction to obtain average even particle diameter among the present invention and be 0.01～0.10 micron pigment, can adopt known methods such as kneader method, sulfuric acid process, alkali reduction of dissolved method with its micronize.Be dispersed in generally well-known method through micronized pigment and make dispersible pigment dispersion in the solvent, and then, use as photosensitive composite with after cementing agent numerical value and other compositions mix.
Photosensitive composite of the present invention can contain pigment by containing pigment dispersing agent under an even disperse state, obtain evenly painted colored pattern, so preferably contain pigment dispersing agent.This pigment dispersing agent, can enumerate for example spreading agents such as polyesters macromolecule dispersing agent, acrylic polymer spreading agent and polyurethane class high molecular spreading agent, surfactants such as cationic surfactant, anionic surface active agent and non-ionics etc., these materials can contain a kind of or two or more combinations and usefulness separately.
Preferably polyethylene imines class spreading agent or polyurethanes spreading agent.
Contain under the situation of this pigment dispersing agent, its content is in more than 0.01 weight portion for 1 weight portion pigment usually, more than preferred 0.05 weight portion, below common 1 weight portion, below preferred 0.5 weight portion.
Below explanation obtains an example of pigment dispersing agent of the present invention.At first pigment is done the air-flow flushing and handle, or mediate with resin with kneader, extruder, bowl mill or two roller or three-roll grinder.As preferred kneading method, can enumerate after in pigment and resin glue, adding the even mixing of solvent, with two rollers or three-roll grinder, mediate while heating in case of necessity, ten make pigment fully mix with resin glue, obtain the method for even one tingle body, and the method for using water-soluble inorganic salt such as salt and a small amount of solvent that pigment is mediated.Be suitable under the situation of inorganic salts such as salt, it removed in advance by washing.
Then with pigment, in case of necessity with spreading agent and other required constituents, resin glue for example described later and other materials and solvent are carried out wet method with various dispersion machines mixing and are disperseed (elementary dispersion).
Use thinner mill pearl with the dispersion liquid wet method dispersion (secondary dispersion) once more that obtains, till becoming the purpose particle size distribution.Perhaps the particle that big particle obtains having purpose particle size and size-grade distribution is removed in the dispersion liquid classification that wet method is disperseed with centrifugal separation or gradient method.Known machine can be used over as dispersion machine,, sand mills such as equal homogenizer, kneader, two roller or three-roll grinder, coating vibrating machine, side grinding machine and Dai Nuo (ダ イ ノ) grinding machine can be enumerated if want illustrative example.
Pigment described in the present invention can also be as required uses after with its particle surface upgrading with polymkeric substance.As the polymkeric substance that the pigment upgrading is used, for example can enumerate the spy and open the above polymkeric substance such as flat 8-259876 communique, and commercially available various pigment dispersing are with polymkeric substance or oligomer etc.Specifically can enumerate acryl resin, vinyl chloride-vinyl acetate copolymer resins, maleic acid resin, ethyl cellulose resin, Nitro cellulose resin etc.Through the processed pigment form of plastic resin treatment, the preferably homodisperse powder of resin and pigment, pastel and particulate material.
Pigment content in the photosensitive composite with regard to regard to the weight % that shape is divided admittedly of fugitive constituent volatilization back, is generally 20% or more and below 60%, preferred more than 25% with below 50%.
Resin glue among the present invention (B), for photosensitive composite is to give its composition without irradiate light zone dissolution properties in developer solution, and is the material that has as the dispersion medium function that pigment is disperseed in photosensitive composite layer and formed colored pattern.
Described resin glue for example both can be an acrylic copolymer, also can be the compound shown in the formula (I):
(in the formula, R
1And R
2Independent separately expression hydrogen atom, 1～5 carbon atom alkyl or halogen atom, R
4Expression hydrogen atom or methyl, the residue of divalent shown in any one structural formula in the X expression (I-1)～(I-6), R
3Expression can have the alkylidene of substituent 1～10 carbon atom, and m represents 0～5 integer, and n represents 1～10 integer.)
And the condensed polymer between polyprotonic acid or its acid anhydrides (open referring to the spy flat 4-355450 communique, spy are opened flat 9-40745 communique, the spy opens flat 09-325494 communique and Te Kaipingtekai 2000-281738 communique).
As acrylic copolymer, can enumerate the multipolymer between other monomers of the monomer that for example contains carbonyl and copolymerization with it.
As the monomer that contains carbonyl, can enumerate for example unsaturated monocarboxylic acid, and the unsaturated carboxylic acid that has a carboxyl in the molecule of unsaturated polybasic carboxylic acid such as unsaturated dicarboxylic acid, unsaturated tricarboxylic acid at least.Wherein said unsaturated monocarboxylic acid can be enumerated for example acrylic acid, methacrylic acid, butenoic acid, α-Lv Daibingxisuan and cinnamic acid etc.Unsaturated dicarboxylic acid can be enumerated for example maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid etc.Unsaturated polybasic carboxylic acid can be enumerated its acid anhydrides, specifically can be maleic anhydride, itaconic anhydride, methyl maleic anhydride etc.
And unsaturated polybasic carboxylic acid, it both can be its single (2-methacryloxy alkyl) ester, particularly, for example mono succinate (2-methacryloxyethyl) ester mono succinate (2-methacryloxyethyl) ester, butyric acid list (2-acryloxy ethyl) ester, butyric acid list (2-methacryloxyethyl) ester etc.Unsaturated polybasic carboxylic acid can also be list (methyl) acrylate of its two terminal dicarboxyl polymkeric substance, specifically can be ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates.This contains the polymkeric substance of carboxyl, can use one or more kinds of potpourris.
As other monomers that can contain the monomer copolymerization of carboxyl with this; for example can enumerate styrene; α-Jia Jibenyixi; adjacent vinyltoluene; between vinyltoluene; to vinyltoluene; to chlorostyrene; O-methoxy styrene; meta-methoxy styrene; to methoxy styrene; adjacent vinyl benzyl methyl ether; between the vinyl benzyl methyl ether; to the vinyl benzyl methyl ether; adjacent vinyl benzyl glycidyl ether; between the vinyl benzyl glycidyl ether; to the vinyl benzyl glycidyl ether; aromatic ethenyl compounds such as indenes; methyl acrylate; methyl methacrylate; ethyl acrylate; Jia Jibingxisuanyizhi; the acrylic acid n-propyl; n propyl methacrylate; isopropyl acrylate; isopropyl methacrylate; n-butyl acrylate; n-BMA; isobutyl acrylate; isobutyl methacrylate; sec-butyl acrylate; the secondary butyl ester of methacrylic acid; tert-butyl acrylate; the metering system tert-butyl acrylate; the 2-hydroxy ethyl methacrylate; the 2-hydroxyethyl meth acrylate; the 2-hydroxypropyl acrylate; 2-hydroxypropyl methyl acrylate; the 3-hydroxypropyl acrylate; 3-hydroxypropyl methyl acrylate; 2-hydroxyl butylacrylic acid ester; 2-hydroxyl butyl methyl acrylate; 3-hydroxyl butylacrylic acid ester; 3-hydroxyl butyl methyl acrylate; 4-hydroxyl butylacrylic acid ester; 4-hydroxyl butyl methyl acrylate; allyl acrylate; allyl methacrylate; the acrylic acid benzyl ester; the methacrylic acid benzyl ester; the acrylic acid cyclohexyl ester; the methacrylic acid cyclohexyl ester; phenyl acrylate; methacrylic acid alkene phenyl ester; 2-methoxy ethyl acrylate; 2-methoxy ethyl methacrylate; the 2-phenoxyethyl acrylate; 2-phenoxy group ethyl-methyl acrylate; methoxyl diethylene glycol acrylate; methoxyl diethylene glycol methacrylate; methoxyl three ethylene glycol acrylate; methoxyl three ethylene glycol methacrylates; the MPEG acrylate; the MPEG methacrylate; methoxyl dipropylene glycol acrylate; methoxyl dipropylene glycol methacrylate; isobornyl acrylate; IBOMA; acrylic acid bicyclopentadiene ester; methacrylic acid bicyclopentadiene ester; 2-hydroxyl-3-phenoxy propyl acrylate; 2-hydroxyl-3-phenoxy propyl methacrylate; the glyceryl mono acrylic ester; the ester class of unsaturated carboxylic acids such as glyceryl monomethacrylates; 2-amino-ethyl acrylate; 2-amino-ethyl methacrylate; the 2-dimethyl amino ethyl acrylate; the 2-dimethyl amino ethyl methacrylate; 2-aminopropyl acrylate; 2-aminopropyl methacrylate; 2-dimethylaminopropyl acrylate; 2-dimethylaminopropyl methacrylate; 3-aminopropyl acrylate; 3-aminopropyl methacrylate; 3-dimethylaminopropyl acrylate; the aminoalkyl ester class of unsaturated carboxylic acids such as 3-dimethylaminopropyl methacrylate; glycidyl acrylate; the glycidyl esters class of unsaturated carboxylic acids such as glycidyl methacrylate; vinyl acetate; propionate; vinyl butyrate; the vinyl ester of carboxylic acids such as vinyl benzoate; vinyl methyl ether; EVE; unsaturated ethers such as allyl glycidyl ether; vinyl cyanide; methacrylonitrile; α-Lv Daibingxijing; vinyl cyanide based compounds such as vinyl cyanide fork; acrylamide; Methacrylamide; the alpha-chloro acrylamide; N-2-hydroxyethyl acrylamide; unsaturated acyl amines such as N-2-hydroxyethyl methacrylamide; maleimide; N-phenylmaleimide; unsaturated acid imides such as N-cyclohexyl maleimide; 1; the 3-butadiene; isoprene; aliphatics conjugated dienes such as chloro isoprene, polystyrene; polymethyl acrylate; polymethylmethacrylate; the positive butyl ester of polyacrylic acid; Vinalac 5920; main polymer chain end at polysiloxane has big monomer class of single acryloyl group or monomethyl acryloyl group etc.These monomers can use separately separately or two or more mixing is used.
The content that contains carboxylic monomer in this multipolymer is generally about 10～50% preferred about 15～40% according to weight % meter.
As this acrylic polymers, for example can enumerate (methyl) acrylic acid/(methyl) methyl acrylate copolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester multipolymer, (methyl) acrylic acid/2-hydroxyethyl (methyl) acrylate/(methyl) acrylic acid benzyl ester multipolymer, (methyl) acrylic acid/big monomer copolymer of (methyl) methyl acrylate/polystyrene, (methyl) acrylic acid/big monomer copolymer of (methyl) methyl acrylate/polymethylmethacrylate, (methyl) acrylic acid/big monomer copolymer of (methyl) acrylic acid benzyl ester/polystyrene, (methyl) acrylic acid/big monomer copolymer of (methyl) acrylic acid benzyl ester/polymethylmethacrylate, (methyl) acrylic acid/2-hydroxyethyl (methyl) acrylate/big monomer copolymer of (methyl) acrylic acid benzyl ester/polystyrene, (methyl) acrylic acid/2-hydroxyethyl (methyl) acrylate/big monomer copolymer of (methyl) acrylic acid benzyl ester/polymethylmethacrylate, methacrylic acid/styrene/(methyl) acrylic acid benzyl ester/N-phenylmaleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloxy ethyl)/styrene/(methyl) benzyl acrylate/N-phenylmaleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloxy ethyl) ester/styrene/(methyl) acrylic acid allyl ester/N-phenylmaleimide multipolymer, (methyl) acrylic acid/(methyl) benzyl acrylate/N-phenylmaleimide/styrene/glyceryl list (methyl) acrylate copolymer etc.Wherein said (methyl) acrylate, expression acrylic or methacrylic acid esters.
Wherein preferably benzyl methacrylate/methacrylic acid copolymer, benzyl methacrylate/methacrylic acid/styrol copolymer, methyl methacrylate/methacrylic acid copolymer, methyl methacrylate/methacrylic acid/styrol copolymer etc.
This acrylic polymers preferably is in its even molecular weight of weight average that is converted into polystyrene in 400,000 scopes, more preferably is in 5,000～50,000 scope.And acid number is preferred 30～250, more preferably 70～140.
Below just can make the product that cementing agent uses, obtained by the compound of following formula (I) expression and polyprotonic acid or multi-anhydride polycondensation and describe.As polyprotonic acid, for example, can enumerate maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl endo-methylene group tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, trimellitic acid, evenly benzene tetracarboxylic acid, benzophenone tetracarboxylic acid, with 4, bibenzene tetracarboxylic headed by 4 '-two phthalic acids and diphenyl ether tetraformic etc.Can enumerate the acid anhydrides of above-mentioned polyprotonic acid etc. as multi-anhydride.These polyprotonic acids or its acid anhydrides can use separately separately or two or more mixing is used.
The consumption of polyprotonic acid or polyprotonic acid acid anhydrides, with respect to the molal quantity (molal quantity that is equivalent to hydroxyl) of compound shown in the formula (I) and the molar percentage of polyprotonic acid or its acid anhydrides molal quantity total mole number, be 5 as below above and 95%, preferred more than 10% and below 90%.The acid number of condensed polymer preferably is in about 70～140.
Condensed polymer between compound shown in the preferred formula in this resin glue (I) and polyprotonic acid or the polyprotonic acid acid anhydrides, more preferably the X in the formula (I) is the compound of residue of divalent shown in the formula (I-1) and the condensed polymer between polyprotonic acid or the polyprotonic acid acid anhydrides.
This resin glue is generally 5% or more in the weight % that accounts for the solid shape of photosensitive composite and divide and below 90%, preferred more than 10% with below 60%.
As the compound (C) that has ethylene unsaturated bond and energy addition polymer among the present invention, for example can have one at least from end, preferably have in the compound of two ethylene unsaturated bonds and select, it both can be monomer, also can be prepolymers such as dimer, tripolymer and oligomer, can also be its potpourri and multipolymer etc.
As described monomer, can enumerate for example ester class of unsaturated fatty acid such as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid and aliphatic polyol compound, and the amide-type of unsaturated carboxylic acid and aliphatic polyamine compound etc.
Ester class as this unsaturated fatty acid and aliphatic polyol compound, can enumerate for example glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, the tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy ethyl) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetrem support omega-diol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanates, esters of acrylic acids such as polyester acrylic ester oligomer, the tetramethylene glycol dimethylacrylate, the triethylene glycol dimethylacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, 1, the 3-butanediol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate, two [right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane, methyl acrylic esters such as two [right-(methacryloxy ethoxy) phenyl] dimethylmethane, the ethylene glycol bisthioglycolate itaconate, the propylene glycol diitaconate, 1,3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, the tetramethylene glycol diitaconate, pentaerythrite alcohol diitaconate, itaconate classes such as D-sorbite four itaconates, the ethylene glycol bisthioglycolate butenoate, tetramethylene glycol dibutene acid esters, pentaerythrite dibutene acid esters, butenoate classes such as D-sorbite four butenoates, glycol ester diisobutylene, pentaerythrite diisobutylene acid esters, methacrylate classes such as D-sorbite tetra methylacrylate, the ethylene glycol bisthioglycolate maleate, three ethylene glycol dimaleates, the pentaerythrite dimaleate, maleate classes such as D-sorbite four maleates etc.
As the acid amides between this unsaturated carboxylic acid and the aliphatic polyamine compound, for example can enumerate methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1,6-hexylidene bisacrylamide, 1, the two Methacrylamides of 6-hexylidene, diethylenetriamine three acrylamides, penylene dimethyl bisacrylamide, the two Methacrylamides of penylene dimethyl etc.
The example of other monomers for example can be enumerated and make the vinyl monomer shown in the formula (II)
(R in the formula
21And R
22Independent separately expression hydrogen atom or methyl) the vinyl carbamate compound that addition obtains in the polyisocyanate compounds of two above isocyanate group arranged in a molecule.
This vinyl carbamate compound is the compound (special public clear 48-41708 communique) that contains two above polymerism vinyl in the molecule.Can enumerate the spy in addition and open the described urethane acrylate class of clear 51-37193 communique, and special open multi-functional acrylate and the methacrylates such as polyester acrylate class described in clear 48-64183, special public clear 49-43191, each communique such as special public clear 52-30490 number.Also can use Japanese bonding association can be the material that topic is introduced as photo-curable monomer and oligomer the 20th the 7th phase of volume of will 300～308 pages (1984).
This has ethylene unsaturated bond and compound amount that can addition polymerization, according to dividing shared weight % meter with respect to the solid shape of composition, is generally 0.5% or more and below 50%, preferred more than 1% with below 40%.
As the Photoepolymerizationinitiater initiater among the present invention (D), so long as can make compound begin polymeric compounds with ethylene unsaturated bond and energy addition polymerization, just be not particularly limited, can use acetophenone is that Photoepolymerizationinitiater initiater, diphenylhydroxyethanone are that Photoepolymerizationinitiater initiater, benzophenone series Photoepolymerizationinitiater initiater, thioxanthones are that Photoepolymerizationinitiater initiater, triazine are that Photoepolymerizationinitiater initiater, oxadiazole is a Photoepolymerizationinitiater initiater etc.
As acetophenone is Photoepolymerizationinitiater initiater, for example can enumerate diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone acetal, 2-methyl-2-morpholino-1-(4-methyl thio-phenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholine filial generation phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone oligomer etc.
As diphenylhydroxyethanone is Photoepolymerizationinitiater initiater, for example can enumerate diphenylhydroxyethanone, diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ethylether, diphenylhydroxyethanone propyl ether, diphenylhydroxyethanone butyl ether etc.
As the benzophenone series Photoepolymerizationinitiater initiater, for example can enumerate benzophenone, adjacent benzyl acyl group methyl benzoate, 4-phenyl benzophenone, 4-benzyl acyl group-4 '-dimethyl diphenyl sulfide, 3,3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone etc.
As thioxanthones is Photoepolymerizationinitiater initiater, for example can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro-thioxanthones, 1-chloro-4-propoxyl group thioxanthones etc.
As triazine is Photoepolymerizationinitiater initiater, for example can enumerate 2, two (the trichloromethyl)-6-of 4-are to methoxybenzene ethyl-s-triazine, 2, (1-is to dimethylaminophenyl-1 for two (the trichloromethyl)-6-of 4-, the 3-butadienyl)-the s-triazine, 2-trichloromethyl-4-amino-6-is to methoxyl-styrene-s-triazine, 2-(naphtho--1 base)-4,6-pair-trichloromethyl-s-triazine, 2-(4-methoxyl-naphtho--1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-ethoxy-naphtho--1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-butoxy-naphtho--1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-methoxy ethyl)-naphtho--1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl group)-naphtho--1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl group)-naphtho--1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-(2-methoxyl-naphtho--1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-5-methyl-naphtho--2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-naphtho--2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(5-methoxyl-naphtho--1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphtho--1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-ethoxy-naphtho--2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4,5-dimethoxy-naphtho--1-yl)-4,6-pair-trichloromethyl-s-triazine, 4-[is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-methyl-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-methyl-right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N-chloroethyl amino phenyl] and-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N-ethoxy carbonyl methylamino phenyl] and-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N, N-two (phenyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-chloroethyl carbonylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N-(p-methoxyphenyl) carbonylamino phenyl] and-2,6-two (trichloromethyl)-s-triazine, between 4-[-N, N-two (ethoxy carbonyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-chloro-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-right-N, N-two (chloro ethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-right-N, N-two (chloro ethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-right-N, N-two (chloro ethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-bromo-right-N, N-two (chloro ethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-right-N, N-two (chloro ethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-fluoro-right-N, N-two (chloro ethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-right-N-ethoxy carbonyl methylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-right-N-ethoxy carbonyl methylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-right-N-ethoxy carbonyl methylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-right-N-ethoxy carbonyl methylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-right-N-ethoxy carbonyl methylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-right-N-ethoxy carbonyl methylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-right-N-chloro ethylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-right-N-chloro ethylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-right-N-chloro ethylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-right-N-chloro ethylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-right-N-chloro ethylamino phenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-right-N-chloro ethylamino phenyl]-2,6-two (trichloromethyl)-s-triazine etc.
Zuo is a Photoepolymerizationinitiater initiater Wei oxadiazole, for example can enumerate 2-trichloromethyl-5-styryl-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(to the cyano styrene base)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(to methoxyl-styrene)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(to the butyl phenyl ether vinyl)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(para hydroxybenzene vinyl)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(to the chlorostyrene base)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(p-methoxyphenyl)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(to butoxy phenyl)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(2-naphthyl)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(β-(2-benzofuranyl) vinyl)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(β-(6-methoxyl-2-benzofuranyl) vinyl)-1,3, the 4-oxadiazoles, 2-trichloromethyl-5-(2-benzofuranyl)-1,3,4-oxadiazoles etc.
And for example can also use 2 as Photoepolymerizationinitiater initiater; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, 2; 2 '-two (adjacent chlorophenyls)-4; 4 ', 5,5 '-tetraphenyl-1; 2 '-diimidazole, 10-butyl-2-chloro acridone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.
Also can preferably use the triazine that can import trichloromethyl in this Photoepolymerizationinitiater initiater is Photoepolymerizationinitiater initiater, and 2-benzyl-2-dimethylamino-1-(4-morpholine subbase phenyl) butane-1-ketone.
As the triazine that can import trichloromethyl is Photoepolymerizationinitiater initiater, for example can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3, the 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1,3 of 4-, the 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1,3,5-triazines, 2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl of 4-]-1,3,5-triazine etc.These Photoepolymerizationinitiater initiaters can use separately or two or more combination and usefulness separately.
Photosensitive composite of the present invention also can contain photopolymerization and cause auxiliary agent.Cause auxiliary agent as this photopolymerization.For example can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, benzoic acid 2-dimethylamino ethyl ester, N, the N-dimethyl is toluidine all, 4,4 '-two (dimethylamino) benzophenone (be commonly referred to rice and sneer Le Shi ketone), 4,4 '-two (diethylamino) benzophenone, 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.。These photopolymerization cause auxiliary agent and can use separately separately or two or more combination and usefulness.
Use this photopolymerization to cause under the situation of auxiliary agent, its use amount is generally for 1 mole of Photoepolymerizationinitiater initiater more than 0.01 mole with below 10 moles.
Photoepolymerizationinitiater initiater and photopolymerization cause the total consumption of auxiliary agent, according to the weight % meter that divides with respect to the solid shape of photosensitive composite, are generally 1% or more and below 50%, preferred more than 3% with below 30%.
For example can enumerate ester class, ethers, ketone and aromatic hydrocarbon based etc. as solvent.
Esters solvent, can enumerate for example ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, alkyl esters such as butyl butyrate, methyl lactate, ethyl lactate, the oxo methyl acetate, oxo ethyl acetate, the oxo butyl acetate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-oxo methyl propionate, 3-oxo alkyl propionates classes such as 3-oxo ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 2-oxo methyl propionate, ethyl 2-oxopropanoate, 2-oxo propyl propionate, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxo-2 Methylpropionic acid methyl esters, 2-oxo-2 Methylpropionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester etc.
As ether solvent, can enumerate for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol list ethylether, diethylene glycol single-butyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.
As ketones solvent, can enumerate for example methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc.As aromatic hydrocarbon solvent, can enumerate for example toluene, dimethylbenzene etc.
Preferred 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, the methyl proxitol acetate etc. of using in these solvents.
These solvents can use separately or two or more mixing is used, its use amount can suitably select usually make in the photosensitive composite solid shape branch concentration (weight %) be in 2% or more with 50% following scope in.
Also should contain compound (F) (hereinafter referred to as " multi-functional epoxy compound ") in the photosensitive composite of the present invention with two above epoxy radicals, for example when color filter forms back roasting in the operation, react preferably in this case because of promoting heat curing.
Described multi-functional epoxy compound, can be low molecular compound or macromolecular compound, it is that epoxy resin, hydrogenated bisphenol A are that epoxy resin, Bisphenol F are that epoxy resin, A Hydrogenated Bisphenol A F are that epoxy resin, linear epoxy resin, cyclic aliphatic epoxy resin, heterocyclic-type epoxy resin, glycidyl esters are that resin, glycidyl group amine are resin, epoxidation wet goods epoxy resin that its instantiation can be enumerated bisphenol-A, the bromo derivative of above-mentioned epoxy resin, and three (glycidyl phenyl) methane, three-glycidyl based isocyanate etc.
In these multi-functional epoxy compounds, bisphenol-A is that epoxy resin, hydrogenated bisphenol A are that epoxy resin, novolac epoxy resin, cyclic aliphatic epoxy resin, glycidyl esters are that resin, glycidyl group amine are that resin and three (glycidyl phenyl) methane etc. has the compound of 2～100 epoxy radicals, and is high and few preferred to the deleterious effect of the developing performance of ray sensitive compositions because of the hardness of color filter.
These multi-functional epoxy compounds can use separately in the present invention or two or more mixing is used.The consumption of multi-functional epoxy compound among the present invention for 100 weight portion resin glues (B), is generally 1～80 weight portion, preferred 5～50 weight portions.
Photosensitive composite of the present invention can also contain thermal polymerization and prevent macromolecular compound, surfactant, adhesion promoter, antioxidant, ultraviolet light absorber, anti-coagulants etc. beyond the agent, filling agent, resin glue.
Contain the purpose that thermal polymerization prevents agent and be to prevent, for example in the preservation process of photosensitive composite (C), have an above ethylene unsaturated bond and compound that can addition polymerization to begin to produce heat polymerization.Described thermal polymerization prevents that agent from can enumerate for example halo benzoquinones, p methoxy phenol, BHT, pyrogallol, tert-butyl catechol, benzo benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-methene two (4-methyl-6-tert butyl phenol), the inferior cerium salt of N-nitroso-phenyl azanol etc.Contain under the situation that thermal polymerization prevents agent, its content is by the weight % with respect to the photosensitive composite total amount, is generally more than 0.01% and below 5%.
Described filling agent can be enumerated for example glass, aluminium oxide etc.
Macromolecular compound beyond the described cementing agent can be enumerated for example polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, polychlorostyrene substituted alkyl acrylate etc.
Surfactant can be any surfactant of non-ionics, cationic surfactant and anionic surface active agent.
As adhesion promoter, can enumerate for example vinyl trihydroxy methyl silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-aminopropyl trihydroxy methyl silane, the amino aminopropyltriethoxywerene werene of 3-, 3-glycidoxypropyl trihydroxy methyl silane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trihydroxy methyl silane, 3-chloro propyl group methyl dimethoxysilane, 3-chloro propyl group trihydroxy methyl silane, 3-methacryloxypropyl trihydroxy methyl silane, 3-sulfydryl propyl group trihydroxy methyl silane etc.
As antioxidant, for example can enumerate 2,2-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol etc.
As ultraviolet absorber, can enumerate for example 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorinated benzotriazole, alkoxy benzophenone etc.Can enumerate for example sodium polyacrylate etc. as anti-coagulants.
Photosensitive composite can also contain organic carboxyl acid, organic amino compounds etc.
As organic carboxyl acid, can enumerate for example formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid, aliphatics monocarboxylic acid such as sad, ethane diacid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brazilic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, dimethyl succinic acid, tetramethyl-succinic acid, aliphatic dicarboxylic acids such as citraconic acid, even propanetricarboxylic acid, aconitic acid, aliphatics tricarboxylic acids such as camphoronic acid, benzoic acid, phenylacetic acid, cumfrey, benzene-1,2,3-tricarboxylic acid, 3, aromatic series monocarboxylic acids such as 5-mesitylenic acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, even benzenetricarboxylic acid, mellophanic acid, aromatic series polybasic carboxylic acids such as even benzenetetracarboxylic acid, phenylacetic acid, α-phenylpropionic acid, beta phenyl propionic acid, mandelic acid, phenylsuccinic acid, atropic acid, the 2-phenylacrylic acid, 2-phenylacrylic acid methyl esters, 2-phenylacrylic acid benzyl ester, Chinese cassia tree fork acetate, coumaric acid, 2, the low-molecular-weight organic carboxyl acid of 4-dihydroxycinnamic acid equimolecular quantity below 1000 etc.
As organic amino compounds, usually can use the low-molecular-weight organic amino compounds of molecular weight below 1000, for example can enumerate n-propylamine, isopropylamine, n-butylamine, isobutyl amine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive 11 carbon amine, positive 12 carbon amine, cyclohexylamine, o-methylcyclohexylamine, between methyl cyclohexylamine, to methyl cyclohexylamine, adjacent ethyl cyclohexylamine, between ethyl cyclohexylamine, to single (ring) alkyl amines such as ethyl cyclohexylamines, Methylethyl amine, diethylamine, methyl n-pro-pyl amine, ethyl n-pro-pyl amine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-t-butyl amine, two n-pentyl amine, di-n-hexyl amine, methylcyclohexyl amine, the ethyl cyclo-hexylamine, dicyclohexyl amine etc. two (ring) alkyl amine, dimethylethyl amine, the methyl diethylamide, triethylamine, dimethyl n propyl group amine, diethyl n-pro-pyl amine, the methyl di-n-propyl amine, the ethyl di-n-propyl amine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, three tert-butylamines, tri-n-amyl amine, three n-hexylamines, dimethyl cyclohexyl amine, diethyl cyclohexylamine, the methyl bicyclic hexylamine, the ethyl dicyclohexyl amine, tricyclohexyltin amine etc. three (ring) alkyl amine, the 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, single (ring) alkanolamine such as 4-amino-1-cyclohexanol, diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine, two n-amyl alcohol amine, two n-hexyl alcohol amine, two (ring) alkanolamine such as two (4-cyclohexanol) amine, triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, three n-hexyl alcohol amine, three (ring) alkanolamine such as three (4-cyclohexanol) amine, 3-amino-1, the 2-propylene glycol, 2-amino-1, ammediol, 4-amino-1, the 2-butylene glycol, 4-amino-1, the 3-butylene glycol, 4-amino-1, the 2-cyclohexanediol, 4-amino-1, the 3-cyclohexanediol, 3-dimethylamino-1, the 2-propylene glycol, 3-diethylamino-1, the 2-propylene glycol, 2-dimethylamino-1, ammediol, 2-diethylamino-1, amino (ring) alkanediol class such as ammediol, Aminocyclopentane methyl alcohol, 4-Aminocyclopentane methyl alcohol, 1-aminocyclohexane methyl alcohol, 4-aminocyclohexane methyl alcohol, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylamino cyclohexane methanol etc. contains amino naphthenic hydrocarbon methyl alcohol class, Beta-alanine, the 2-aminobutyric acid, the 3-aminobutyric acid, the 4-aminobutyric acid, the 2-aminoisobutyric acid, the 3-aminoisobutyric acid, the 2-aminovaleric acid, the 5-aminovaleric acid, 6-aminocaprolc acid, the amino cyclopropionate of 1-, the amino cyclohexylenedinitrilotetraacetic acid of 1-, aminocarboxylic acids such as the amino cyclohexylenedinitrilotetraacetic acid of 4-etc.
But also for example can enumerate amino on phenyl the direct compound of combination, and amino compound by carbochain combination on phenyl etc.Compound as amino direct combination on phenyl, can enumerate for example o-toluidine, between methylaniline, to methylaniline, to ethylaniline, to n-propylbenzene amine, cumidine, to n-butyl aniline, align tert-butyl group aniline, 1-naphthyl aniline, 2-naphthyl aniline, N, accelerine, N, the N-diethylaniline, to methyl-N, aromatic amines such as accelerine, o-benzyl alcohol, m-aminophenyl methyl alcohol, p-aminophenyl methyl alcohol, to the dimethylamino phenmethylol, to aminobenzoic alcohols such as diethylamino phenmethylols, o-aminophenol, m-aminophenol, para-aminophenol, to dimethylamino phenol, to amino phenols such as diethylamino phenol, gavaculine, p-aminobenzoic acid, ESCAROL 507, to aminobenzoic acids such as diethyl amino yl benzoic acid (derivant) class etc.
This organic carboxyl acid, organic amino compounds can use separately separately or two or more mixing is used.Use under the situation of this organic carboxyl acid, organic amino compounds, its content in photosensitive composite is generally 0.001% or more and below 15% according to weight % shared in photosensitive composite meter, preferred more than 0.01% with below 10%.
This photosensitive composite is being coated on (referring to accompanying drawing 2 (a)) on the substrate 2 usually under the solvent dilution state.
Though the method that this photosensitive composite can be coated with on substrate 2 with common coating processes such as method of spin coating (spin-coating method), curtain coating rubbing method, rolling method for example, but for making better significantly employing of effect make coating fluid from gap nozzle, flow out the mode that is coated with and coating fluid is flowed out be coated with the mode that makes it to rotate of continuing, promptly so-called slit spin-coating method etc. flows out coating fluid from slit mode from gap nozzle.
As substrate 2, except that for example glass substrate and silicon substrate, can also use resin substrates such as polycarbonate substrate, polyester substrate, aromatic polyamide substrate, polyamideimide-based plate, polyimide substrate.Described substrate also can be implemented pre-treatments such as the medicine processing, plasma treatment, ion plating processing, sputter process, gas-phase reaction processing, application of vacuum through medicines such as silane coupling agents.
Photosensitive composite is after coating on the substrate 2, and drying makes solvent evaporates, can form photosensitive composite layer 1 (referring to accompanying drawing 2 (a)) on substrate.This layer is the layer that the solid shape by photosensitive composite is grouped into, and its thickness is generally 0.1～10 micron, is preferably 0.2～5.0 micron, is preferably 0.2～3.0 micron especially.
Then by 3 pairs of photosensitive composite layers of photomask, 1 irradiation light 4 (referring to accompanying drawing 2 (b)).
The irradiate light amount, though can suitably select according to the kind and the content of the color of the pigment (A) that is suitable for and content, resinoid bond (B), kind and the kind and the content of content and Photoepolymerizationinitiater initiater (D) with an above ethylene unsaturated bond and compound (C) that can addition polymerization, but owing to can form the good colored pattern of sensitivity, thereby can the irradiation time more used lack than the common colored pattern method of formationing according to formation method of the present invention.(referring to accompanying drawing 2 (c)) develops in the exposure back.Can make the photosensitive composite layer after the exposure during development) contact with developer solution.By contacting with developer solution, the zone 11 of crystallite irradiate light will be dissolved in the developer solution in the photosensitive composite layer.
As developer solution, for example can adopt alkaline aqueous solution.Described alkaline aqueous solution can use NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, Kelin, pyrroles, piperidines, 1,8-diazabicyclo [5,4,0]-aqueous solution of water-soluble interstitial compounds such as 7-undecylene, its concentration is generally more than 0.001% with below 10%, preferably more than 0.01% and below 1% by weight % shared in the alkaline aqueous solution.This alkaline aqueous solution thereby can contain water-miscible organic solvents such as methyl alcohol, ethanol and surfactant etc.Thereby can for example can the appropriate combination use dilute with the same organic solvent of solvent as photosensitive composite with organic solvent as developer solution with top.
There is no particular restriction for developing method, can adopt and for example soak development method (immersion development method), spray development method, spray development method, the development of stirring development method methods such as (rich solution development methods).Development temperature is in 10～40 ℃ of scopes usually, and development time is generally 10～300 seconds.
Without the light of irradiate light irradiation area 11 not, be dissolved in the developer solution through development and be removed in the photosensitive composite layer.On the other hand, residually down form colored pattern 5 through the zone 12 of irradiate light.
Embodiment
Below further describe the present invention by means of embodiment, but the present invention is not limited to embodiment.
The manufacturing of the blue photosensitive composite of embodiment 1[] [methacrylic acid unit is 30: 70 with the ratio (mole) of benzyl methacrylate unit with the multipolymer of (B) 0.828 weight portion methacrylic acid and benzyl methacrylate, acid number 113, weight average is spared molecular weight 25000], (C) 0.828 weight portion dipentaerythritol acrylate, (D) 0.199 weight portion Photoepolymerizationinitiater initiater 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, (D) 0.099 weight portion photopolymerization causes auxiliary agent [2,4-diethyl thioxanthone], (E) 0.151 weight portion epoxy compound [orthoresol novolac epoxy resin, " SUMIEPOXYESCN-195XL-80 " (Sumitomo Chemical Company Ltd's manufacturing)] and (F) 6.522 weight portion propylene glycol monomethyl ether obtain potpourri 1 through after mixing.
With this mixing 1 and by (A) 1.030 weight portion pigment [C.I. alizarol saphirol-15: 6] (0.06 micron of on average even particle diameter), (A) 0.016 weight portion pigment [C.I. pigment violet-23] (0.04 micron of on average even particle diameter), (E) 0.298 weight portion polyethyene diamine spreading agent, (F) 5.178 weight portion propylene glycol monomethyl ether, mix the potpourri 2 that obtains and mix, obtained photosensitive composite (blueness).[dissolubility of filming]
Behind the above-mentioned photosensitive composite that obtains of coating on the surface of glass substrate [Corning Incorporated makes, (#7059)] 3, made the fugitive constituent volatilization down in dry 3 minutes with spin-coating method, formed photosensitive composite layer (1.6 microns of thickness) 4 at 100 ℃.This is filmed, and (5cm * 5cm) be immersed in 25 milliliters of propylene glycol monomethyl ether observes substrate and finds to film dissolving after 5 minutes, dissolving back visualization propylene glycol monomethyl ether becomes the blue solution state that is colored as.
The spinner that use has a gap nozzle forms the colored pattern of embodiment 1 preparation with after the coating of sensitization liquid, even also do not detect painted attachment when being coated with 150.
Above-mentioned photosensitive composite is highly sensitive, and the transmitance of the coated film that obtains, contrast, resolution, solvent resistance and liquid crystal structure cell reliability are also good.
The manufacturing of the blue photosensitive composite of embodiment 2[] [methacrylic acid unit is 30: 70 with the ratio (mole) of benzyl methacrylate unit with the multipolymer of (B) 0.828 weight portion methacrylic acid and benzyl methacrylate, acid number 113, weight average is spared molecular weight 25000], (C) 0.828 weight portion dipentaerythritol acrylate, (D) 0.298 weight portion Photoepolymerizationinitiater initiater 2, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3, the 5-triazine and (F) 6.522 weight portion propylene glycol monomethyl ether obtain potpourri 1 through after mixing.
With this mixing 1 and by (A) 1.030 weight portion pigment [C.I. alizarol saphirol-15: 6] (0.06 micron of on average even particle diameter), (A) 0.016 weight portion pigment [C.I. pigment Violet 23] (0.04 micron of on average even particle diameter), (E) 0.298 weight portion carbamate spreading agent and (F) 5.178 weight portion propylene glycol monomethyl ether mix the potpourri 2 obtain and mix, obtained photosensitive composite (blueness).[dissolubility of filming]
Behind the above-mentioned photosensitive composite that obtains of coating on the surface of glass substrate [Corning Incorporated makes, (#7059)] 3, made the fugitive constituent volatilization down in dry 3 minutes with spin-coating method, formed photosensitive composite layer (1.6 microns of thickness) 4 at 100 ℃.This is filmed, and (5cm * 5cm) be immersed in 25 milliliters of propylene glycol monomethyl ether observes substrate and finds to film dissolving after 5 minutes, dissolving back visualization propylene glycol monomethyl ether becomes the blue solution state that is colored as.
The spinner that use has a gap nozzle forms the colored pattern of embodiment 2 preparations with after the coating of sensitization liquid, even also do not detect painted attachment when being coated with 150.
Above-mentioned photosensitive composite is highly sensitive, and the transmitance of the coated film that obtains, contrast, resolution, solvent resistance and liquid crystal structure cell reliability are also good.The manufacturing of the blue photosensitive composite of Comparative Examples 1[] [methacrylic acid unit is 30: 70 with the ratio (mole) of benzyl methacrylate unit with the multipolymer of (B) 0.828 weight portion methacrylic acid and benzyl methacrylate, acid number 113, weight average is spared molecular weight 25000], (C) 0.828 weight portion dipentaerythritol acrylate, (D) 0.199 weight portion Photoepolymerizationinitiater initiater [2-methyl-2-morpholino-1-(4-aminomethyl phenyl) propane-1-ketone], (D) 0.099 weight portion photopolymerization causes auxiliary agent [2, the 4-diethyl thioxanthone] and (F) 6.522 weight portion propylene glycol monomethyl ether obtain potpourri 1 through after mixing.
With this mixing 1 and by (A) 1.030 weight portion pigment [C.I. alizarol saphirol-15: 6] (0.06 micron of on average even particle diameter), (A) 0.016 weight portion pigment [C.I. pigment Violet 23] (0.04 micron of on average even particle diameter), (E) 0.298 weight portion modified acroleic acid be spreading agent and (F) 5.178 weight portion propylene glycol monomethyl ether mix the potpourri 2 obtain and mix, obtained photosensitive composite (blueness).[dissolubility of filming]
Except replace photosensitive composite that embodiment 1 obtains with the above-mentioned photosensitive composite that obtains, operation similarly to Example 1 is in case filming of obtaining is immersed in the piece of just filming in the propylene glycol monomethyl ether vinyl acetate and comes off.Under the level of visualization, almost do not make propylene glycol monomethyl ether painted.
Form with after the coating of sensitization liquid with the colored pattern of the spinner with gap nozzle, just detected painted attachment when being coated with 60 Comparative Examples 1 preparation.
Even use photosensitive composite of the present invention under the situation that adopts slit spin coating mode to be coated with, also can suppress the generation of painted attachment on the color filter, because it is removed the frequency reduction and can boost productivity, have very big industrial utilization and be worth.
And use photosensitive composite of the present invention, and can form evenly good rendered image of transmitance, contrast, sensitivity, resolution, solvent resistance and liquid crystal structure cell reliability, be very suitable for color filter and use.
Claims (8)
1, a kind of photosensitive composite, it is characterized in that it being that to contain (A) on average even particle diameter be 0.01～0.10 micron pigment, (B) resin glue, (C) has the compound of an ethylenic unsaturated double bond and energy addition polymerization at least, the photosensitive composite of (D) Photoepolymerizationinitiater initiater and (E) solvent, the film immersion that described photosensitive composite forms in 10 times of above-described solvents of weight the time dissolution time be within 5 minutes.
2,, it is characterized in that wherein said photosensitive composite also contains the compound that (F) has two above epoxy radicals according to the described photosensitive composite of claim 1.
3,, it is characterized in that wherein containing and be divided into benchmark by solid shape in the composition and count the described pigment of 25～50 weight % according to claim 1 or 2 described photosensitive composites.
4,, it is characterized in that the acid number of wherein said resin glue is in 70～140 scopes according to any one described photosensitive composite in the claim 1～3.
5,, it is characterized in that the even molecular weight of number average of wherein said resin glue is in 5,000～50, in 000 scope according to any one described photosensitive composite in the claim 1～4.
6, a kind of color filter is characterized in that making with any one described photosensitive composite in the claim 1～5.
7, a kind of manufacturing method of color filter is characterized in that wherein using any one described photosensitive composite in the claim 1～5.
8, a kind of formation method of rendered image is characterized in that wherein using any one described photosensitive composite in the claim 1～5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001379809 | 2001-12-13 | ||
| JP2001379809A JP2003177530A (en) | 2001-12-13 | 2001-12-13 | Photosensitive composition |
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| Publication Number | Publication Date |
|---|---|
| CN1424624A true CN1424624A (en) | 2003-06-18 |
| CN1287222C CN1287222C (en) | 2006-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02155958 Expired - Fee Related CN1287222C (en) | 2001-12-13 | 2002-12-12 | Photosensitive composition |
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|---|---|
| JP (1) | JP2003177530A (en) |
| CN (1) | CN1287222C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101876790A (en) * | 2008-12-26 | 2010-11-03 | 东京应化工业株式会社 | Photocurable resin composition for transparent electrode formation and method for producing transparent electrode |
| CN1770012B (en) * | 2004-09-29 | 2011-05-25 | 住友化学株式会社 | Staining light-sensitive resin composition |
| US8168689B2 (en) | 2007-10-01 | 2012-05-01 | Industrial Technology Research Institute | High optical contrast pigment and colorful photosensitive composition employing the same and fabrication method thereof |
| CN103080162A (en) * | 2011-06-13 | 2013-05-01 | Dic株式会社 | Radically polymerizable composition, cured product, and plastic lens |
| WO2014187170A1 (en) | 2013-05-20 | 2014-11-27 | 常州强力先端电子材料有限公司 | Acrylic photocurable composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4897270B2 (en) * | 2005-11-01 | 2012-03-14 | 富士フイルム株式会社 | Photosensitive resin composition, color filter, method for producing the same, and liquid crystal display device |
| JP2008003321A (en) | 2006-06-22 | 2008-01-10 | Tokyo Ohka Kogyo Co Ltd | Photosensitive resin composition, bump for control of liquid crystal alignment using the same and method for forming bump for control of liquid crystal alignment |
| TW201116929A (en) * | 2009-08-10 | 2011-05-16 | Sumitomo Chemical Co | Photoresist composition |
-
2001
- 2001-12-13 JP JP2001379809A patent/JP2003177530A/en active Pending
-
2002
- 2002-12-12 CN CN 02155958 patent/CN1287222C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1770012B (en) * | 2004-09-29 | 2011-05-25 | 住友化学株式会社 | Staining light-sensitive resin composition |
| US8168689B2 (en) | 2007-10-01 | 2012-05-01 | Industrial Technology Research Institute | High optical contrast pigment and colorful photosensitive composition employing the same and fabrication method thereof |
| CN101876790A (en) * | 2008-12-26 | 2010-11-03 | 东京应化工业株式会社 | Photocurable resin composition for transparent electrode formation and method for producing transparent electrode |
| CN103080162A (en) * | 2011-06-13 | 2013-05-01 | Dic株式会社 | Radically polymerizable composition, cured product, and plastic lens |
| CN103080162B (en) * | 2011-06-13 | 2013-11-13 | Dic株式会社 | Radically polymerizable composition, cured product, and plastic lens |
| WO2014187170A1 (en) | 2013-05-20 | 2014-11-27 | 常州强力先端电子材料有限公司 | Acrylic photocurable composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003177530A (en) | 2003-06-27 |
| CN1287222C (en) | 2006-11-29 |
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