CN102073216A - Colored photosensitive resin composition, pattern forming method, manufacture method for color filter, color filter, and display apparatus - Google Patents

Abstract

The invention provides a colored photosensitive resin composition and a pattern forming method with good developing performance and capable of inhibiting generation of reticulation on the baked surface, and a manufacture method for a color filter, a color filter, and a display apparatus for colored patterns with no reticulation on the surface, as well as good line width sensibility, straightness, and heat resistance. The colored photosensitive resin composition comprises a colorant, adhesive resin, a polymerizable compound, a photopolymerization initiator, and a solvent, the content of the colorant relative to a solid content of the colored photosensitive resin composition is 15 to 60 percent by mass based on mass fraction, the adhesive resin is provided with a structure unit selected from allyl, an N-stubstituted maleimide structure unit, a structure unit in an annular imide structure unit, and an acidic group structure unit in molecules, the polymerizable compound is a multifunctional monomer comprising carboxyl, the photopolymerization initiator is an ibuprofen alkali photopolymerization initiator or oxime photopolymerization initiator.

Description

Photosensitive composition, pattern formation method, manufacturing method of color filter, color filter and display device

Technical field

The present invention relates to manufacture method, the color filter of photosensitive composition, pattern formation method, color filter (color filter) and possess the display device of this color filter.

Background technology

As manufacturing method of color filter, known use contains the photosensitive composition of colorant (organic pigment etc.), adhesive resin (binder resin), polymerizable compound and Photoepolymerizationinitiater initiater and uses the method for photoetching process (photolithography).In order to obtain high more meticulous color filter, require the development of photosensitive composition or pattern to form excellences such as property, and require to use excellences such as the thermotolerance of the film that photosensitive composition forms or flatness.

As above-mentioned photosensitive composition, various compositions have been proposed from the aspect of ingredient.For example, in order to reduce the residue after the development, developed the photosensitive composition (for example with reference to TOHKEMY 2007-328148 communique) that has feature aspect the kind of the content of colorant and polymerizable compound.

In addition,, also proposed to specify the device that is used for the photoetching process exposure-processed, and this exposure-processed device has been had the photosensitive composition of high sensitivity as other motion.For example, developed the exposure-processed colored resin composition (for example with reference to the WO2008/084853 communique) that utilizes excimer laser (excimer laser).

Along with the LCD expansion of display device in TV (television) purposes such as (1iquid crystal display), expectation color filter further height becomes more meticulous, and with higher level require photosensitive composition development, use the flatness of the film that photosensitive composition forms.But, disclosed photosensitive composition and having used in the manufacturing method of color filter of said composition in above-mentioned TOHKEMY 2007-328148 communique and WO2008/084853 communique, development property is abundant hardly, and also is difficult to suppress the generation of surperficial reticulation (reticulation) (netted wrinkle).

Summary of the invention

In view of the foregoing, problem of the present invention is to provide development good and can suppress the photosensitive composition of generation of the surperficial reticulation after the back baking (post-bake) and the pattern formation method of having used said composition.

In addition, problem of the present invention also be to provide have being inhibited of surperficial reticulation, the manufacturing method of color filter of the colored pattern of live width sensitivity, rectilinearity and excellent heat resistance, and color filter that obtains by this manufacturing method of color filter and the display device that possesses this color filter.

Found that of inventor's further investigation can solve above-mentioned problem by the following method.

＜1〉a kind of photosensitive composition, it is for containing (A) colorant, (B) adhesive resin, (C) polymerizable compound, (D) Photoepolymerizationinitiater initiater and (E) photosensitive composition of solvent at least, wherein,

The content of above-mentioned (A) colorant is counted 15 quality %～60 quality % with respect to the solid constituent of photosensitive composition with mass fraction,

Above-mentioned (B) adhesive resin has the structural unit, (B-2) that are selected from (B-1) following general formula (I) expression and has the structural unit of N position-substituted maleimide amido and (B-3) at least a kind of structural unit in the structural unit of following general formula (II) expression and have the structural unit of acidic-group in molecule

At least a kind in above-mentioned (C) polymerizable compound is the multi-functional monomer that contains carboxyl,

At least a kind in above-mentioned (D) Photoepolymerizationinitiater initiater is that Photoepolymerizationinitiater initiater or oxime (oxime) are Photoepolymerizationinitiater initiater for lophine (lophine).

In the general formula (I), R ¹¹～R ¹⁵Represent hydrogen atom, halogen atom, cyano group, alkyl or aryl independently of one another, R ¹⁶Expression hydrogen atom or methyl,

In the general formula (II), R ²¹Expression hydrogen atom or methyl, R ²²The expression carbon number is 1～6 alkylidene.R ²³And R ²⁴Represent that independently of one another hydrogen atom or carbon number are alkyl, the R below 4 ²³And R ²⁴Bonding forms carbocyclic ring mutually.

＜2〉according to＜1〉described photosensitive composition, wherein, above-mentioned oxime is that Photoepolymerizationinitiater initiater is that the ketoxime (ketoxime) that following general formula (III) is represented is a Photoepolymerizationinitiater initiater.

In the general formula (III), R and X represent that independently of one another monovalence substituting group, A represent that divalent organic group, Ar represent that aryl, n are 0～5 integer, and when X exists when a plurality of, a plurality of X represent the monovalence substituting group independently of one another, and they can be the same or different.

＜3〉according to＜1〉or＜2〉described photosensitive composition, wherein, the above-mentioned acid number that contains the multi-functional monomer of carboxyl is 80mgKOH/g～200mgKOH/g.

＜4〉according to＜1 〉～＜3〉each described photosensitive composition, it further contains (F) sensitizer, and at least a kind in above-mentioned (F) sensitizer is the simple function mercaptan compound.

＜5〉a kind of pattern formation method, it comprises following operation: will＜1 〉～＜4〉each described photosensitive composition be applied on the substrate, thus the dyed layer that forms dyed layer forms operation; Utilize the ultraviolet laser of pattern sample to expose to above-mentioned dyed layer, thereby form the exposure process of sub-image; With the above-mentioned dyed layer that is formed with sub-image is developed, thereby form the developing procedure of pattern.

＜6〉according to＜5〉described pattern formation method, wherein, the exposure wavelength of above-mentioned ultraviolet laser is the scope of 300nm～380nm.

＜7〉according to＜5〉or＜6〉described pattern formation method, wherein, the pulse laser of above-mentioned ultraviolet laser under the frequency of 20Hz～2000Hz, vibrating.

＜8〉a kind of manufacturing method of color filter, it has by＜5 〉～＜7〉each described pattern formation method on substrate, form the operation of pattern.

＜9〉a kind of color filter, it is for passing through＜8〉described manufacture method manufacturing.

＜10〉a kind of display device, it possesses＜and 9〉described color filter.

According to the present invention, can provide development good and can suppress the photosensitive composition of generation of the surperficial reticulation after the baking of back and the pattern formation method of having used said composition.

In addition, the present invention can also provide has being inhibited and the manufacturing method of color filter of the colored pattern of live width sensitivity, rectilinearity and excellent heat resistance of surperficial reticulation, and color filter that obtains by this manufacturing method of color filter and the display device that possesses this color filter.

Embodiment

Below, explain and be used to implement embodiments of the present invention.

" photosensitive composition "

Photosensitive composition of the present invention contains (A) colorant at least, (B) adhesive resin, (C) polymerizable compound, (D) Photoepolymerizationinitiater initiater and (E) solvent, the content of above-mentioned (A) colorant is counted 15 quality %～60 quality % with respect to the solid constituent of photosensitive composition with mass fraction, above-mentioned (B) adhesive resin has the structural unit that is selected from (B-1) following general formula (I) expression in molecule, (B-2) have the structural unit of N position-substituted maleimide amido and (B-3) at least a kind of structural unit in the structural unit of following general formula (II) expression and have the structural unit of acidic-group, at least a kind in above-mentioned (C) polymerizable compound is the multi-functional monomer that contains carboxyl, and at least a kind in above-mentioned (D) Photoepolymerizationinitiater initiater is that Photoepolymerizationinitiater initiater or oxime (oxime) are Photoepolymerizationinitiater initiater for lophine (lophine).

Below each constituent of photosensitive composition of the present invention is elaborated.

＜(A) colorant 〉

Photosensitive composition of the present invention contains at least a kind of (A) colorant.

The content of (A) colorant in the photosensitive composition of the present invention is counted 15 quality %～60 quality % with respect to the solid constituent of photosensitive composition with mass fraction.When the content of (A) colorant during, can take place to set thickness thickly, be difficult to problems such as development, (tact time) prolongation interval time in order to reach desired tone less than 15 quality %.On the other hand, when the content of (A) colorant surpassed 60 quality %, development time prolonged and contour shape also becomes the bevelling shape, and is therefore not preferred.

The content of (A) colorant in the photosensitive composition of the present invention is 20 quality %～50 quality %, 25 quality %～40 quality % more preferably more preferably.

As (A) colorant, can suitably select dyestuff and pigment to use.From viewpoints such as thermotolerances, more preferably pigment.

The pigment that uses as (A) colorant can be that inorganic pigment also can be an organic pigment, from reaching the viewpoint of high permeability, preferably uses the particle little person of size as far as possible.The mean value of the primary particle size of pigment is preferably 0.01 μ m～0.1 μ m, the scope of 0.01 μ m～0.05 μ m more preferably.

In the photosensitive composition of the present invention, by using macromolecule dispersing agent described later, even the size of pigment is little, pigment-dispersing and dispersion stabilization are also good, even therefore thickness is very thin, also can form the colored pixels of excitation excellence.

In addition, among the present invention, in the contained pigment of photosensitive composition, preferred primary particle size less than the ratio of the pigment of 0.02 μ m in the total amount of this pigment less than 10% and primary particle size surpass 0.08 μ m the ratio of pigment in the total amount of this pigment less than 5%.

By primary particle size less than the ratio of the pigment of 0.02 μ m less than 10%, can prevent that thermotolerance and colourity from changing; The ratio of pigment that surpasses 0.08 μ m by primary particle size can be optimized contrast (contrast) less than 5%, can optimize photosensitive composition ageing stability, and can further prevent the foreign matter fault.

Primary particle size from thermotolerance with prevent the viewpoint that colourity changes, is more preferably less than 5% less than the ratio of the pigment of 0.02 μ m.

Primary particle size surpasses the ratio of pigment of 0.08 μ m from optimizing the viewpoint of contrast, preferably less than 3%.

The primary particle size of pigment can use TEM (transmission electron microscope) (transmission electron microscope) to measure.That is, by the TEM photo is carried out graphical analysis, research size distribution carry out.For example, can be by calculating the total population in the observation sample under 30,000 times～100,000 times and grasping size-grade distribution less than the population of the pigment of 0.02 μ m and the population that surpasses the pigment of 0.08 μ m.More specifically, utilize transmission electron microscope to observe down the pigment powder, take pictures, measure the major diameter of 1000 primary particles, calculate less than the primary particle of 0.02 μ m and surpass the ratio of the primary particle of 0.08 μ m at 30,000 times～100,000 times.The position that changes the pigment powder amounts to carries out this operation to 3 positions, and the result is average.

As can be used as the inorganic pigment that (A) colorant uses, can list the metallic compound of expression such as metal oxide and metal complex, particularly can enumerate tap a blast furnace, the composite oxides of metal oxide such as cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and above-mentioned metal etc.

As above-mentioned organic pigment, for example can list:

C.I. paratonere 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279;

C.I. pigment yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214;

C.I. pigment orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73;

C.I. pigment Green 7,10,36,37;

C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,79 Cl substituting group change over the material, 80 of OH;

C.I. pigment violet 1,19,23,27,32,37,42;

C.I. pigment brown 25,28 etc.

Wherein, can list following substances as the pigment that can preferably use.But the present invention is not limited to these.

C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;

C.I. pigment orange 36,71;

C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264;

C.I. pigment violet 19,23,32;

C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36,37.

These organic pigments can use separately or multiple being used in combination in order to improve excitation.The object lesson of combination below is shown.

For example, pigment as red color tone (R) usefulness, can use anthraquinone (anthraquinone) series pigments perylene (perylene) series pigments separately, diketopyrrolo-pyrrole (diketopyrrolopyrrole) series pigments, perhaps can use at least a kind in them is yellow uitramarine with bisdiazo (disazo), isoindoline (isoindoline) is a yellow uitramarine, perhaps quinophthalone (quinophthalone) is that yellow uitramarine Huo perylene (perylene) is a red pigment, anthraquinone is a red pigment, the condensation bisdiazo is a red pigment, perhaps diketopyrrolo-pyrrole is the potpourri of red pigment etc.For example, as anthraquione pigmentss, can list C.I. paratonere 177; Zuo is a perylene pigment, can list C.I. paratonere 155, C.I. paratonere 224; As the condensation azo is red pigment, can list C.I. paratonere 242; As the diketopyrrolo-pyrrole series pigments, can list C.I. paratonere 254; From the angle of Color reproduction, the preferred potpourri of at least a kind in these red pigments and C.I. pigment yellow 13 9 or C.I. paratonere 177.

In addition, the mass ratio of red pigment and other pigment (red pigment: other pigment) be preferably 100: 5～100: 80.When being 100: 4 when following, may be difficult to suppress sometimes 400nm～500nm transmittance, can't improve excitation.In addition, when being 100: 81 when above, the situation that has the colour developing ability to reduce.Above-mentioned mass ratio most preferably is 100: 10～100: 65 scope especially.Wherein, when being combination between the red pigment, can adjust according to colourity.

In addition, pigment as green hue (G) usefulness, can use the halogenated phthalocyanines series pigments separately, perhaps can use itself and bisdiazo is that yellow uitramarine, quinophthalone are that yellow uitramarine, azomethine (azomethine) are that yellow uitramarine or isoindoline are the potpourri of yellow uitramarine.For example, as such example, preferred C.I. pigment Green 7,36 or 37 and the potpourri of C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.

The mass ratio of viridine green and yellow uitramarine (viridine green: yellow uitramarine), be preferably 100: 5～100: 150, be preferably 100: 30～100: 120 scope especially from obtaining the viewpoint that sufficient excitation and inhibition depart from NTSC (National Television System Committee) target tone.

As the pigment of blue cast (B) usefulness, can use phthualocyanine pigment separately or use it Yu dioxazine (dioxazine) is the potpourri of violet pigment.For example, preferred C.I. pigment blue 15: 6 with the potpourri of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment (blue pigment: violet pigment) be preferably 100: 0～100: 50, more preferably 100: 5～100: 30.

Especially preferably use as colorant among the present invention and belong to organic pigment and the miniaturization operation by pigment or dispersion step and pigment is coated the colorant that obtains with macromolecular compound.By with macromolecular compound pigment being coated, inhibition is through the formation of 2 aggregations of the pigment of miniaturization.Among the present invention, more preferably use the coating pigment to make the dispersion stabilization excellence that coating pigment that its dispersiveness of disperseing with the state of 1 particle is improved or through disperseing 1 time keeps particle-stabilisedly.

Coating pigment as optimal way among the present invention is meant the pigment that utilizes macromolecular compound that pigment is coated and obtain.Here, coat and to be meant, obtain to have the more coating pigment of high dispersion stability thus by on the new interface of the high pigment of the surfactivity that produces by miniaturization, forming the firm clad of this macromolecular compound with the strong electrostatic interaction of macromolecular compound.That is, among the present invention, the pigment that coats after handling promptly uses and can wash coating the organic solvent of handling employed macromolecular compound dissolving, and the macromolecular compound that is coated can not dissociate substantially yet.

The said coating pigment macromolecular compound that to be pigment particles such as organic pigment had a heterocycle isopolarity group by side chain coats and the material that forms among the present invention, this macromolecular compound is by coating part or all of pigment particles surface securely, thereby play the effect of higher dispersion stabilization, be adsorbed in pigment with general macromolecule dispersing agent and the material that forms is different.This coated state can be confirmed as getting off: the free amount (ionization rate) of measuring macromolecular compound by the washing that utilizes organic solvent shown below.Promptly, only depend on of the washing of the formed macromolecular compound of absorption by utilizing organic solvent to carry out, its major part, particularly take place free more than 65% and be removed, but as the situation of the pigment of surface of the present invention through coating under, ionization rate is minimum, be below 30%.

Above-mentioned free amount (ionization rate) is by calculating with the pigment that the 1-methoxyl-washing of 2-propyl alcohol coats after handling.Promptly, pigment 10g is put among 1-methoxyl-2-propyl alcohol 100ml, use vibrating machine at room temperature to vibrate 3 hours, utilize centrifugal separator afterwards 80,000rpm tries to achieve the quality of supernatant solid constituent partly down with 8 hours time chien shih pigment precipitation by seasoning.The ratio of the quality of used macromolecular compound calculates ionization rate (%) in being handled by the quality of this solid constituent and the coating of pigment.

The commercially available above-mentioned free amount (ionization rate) of pigment that waits can be measured by following method.Promptly, the solvent (for example dimethyl sulfoxide (DMSO), dimethyl formamide, formic acid, sulfuric acid etc.) that utilizes dissolving pigment is with after whole pigment dissolved, utilize deliquescent difference with an organic solvent macromolecular compound to be separated with pigment, " quality of the coating of pigment used macromolecular compound in handling " obtained.In addition, with 1-methoxyl-2-propyl alcohol washing pigment, divided by this " quality of the coating of pigment used macromolecular compound in handling ", try to achieve ionization rate (%) with the above-mentioned free amount that obtains.

Ionization rate is more little, and then the clad ratio to pigment is high more, and is dispersed, dispersion stabilization is good more.The preferable range of ionization rate is below 30%, more preferably below 20%, most preferably be below 15%.Be desirably 0%.

Coat to handle and preferably in the miniaturization operation of pigment, carry out simultaneously, particularly implement through following operation: add (i) pigment, (ii) water miscible inorganic salts, (iii) do not dissolve (ii) a spot of water-miscible organic solvent and (iv) macromolecular compound basically, utilize kneader (kneader) to wait and mechanically carry out the mixing operation (be called salt and grind method (salt-milling) operation) that obtains potpourri; This potpourri is put in the water, utilized high-speed mixer (high-speed mixer) etc. to stir the operation of making slip (slurry) shape; And, carry out dry operation as required with this slurry filtration, washing.

For above-mentioned salt mill method, further describe particularly.At first, at (i) organic pigment with (ii) add a spot of (iii) water-miscible organic solvent as wetting agent in the potpourri of water miscible inorganic salts, utilize kneader etc. violent mixing after, this potpourri is dropped in water, utilize high-speed mixer etc. to stir, make the slip shape.Then, this slip is filtered, washes, carries out as required drying, thereby obtain pigment through miniaturization.In addition, be scattered in when using in the oil varnish (varnish), can also water removed, simultaneously the processing pigment (being called filter cake) before dry is scattered in oil varnish by the method that is generally known as flash distillation.In addition, when being scattered in the varnish of water system, handling pigment and there is no need to carry out drying, can directly filter cake be scattered in the varnish.

During salt mill method, as above-mentioned (iv) macromolecular compound, by in above-mentioned (iii) organic solvent and with partly soluble at least resin, can obtain finer, surface by (iv) macromolecular compound coat dry the time pigment assemble few material.

In addition, add the opportunity of (iv) macromolecular compound and can all add, also can disperse to add at the initial stage that salt grinds the method operation.In addition, can also in dispersion step, add.

As long as the employed macromolecular compound of the coating of pigment has the adsorbability group of adsorption pigment.Particularly preferably use side chain to have the macromolecular compound of heterocycle.As such macromolecular compound, for example can use paragraph (0029)～(0030) of TOHKEMY 2008-83089 communique, the paragraph (0044) of TOHKEMY 2009-62457 communique～(0047) disclosed material.

When stating pigment in the use, more preferably use in the spreading agent at least a kind with pigment dispersing, use with the form of pigment dispensing composition through coat handling.By containing this spreading agent, can further improve dispersing of pigments.

As spreading agent, for example can suitably select known pigment dispersing agent or surfactant to use.

Particularly, can use the compound of a plurality of kinds, organic siloxane polymer (organosiloxane polymer) KP341 (trade name for example, (the Shin-Etsu Chemical Co. of Shin-Etsu Chemial Co., Ltd, Ltd.) system), (methyl) acrylic acid series (being total to) polymer P OLYFLOW No.75, No.90, No.95 (trade name, (the KYOEISHA CHEMICAL Co. of chemical industry Co., Ltd. of common prosperity society, Ltd.) system), W001 (trade name, company of Yu Business Co., Ltd kations such as (Yusho Co., Ltd.) systems) is a surfactant; Nonionics such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid esters are surfactant; W004, W005, W017 negative ion such as (trade name, Yu Business Co., Ltd's corporate systems) are surfactant; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (are trade name, Ciba Specialty Chemicals company (BASF Japan Ltd.) system), (DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID9100 macromolecule dispersing agents such as (being trade name, SAN NOPCO company (SAN NOPCO LIMITED) system); Various SOLSPERSE spreading agents such as SOLSPERSE 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 (trade name, Japanese Lubrizol Co., Ltd. (Lubrizol Japan Ltd.) system); ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (trade name, rising sun electrification Co., Ltd. (ADEKA Corporation) makes) and IONET S-20 (trade name, (the Sanyou Chemical Industries Co. of Sanyo Chemical Industries Co., Ltd., Ltd.) system), Disperbyk 101,103,106,108,109,111,112,116,130,140,142,161,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (trade name, BYK Co., Ltd. (BYK Japan KK) systems).In addition, also can list oligomer or the polymkeric substance that acrylic acid series copolymer equimolecular end or side chain have polar group.

As the content of spreading agent in pigment dispensing composition, be 1～100 quality %, 3～70 quality % more preferably with respect to the quality optimization of above-mentioned pigment.

Pigment derivative is one of macromolecular compound that is used for the pigment coating, makes an addition in the pigment dispensing composition as required.There is the pigment derivative that has the part of compatibility or a polar group with spreading agent to be adsorbed in surface of pigments and its adsorption site as spreading agent is used by making to import, pigment is scattered in the photosensitive polymer combination as fine particle, thereby it is prevent that it from reassociating, and effective to the color filter that constitutes contrast height, transparency excellence.

Pigment derivative with the organic pigment be specifically precursor skeleton, side chain import acidic-group or basic group are arranged, aromatic group is as substituent compound.Organic pigment is in particular quinoline a word used for translation ketone series pigments, phthualocyanine pigment, azo pigment, quinophthalone series pigments, isoindoline series pigments, isoindolone series pigments, quinoline pigment, diketopyrrolo-pyrrole pigment, benzimidazolone pigment etc.Also comprise flaxen aromatic series polycyclic compunds such as the naphthalene system that generally is not known as pigment, anthraquinone system, triazine system, quinoline system.As pigment derivative, for example can use the material of record in Japanese kokai publication hei 11-49974 communique, Japanese kokai publication hei 11-189732 communique, Japanese kokai publication hei 10-245501 communique, TOHKEMY 2006-265528 communique, Japanese kokai publication hei 8-295810 communique, Japanese kokai publication hei 11-199796 communique, TOHKEMY 2005-234478 communique, TOHKEMY 2003-240938 communique, the TOHKEMY 2001-356210 communique etc.

The content of pigment derivative in pigment dispensing composition is 1 quality %～30 quality %, 3 quality %～20 quality % more preferably with respect to the quality optimization of pigment.This content is in above-mentioned scope the time, can be when suppressing viscosity, and disperse well and improves dispersion stabilization after disperseing, obtain the look characteristic of the high excellence of transmissivity, when the making color filter, can constitute high-contrast with good color characteristic.

The bead dispersion machine etc. that the method for disperseing for example can have been utilized zirconia bead etc. by use is to being pre-mixed pigment and spreading agent and carrying out differential with the potpourri that homogenizer etc. has carried out disperseing in advance and loose and carry out.

Among the present invention, when using dyestuff, can obtain the photosensitive composition of uniform dissolution as (A) colorant.

As being not particularly limited, can use the known dyestuff that in the past used as the color filter purposes as the dyestuff that (A) colorant uses.Japanese kokai publication sho 64-90403 communique is for example arranged, Japanese kokai publication sho 64-91102 communique, Japanese kokai publication hei 1-94301 communique, Japanese kokai publication hei 6-11614 communique, the Japan spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 instructionss, United States Patent (USP) the 5th, 667, No. 920 instructionss, United States Patent (USP) the 5th, 059, No. 500 instructions, Japanese kokai publication hei 5-333207 communique, Japanese kokai publication hei 6-35183 communique, Japanese kokai publication hei 6-51115 communique, Japanese kokai publication hei 6-194828 communique, Japanese kokai publication hei 8-211599 communique, Japanese kokai publication hei 4-249549 communique, Japanese kokai publication hei 10-123316 communique, Japanese kokai publication hei 11-302283 communique, Japanese kokai publication hei 7-286107 communique, TOHKEMY 2001-4823 communique, Japanese kokai publication hei 8-15522 communique, Japanese kokai publication hei 8-29771 communique, Japanese kokai publication hei 8-146215 communique, Japanese kokai publication hei 11-343437 communique, Japanese kokai publication hei 8-62416 communique, TOHKEMY 2002-14220 communique, TOHKEMY 2002-14221 communique, TOHKEMY 2002-14222 communique, TOHKEMY 2002-14223 communique, Japanese kokai publication hei 8-302224 communique, Japanese kokai publication hei 8-73758 communique, Japanese kokai publication hei 8-179120 communique, the pigment of record in the Japanese kokai publication hei 8-151531 communique etc.

Can use as chemical constitution have pyrazoles azo system, aniline azo system, triphenyl methane system, anthraquinone system, Anthrapyridone system, benzylidene system, oxygen alcohol system, pyrazolone three pyrazoles azos system, pyridone azo system, cyanines system, phenothiazine system, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system or indigo be isostructural dyestuff.

＜(B) adhesive resin 〉

Photosensitive composition of the present invention contains at least a kind of (B) adhesive resin.

(B) adhesive resin has the structural unit, (B-2) that are selected from (B-1) following general formula (I) expression and has the structural unit of N position-substituted maleimide amido and (B-3) at least a kind of structural unit in the structural unit of following general formula (II) expression and have the structural unit of acidic-group in molecule.

(structural unit (B-1))

(B-1) structural unit is represented with following general formula (I).

In the general formula (I), R ¹¹～R ¹⁵Represent hydrogen atom, halogen atom, cyano group, alkyl or aryl independently of one another, R ¹⁶Expression hydrogen atom or methyl.

As the R in the general formula (I) ¹¹～R ¹⁵Preferred independently of one another for hydrogen atom, halogen atom, cyano group, carbon number are that 1～12 alkyl or carbon number are 5～14 aryl, wherein more preferably hydrogen atom, bromine atoms, chlorine atom, cyano group, carbon number are that 1～7 alkyl or carbon number are 5～10 aryl.

Abovementioned alkyl can have substituting group, can be the substituting group of straight chain, side chain or ring-type as this substituting group, can list methyl, n-pro-pyl, isopropyl, the tert-butyl group etc., and preferred carbon number is 1～7 alkyl.

In addition, above-mentioned aryl also can have substituting group, and can list carbon number as this substituting group is that 1～7 alkyl or carbon number are 5～14 aryl etc., preferred phenyl, furyl, naphthyl.

Wherein, be R as general formula (I) preferred construction unit ¹¹～R ¹⁵Be hydrogen atom, methyl, phenyl or halogen atom independently of one another, R ¹⁶Structural unit for hydrogen atom or methyl.

(structural unit (B-2))

Have the structural unit of N position-substituted maleimide amido as (B-2), for example can list the structural unit shown in following.

(structural unit (B-3))

(B-3) structural unit is represented with following general formula (II).

In the general formula (II), R ²¹Expression hydrogen atom or methyl, R ²²The expression carbon number is 1～6 alkylidene.R ²³And R ²⁴Represent that independently of one another hydrogen atom or carbon number are the alkyl below 4.R ²³And R ²⁴Bonding forms carbocyclic ring mutually.

As general formula (II) preferred construction unit is R ²¹Be hydrogen atom, R ²²Be methylene or ethylidene, R ²³And R ²⁴Bonding forms the structural unit of 6 yuan of rings mutually.

(B) adhesive resin as long as have in the molecule structural unit, (B-2) that are selected from (B-1) general formula (I) expression has the structural unit of N position-substituted maleimide amido and (B-3) at least a kind of structural unit in the structural unit of general formula (II) expression, also can have more than 2 kinds.

(B) adhesive resin is at (B-1), (B-2) with (B-3), and the viewpoint from the generation that suppresses surperficial reticulation (netted wrinkle) preferably has (B-1).

(B) adhesive resin preferably in molecule, amount to have 50 moles of %～90 mole %, structural unit, (B-2) of more preferably 50 moles of %～80 mole %, further (B-1) general formula (I) expression of preferred 60 moles of %～80 mole % contain the structural unit of N position-substituted maleimide amido and (B-3) structural unit of general formula (II) expression.In the time of in this scope, thickness loss minimizing, surface smoothing and development tolerance when developing after the exposure are good.

(structural unit) with acidic-group

In addition, (B) adhesive resin has the structural unit that has acidic-group in molecule.

As structural unit, can list the structural unit in the unsaturated monomer source of containing carboxyl with acidic-group.Unsaturated monomer as containing carboxyl has unsaturated monocarboxylic acid classes such as (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid; Unsaturated dicarboxylic acid or its anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; Unsaturated polybasic carboxylic acid more than 3 yuan or its anhydrides; List ((methyl) acryloxyalkyl) the ester class of mono succinate (2-(methyl) acryloxy ethyl ester), the phthalic acid list polybasic carboxylic acids more than 2 yuan such as (2-(methyl) acryloxy ethyl esters); ω-carboxyl polycaprolactone list (methyl) acrylate etc. have list (methyl) esters of acrylic acid of the polymkeric substance of carbonyl and hydroxyl etc. at two ends.

These contain in the unsaturated monomer of carboxyl, mono succinate (2-acryloxy ethyl ester) and phthalic acid list (2-acryloxy ethyl ester) are respectively with M-5300 and M-5400 (the trade name sale of Toagosei Co., Ltd's (Toa Gosei Co., Ltd.) system).

The above-mentioned unsaturated monomer that contains carboxyl can contain separately also in resin and can contain more than 2 kinds.

Wherein, as structural unit, can list chalcogen (chalcogen) analog, carbon hydrazoic acid (carbohydrazonic acid) [the RC (=NNH of carboxylic acid, carboxylic acid with preferred acidic-group ₂) OH], azomethine acid (carboximidic acid) [RC (=NH) OH], sulfonic acid [RS (O) ₂OH], sulfinic acid [RS (O) OH], sulfenic acids [RSOH], selenic acid (selenonic acid) [RSE (O) ₂OH], the structural unit in the analog source of selenous acid (seleninic acid) [RSE (O) OH], inferior selenic acid (selenenicacid) [RSEOH], phosphoric acid and its acid related compound, silicic acid, boric acid, the structural unit in preferred especially acrylic acid, methacrylic acid and phosphoric acid source.

(B) content of the structural unit with acidic-group in the adhesive resin is preferably 5 moles of %～50 mole %, 10 moles of %～30 mole % more preferably.When in this scope, surface smoothness and thermotolerance during development are good.

(B) adhesive resin can also contain other structural unit except above-mentioned each structural unit.As other structural unit, can list the structural unit in following unsaturated monomer source.

Styrene, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to aromatic ethenyl compounds such as vinyl benzyl glycidyl ethers; Indenes classes such as indenes, 1-methyl indenes; (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) acrylic acid allyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid cyclohexyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid methoxyl binaryglycol ester, (methyl) acrylic acid methoxyl triglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 ^2,6] unsaturated carboxylate types such as decane-8-base ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy propyl ester, list (methyl) acrylic acid glyceride; Unsaturated carboxylic acid aminoalkyl ester classes such as (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of (methyl) acrylic acid 2-, (methyl) acrylic acid 2-dimethylamino propyl ester, the amino propyl ester of (methyl) acrylic acid 3-, (methyl) acrylic acid 3-dimethylamino propyl ester; Unsaturated carboxylic acid ethylene oxidic ester classes such as (methyl) glycidyl acrylate; Unsaturated carboxylic acid oxetanyl ester classes such as (methyl) acrylic acid oxetanyl ester; Vinyl carboxylates classes such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether; Vinyl cyanide compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing, vinylidene dinitrile; Unsaturated acyl amines such as (methyl) acrylamide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylamide; Unsaturated acid imides such as maleimide, N-phenylmaleimide, N-cyclohexyl maleimide; Aliphatics conjugated dienes such as 1,3-butadiene, isobutylene, chlorobutylene; Polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane etc. have the macromonomer class of list (methyl) acryloyl group at the end of polymer molecular chain.

The constituent in these unsaturated monomer sources can contain separately, also can contain more than 2 kinds.

Example compound 1-1～the 1-8 and 2～39 of (B) adhesive resin below is shown.(B) adhesive resin is not limited to these example compound.

As the weight-average molecular weight of (B) adhesive resin, be preferably 10000～100000 scope, more preferably 10000～50000 scope, 10000～40000 scope more preferably.When being in this scope, development, rectilinearity are good.

The content of (B) adhesive resin in the photosensitive composition of the present invention is preferably the scope of 10 quality %～50 quality %, the scope of 15 quality %～40 quality % more preferably with respect to the solid constituent of photosensitive composition.

Photosensitive composition of the present invention can contain the resin of the structure except that (B) adhesive resin.Resin as the structure except that (B) adhesive resin, so long as to colorant play a role as bonding agent and to when making color filter in its development treatment operation used developer solution, the material that preferred especially alkaline-based developer has solubility, then be not particularly limited, the acrylic acid series copolymer that preferably has carboxyl, but the multipolymer of the ethylenically unsaturated monomers of the ethylenically unsaturated monomers of 1 above carboxyl and other copolymerization especially preferably had.

Among the present invention, the object lesson as the resin of the structure except that (B) adhesive resin can list:

(methyl) acrylic acid/(methyl) methyl acrylate copolymer,

(methyl) acrylic acid/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/(methyl) methyl acrylate/polystyrene macromolecular monomer copolymer,

(methyl) acrylic acid/(methyl) methyl acrylate/polymethylmethacrylate macromonomer multipolymer,

(methyl) acrylic acid/(methyl) benzyl acrylate/polystyrene macromolecular monomer copolymer,

(methyl) acrylic acid/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate/polystyrene macromolecular monomer copolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate/polymethylmethacrylate macromonomer multipolymer etc.

In addition, can also use the resin that contains such epoxide ring or oxetanes ring:

Styrene/methacrylic acid/methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester/glycidyl methacrylate copolymer,

Styrene/acrylic/acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester/glycidyl acrylate multipolymer,

Benzyl methacrylate/methacrylic acid/3-(methacryloxy methyl) oxetanes/metering system tert-butyl acrylate multipolymer,

Benzyl methacrylate/methacrylic acid/3-(methacryloxy methyl)-3-ethyl oxetanes/styrol copolymer,

Butadiene/methacrylic acid/methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester/glycidyl methacrylate copolymer,

Butadiene/methacrylic acid/methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester/glycidyl methacrylate copolymer,

Styrene/methacrylic acid/methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester/methacrylic acid-6,7-epoxy radicals heptyl ester multipolymer,

Styrene/acrylic/maleic anhydride/methacrylic acid-6,7-epoxy radicals heptyl ester multipolymer,

Metering system tert-butyl acrylate/acrylic acid/maleic anhydride/methacrylic acid-6,7-epoxy radicals heptyl ester multipolymer,

Styrene/methacrylic acid/methyl methacrylate/glycidyl methacrylate copolymer,

To methoxy styrene/methacrylic acid/acrylic acid cyclohexyl ester/glycidyl methacrylate copolymer.

＜(C) polymerizable compound 〉

Photosensitive composition of the present invention contains at least a kind of (C) polymerizable compound, and (C) at least a kind in the polymerizable compound is for containing the multi-functional monomer of carboxyl.

[the multi-functional monomer that contains carboxyl]

Among the present invention the spendable multi-functional monomer that contains carboxyl be meant in molecule, have at least 1 carboxyl, preferred 1～4, the more preferably monomer of 1～3 carboxyl.As multifunctional, have more than 2, preferred 2～12, more preferably 3～6 polymerism unsaturated double-bonds.

Particularly, for example can list the multi-functional carboxylate that contains free carboxy that polyalcohols and the polymerizable unsaturated carboxylic acids class with 2 above carboxyls more than 2 yuan form; (c1) polyvalent alcohol more than 3 yuan and the polymerizable unsaturated carboxylic acids that (c2) has 1 above carboxyl (T1) that form contain the multi-functional ester class of free carboxy and (c3) with the carboxylate that contains free carboxy of dicarboxylic acids class formation (below be called (C1) multi-functional monomer); (c4) the multi-functional carboxylate that contains free carboxy that forms of the polybasic carboxylic acid class more than 3 yuan and the polymerizable unsaturated compound that (c5) has 1 above hydroxyl (below be called (C2) multi-functional monomer) etc.

(c1)+(c2)→(T1)(1-1)

(T1)+(c3)→(C1)(1-2)

(c4)+(c5)→(C2)(2)

As the multi-functional monomer that contains carboxyl among the present invention, preferably (C1) multi-functional monomer or (C2) multi-functional monomer.(C1) in the multi-functional monomer, for example can list glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol etc. as above-mentioned polyvalent alcohol more than 3 yuan.

As above-mentioned polymerizable unsaturated carboxylic acids, for example can list (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. with 1 above carboxyl.

As above-mentioned dicarboxylic acids class, for example can list oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane-1,2-dicarboxylic acids, cyclohexane-1,3-dicarboxylic acids, cyclohexane-1,4-dicarboxylic acids, phthalic acid, m-phthalic acid, terephthalic acid (TPA) etc.

In addition, (C2) in the multi-functional monomer, as the polybasic carboxylic acid class more than 3 yuan, for example can list propane-1,2,3-tricarboxylic acid (the third three acid), butane-1,2,4-tricarboxylic acid, aconitic acid, norcamphor three acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid etc.

As above-mentioned polymerizable unsaturated compound, for example can list (methyl) allyl alcohol, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester etc. with 1 above hydroxyl.

If preferred (C1) the multi-functional monomer and (C2) example of multi-functional monomer more specifically are shown among the present invention, then can list trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc. and contain widow's (methyl) esters of acrylic acid of monohydroxy and the mono-esterification thing that contains free carboxy of dicarboxylic acids class formation such as malonic acid, succinic acid, glutaric acid, phthalic acid, terephthalic acid (TPA); Propane-1,2,3-tricarboxylic acid, butane-1,2,4-tricarboxylic acid, benzene-1,2, the few carboxylate that contains free carboxy that (methyl) acrylic acid monohydroxy alkyl esters such as tricarboxylic acid classes such as 3-tricarboxylic acid, trimellitic acid, trimesic acid and (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester form etc.

In addition, the multi-functional monomer as containing carboxyl for example can list following M-1～M-4, from the viewpoint of photo-curable, alkali-developable, and more preferably following monomer M-1.

The multi-functional monomer that contains carboxyl among the present invention is from shortening the viewpoint of development time and the caused development of compatibility (lines shakiness, surface smoothing), and preferably its acid number is 80mgKOH/g～200mgKOH/g.More preferably 80mgKOH/g～150mgKOH/g, 80mgKOH/g～120mgKOH/g more preferably.Among the present invention, acid number is obtained by the method for record in the test method (JISK0070:1992) of the acid number of known chemicals.

Among the present invention, the multi-functional monomer that contains carboxyl can be used singly or two or more kinds mixed.

The multi-functional monomer that contains carboxyl among the present invention is a well-known material in this industrial field, can be not particularly limited to use these materials in the present invention, can use commercially available product also can use suitably synthetic material.

In the photosensitive composition of the present invention, except the multi-functional monomer that contains carboxyl, also can and with other multi-functional monomer conduct (C) polymerizable compound.

Here, the multi-functional monomer that contains carboxyl with respect to the usage ratio of total multi-functional monomer be preferably 10 quality %～100 quality %, more preferably 20 quality %～100 quality %, be preferably 50 quality %～100 quality % especially.By being above-mentioned scope, it is good that the formation of required pattern becomes easily, development becomes.

As spendable multi-functional monomer except that the multi-functional monomer that contains carboxyl among the present invention, for example can list have monomer, prepolymer, the i.e. material of 2 aggressiveness, 3 aggressiveness and oligomer or their potpourri and their chemical forms such as multipolymer.Example as monomer and its multipolymer, can list unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) or its ester class, amide-type, preferably use the amide-type of ester, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acid and aliphatic polyol compound.

In addition, the also preferred addition reaction that uses with hydroxyl or the substituent esters of unsaturated carboxylic acids of nucleophilicities such as amino, sulfydryl or unsaturated carboxylic acid amide-type and simple function or polyfunctional isocyanate's class or simple function or multi-functional epoxy's class; And the dehydration condensation thing of above-mentioned esters of unsaturated carboxylic acids or unsaturated carboxylic acid amide-type and simple function or polyfunctional carboxylic acid etc.

In addition, the addition reaction that also preferably has substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanate group or epoxy radicals or unsaturated carboxylic acid amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol; The substituted reactant that more preferably has the esters of unsaturated carboxylic acids of the substituents of leaving away such as halogen atom, tolysulfonyl oxygen base or unsaturated carboxylic acid amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol.

In addition, as other examples, can also use above-mentioned unsaturated carboxylic acid is replaced to unsaturated phosphonic acids, styrene, vinyl ether etc. and the compound group of acquisition.

Object lesson as the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid: as acrylate, can list glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, the tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol 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, the polyester acrylic oligomer ester, acid isocyanate EO modification triacrylate etc.;

As methacrylate, can list the tetramethylene glycol dimethylacrylate, the triethylene glycol dimethylacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, the 1,3 butylene glycol 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 (to (3-metacryloxy-2-hydroxyl propoxyl group) phenyl) dimethylmethane, two-(to (metacryloxy ethoxy) phenyl) dimethylmethane etc.;

As itaconate, can list ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc.;

As crotonates, can list ethylene glycol bisthioglycolate crotonates, tetramethylene glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four or two crotonatess etc.;

As the iso-crotonic acid ester, can list ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters etc.;

As maleate, can list ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc.

As other the example of ester, the aliphatic alcohol of putting down in writing in for example also preferred use Japanese Patent Publication 51-47334 communique, the Japanese kokai publication sho 57-196231 communique is the ester class, the material of putting down in writing in Japanese kokai publication sho 59-5240 communique, Japanese kokai publication sho 59-5241 communique, the Japanese kokai publication hei 2-226149 communique with aromatic series pastern bone frame, or the material of putting down in writing in the Japanese kokai publication hei 1-165613 communique that contains amino etc.In addition, above-mentioned ester monomer can also form of mixtures use.

In addition, object lesson as the monomer of the acid amides of aliphatic polyamine compound and unsaturated carboxylic acid, can list di-2-ethylhexylphosphine oxide-acrylamide, di-2-ethylhexylphosphine oxide-Methacrylamide, 1, the 6-hexa-methylene is two-acrylamide, 1, and the 6-hexa-methylene is two-Methacrylamide, diethylene triamine three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.Preferred acid amides as other is the example of monomer, can list the material of putting down in writing in the Japanese Patent Publication 54-21726 communique with cyclohexene structure.

In addition, the carbamate that also preferably utilizes the addition reaction of isocyanates and hydroxyl and make is the addition polymerization compound, as such object lesson, for example can list put down in writing in the Japanese Patent Publication 48-41708 communique at 1 molecule had addition on the polyisocyanate compounds of 2 the above isocyanate group vinyl carbamate compound that in 1 molecule, contains 2 above polymerism vinyl that forms of the vinyl monomer that contains hydroxyl of following general formula (V) expression etc.

CH ₂＝C(R ⁴)COOCH ₂CH(R ⁵)OH (V)

(wherein, in the general formula (V), R ⁴And R ⁵Expression H or CH ₃)

In addition, the urethane acrylate class of putting down in writing in also preferred Japanese kokai publication sho 51-37193 communique, the special fair 2-32293 communique of Japan, the special fair 2-16765 communique of Japan; The carbamate compounds class of putting down in writing in Japanese Patent Publication 58-49860 communique, Japanese Patent Publication 56-17654 communique, Japanese Patent Publication 62-39417 communique, the Japanese Patent Publication 62-39418 communique with oxirane pastern bone frame.In addition, by using the addition polymerization compounds of putting down in writing in Japanese kokai publication sho 63-277653 communique, Japanese kokai publication sho 63-260909 communique, the Japanese kokai publication hei 1-105238 communique that in molecule, has amino structure or sulfide structure, also can obtain the very excellent optical polymerism composition of film speed.

As other example, also can list the polyester acrylate class of putting down in writing in Japanese kokai publication sho 48-64183 communique, Japanese Patent Publication 49-43191 communique, the Japanese Patent Publication 52-30490 communique, polyfunctional acrylic ester or the methacrylates such as epoxy acrylate class that epoxy resin is obtained with the reaction of (methyl) acrylic acid.In addition, also can list the specific unsaturated compound of putting down in writing in Japanese Patent Publication 46-43946 communique, the special fair 1-40337 communique of Japan, the special fair 1-40336 communique of Japan, the vinyl phosphonate based compound of putting down in writing in the Japanese kokai publication hei 2-25493 communique etc.In addition, also preferably use the structure of putting down in writing in the Japanese kokai publication sho 61-22048 communique that contains perfluoroalkyl in some cases.In addition, can also use Japanese Jie disclosed photo-curable monomer and oligomer in Association Hui Chi (Journal of the AdhesionSociety of Japan) vol.20, No.7,300～308 pages (1984).

Above-mentioned other multi-functional monomer can also be used in combination more than 2 kinds except a kind of independent use.

For these multi-functional monomers, its structure, separately use or and the details of the using method of usefulness, addition etc. can at random set according to the final performance design of photosensitive composition.For example, select from following viewpoint.

From the angle of sensitivity, the structure that the unsaturated group mass contg of preferred per 1 molecule is many.In addition, in order to improve the curing film strength, preferred 3 officials can above material, in addition by and also be effective with the method that the material of different functional number and/or different polymerizable group (for example acrylate, methacrylate, polystyrene compound, vinyl ether based compound) is regulated sensitivity and intensity.

In addition, for for the compatibility of contained other compositions (for example Photoepolymerizationinitiater initiater, colorant (pigment, dyestuff) etc., binder polymer etc.) of solidification compound, dispersiveness, the selection of multi-functional monomer and/or to make usage also be important factor is for example sometimes by using the low-purity compound or and with improving compatibility more than 2 kinds.In addition, in order to improve the adaptation with substrate etc., also can select specific structure.

As (C) of the present invention polymerizable compound, can and use the simple function monomer.The content of simple function monomer is preferably 5～90 weight portions, 10～50 weight portions more preferably with respect to multi-functional monomer (containing the multi-functional monomer of carboxyl+other multi-functional monomer) 100 weight portions.

In the photosensitive composition of the present invention, (C) total content of polymerizable compound, promptly " content that contains the content+simple function monomer of content+other multi-functional monomers of the multi-functional monomer of carboxyl " with respect to adhesive resin 100 mass parts be generally 5～500 mass parts, be preferably 20～300 mass parts, 50～150 mass parts more preferably.By reaching above-mentioned scope, it is good that pixel intensity, surface smoothing, development become.

In the photosensitive composition of the present invention, (C) total content of polymerizable compound is preferably 5 quality %～40 quality %, more preferably 15 quality %～40 quality %, 20 quality %～40 quality % more preferably in the total solid composition of photosensitive composition.

In the photosensitive composition of the present invention, (C) mass ratio of polymerizable compound and (D) described later Photoepolymerizationinitiater initiater " (D) Photoepolymerizationinitiater initiater/(C) polymerizable compound " is 0.1～2.0, is preferably 0.1～1.0, is preferably 0.3～0.9 especially.By in above-mentioned scope, pattern form property good, with the adaptation excellence of substrate.In addition, exposure, the mask rugosity amount after developing are fully and suppressed pattern and peeled off.

＜(D) Photoepolymerizationinitiater initiater 〉

Photosensitive composition of the present invention contains at least a kind in (D) Photoepolymerizationinitiater initiater, and (D) at least a kind in the Photoepolymerizationinitiater initiater is that Photoepolymerizationinitiater initiater or oxime are Photoepolymerizationinitiater initiater for lophine.

As the lophine as (D) Photoepolymerizationinitiater initiater is Photoepolymerizationinitiater initiater, for example can list six aryl united imidazoles.As six aryl bisglyoxaline based compounds, for example can list 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5.5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-cyano-phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-ethylphenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-four (4-methoxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl) bisglyoxaline, 2,2 '-two (2-phenyl)-4,4 ', 5,5 '-four (4-phenyloxycarbonyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four-(4-methoxyphenyl) bisglyoxalines, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four-(3-methoxyphenyl) bisglyoxalines, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4-dicyano phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-tricyano phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 4-3,5-dimethylphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4, the 6-trimethylphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4-diethyl phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-triethyl phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4-diphenyl phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,4,6-triphenyl phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-fluorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline etc.

As particularly preferred compound, can list 2,2 '-two (2-chlorphenyls)-4 in above-mentioned, 4 ', 5,5 '-tetraphenyl bisglyoxaline (for example, hodogaya chemical industry (Hodogaya Chemical Co., Ltd.) system, trade name: B-CIM,), 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four-(3, the 4-Dimethoxyphenyl) bisglyoxaline is (for example, DKSH Japan (DKSH Ltd.) system, trade name: HABI-1311), 2,2 '-two (2-aminomethyl phenyl)-4,4 ', 5, (for example, dark fund changes into (Kurogane Kasei Co., Ltd.)) to 5 '-tetraphenyl bisglyoxaline.

These materials may be used alone, two or more kinds can also be used in combination.

As the oxime as (D) Photoepolymerizationinitiater initiater is Photoepolymerizationinitiater initiater, for example can list oxime ester (oxime ester) compound, ketoxime compound etc.Wherein, the painted viewpoint after sensitivity or the baking, the ketoxime of preferred following general formula (III) expression is a Photoepolymerizationinitiater initiater.

In the general formula (III), R and X represent that independently of one another monovalence substituting group, A represent that divalent organic group, Ar represent aryl.N is 0～5 integer.X exists when a plurality of, and a plurality of X represent the substituting group of monovalence independently of one another.

As the monovalence substituting group that above-mentioned R represents, be preferably the nonmetallic atom group of monovalence shown below.

The nonmetallic atom group of the monovalence of representing as R can list and can have substituent alkyl; can have substituent aryl; can have substituent alkenyl; can have substituent alkynyl; can have substituent alkyl sulphinyl; can have substituent aryl sulfonyl kia; can have substituent alkyl sulphonyl; can have substituent aryl sulfonyl; can have substituent acyl group; can have substituent alkoxy carbonyl; can have substituent aryloxycarbonyl; can have substituent phosphinyl; can have substituent heterocyclic radical; can have substituent alkyl thiocarbonyl; can have substituent thiocarbonyl aryl; can have substituent dialkyl amino carbonyl; can have substituent dialkyl amido thiocarbonyl etc.

As having substituent alkyl; preferred carbon number is 1～30 alkyl, for example can list methyl; ethyl; propyl group; butyl; hexyl; octyl group; decyl; dodecyl; octadecyl; isopropyl; isobutyl; sec-butyl; the tert-butyl group; the 1-ethyl pentyl group; cyclopentyl; cyclohexyl; trifluoromethyl; the 2-ethylhexyl; phenacyl; 1-naphthoyl ylmethyl; 2-naphthoyl ylmethyl; 4-methyl sulfane base phenacyl; 4-phenyl sulfane base phenacyl; 4-dimethylamino phenacyl; 4-cyano group phenacyl; 4-methyl phenacyl; 2-methyl phenacyl; 3-fluorobenzene acyl methyl; 3-trifluoromethyl benzoyl methyl; 3-nitro phenacyl etc.

As having substituent aryl, preferred carbon number is 6～30 aryl, for example can list phenyl, xenyl, the 1-naphthyl, the 2-naphthyl, the 9-anthryl, the 9-phenanthryl, the 1-pyrenyl, 5-naphtho-naphthyl, the 1-indenyl, 2-base difficult to understand, the 9-fluorenyl, the terphenyl base, the connection tetraphenyl, o-tolyl, between tolyl, p-methylphenyl, xylyl, adjacent cumenyl, between cumenyl, to cumenyl, the sym-trimethyl benzene base, the pentalene base, binaphthyl, the trinaphthylene base, join four naphthyls, the heptalene base, diphenylene, benzo two indenyls, the fluoranthene base, the acenaphthylene base, aceanthrene thiazolinyl; Fu base, fluorenyl, anthryl, the di-anthryl, join three anthryls, join four anthryls, the anthraquinoline base, phenanthryl, the Sanya phenyl, pyrenyl, Qu Ji, the naphtho-naphthyl, seven days of the week thiazolinyl Pi base perylene base, connection pentaphene base, the pentacene base, four phenylenes, the sexiphenyl base, the hexacene base, the rubicene base, the coronene base, three naphthylenes, join seven phenyl, the heptacene base, the pyrrole anthryl, ovalene base etc.

As having substituent alkenyl, preferred carbon number is 2～10 alkenyl, for example can list vinyl, allyl, styryl etc.

As having substituent alkynyl, preferred carbon number is 2～10 alkynyl, for example can list ethinyl, propinyl, propargyl etc.

As having substituent alkyl sulphinyl; preferred carbon number is 1～20 alkyl sulphinyl, for example can list methylsulfinyl, ethyl sulfinyl, propyl group sulfinyl, isopropyl sulfinyl, butyl sulfinyl, hexyl sulfinyl, cyclohexyl sulfinyl, octyl group sulfinyl, 2-ethylhexyl sulfinyl, capryl sulfinyl, dodecane acyl group sulfinyl, octadecanoyl sulfinyl, cyano methyl sulfinyl, methoxy sulfinyl etc.

As having substituent aryl sulfonyl kia; preferred carbon number is 6～30 aryl sulfonyl kia, for example can list the phenyl sulfinyl; 1-naphthyl sulfinyl; 2-naphthyl sulfinyl; 2-chlorphenyl sulfinyl; 2-aminomethyl phenyl sulfinyl; 2-methoxyphenyl sulfinyl; 2-butoxy phenyl sulfinyl; 3-chlorphenyl sulfinyl; 3-trifluoromethyl sulfinyl; 3-cyano-phenyl sulfinyl; 3-nitrobenzophenone sulfinyl; 4-fluorophenyl sulfinyl; 4-cyano-phenyl sulfinyl; 4-methoxyphenyl sulfinyl; 4-methyl sulfane base phenyl sulfinyl; 4-phenyl sulfane base phenyl sulfinyl; 4-dimethylaminophenyl sulfinyl etc.

As having substituent alkyl sulphonyl; preferred carbon number is 1～20 alkyl sulphonyl, for example can list methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropyl sulfonyl, butyl sulfonyl, hexyl sulfonyl, cyclohexyl sulfonyl, octyl group sulfonyl, 2-ethylhexyl sulfonyl, capryl sulfonyl, dodecane acyl group sulfonyl, octadecanoyl sulfonyl, cyano methyl sulfonyl, methoxy sulfonyl, perfluoroalkyl group sulfonyl etc.

As having substituent aryl sulfonyl; preferred carbon number is 6～30 aryl sulfonyl, for example can list phenyl sulfonyl; 1-naphthyl sulfonyl; 2-naphthyl sulfonyl; 2-chlorphenyl sulfonyl; 2-aminomethyl phenyl sulfonyl; 2-methoxyphenyl sulfonyl; 2-butoxy phenyl sulfonyl; 3-chlorphenyl sulfonyl; 3-trifluoromethyl sulfonyl; 3-cyano-phenyl sulfonyl; 3-nitrobenzophenone sulfonyl; 4-fluorophenyl sulfonyl; 4-cyano-phenyl sulfonyl; 4-methoxyphenyl sulfonyl; 4-methyl sulfane base phenyl sulfonyl; 4-phenyl sulfane base phenyl sulfonyl; 4-dimethylaminophenyl sulfonyl etc.

As having substituent acyl group; preferred carbon number is 2～20 acyl group, for example can list acetyl group; propiono; bytyry; the trifluoromethyl carbonyl; valeryl; benzoyl; 1-naphthoyl base; 2-naphthoyl base; 4-methyl sulfane base benzoyl; 4-phenyl sulfane base benzoyl; 4-dimethylamino benzoyl; 4-diethylamino benzoyl; the 2-chlorobenzene formacyl; the 2-methyl benzoyl; 2-methoxybenzoyl base; 2-butyl phenyl ether formoxyl; the 3-chlorobenzene formacyl; 3-trifluoromethyl benzoyl; 3-cyano group benzoyl; the 3-nitro benzoyl; the 4-fluoro benzoyl; 4-cyano group benzoyl; 4-methoxybenzoyl base etc.

As having substituent alkoxy carbonyl, be preferably carbon number and be 2～20 alkoxy carbonyl, for example can list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl, hexyloxy carbonyl, carbonyl octyloxy, last of the ten Heavenly stems oxygen base carbonyl, octadecane oxygen base carbonyl, trifluoromethyl oxygen base carbonyl etc.

As having substituent aryloxycarbonyl, can list phenyloxycarbonyl, 1-naphthoxy carbonyl, 2-naphthoxy carbonyl, 4-methyl sulfane phenoxyl carbonyl, 4-phenyl sulfane phenoxyl carbonyl, 4-dimethylamino phenyloxycarbonyl, 4-diethylamino phenyloxycarbonyl, 2-chlorophenoxy carbonyl, 2-methylphenoxy carbonyl, 2-methoxyl phenyloxycarbonyl, 2-phenoxy butoxy base carbonyl, 3-chlorophenoxy carbonyl, 3-4-trifluoromethylphenopendant carbonyl, 3-cyano-benzene oxygen carbonyl, 3-nitro-phenoxy carbonyl, 4-fluorophenoxy carbonyl, 4-cyano-benzene oxygen carbonyl, 4-methoxyl phenyloxycarbonyl etc.

As having substituent phosphinyl; preferred total carbon atom number is 2～50 phosphinyl; for example can list dimethyl oxygen phosphino-, diethyl phosphinyl, dipropyl phosphinyl, two phenenyl phosphinyl, dimethoxy phosphinyl, diethoxy phosphinyl, dibenzoyl phosphinyl, two (2; 4, the 6-trimethylphenyl) phosphinyl etc.

As having substituent heterocyclic radical, preferably contain the aromatic series or the aliphatic heterocycle of nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms.For example can list thienyl, benzo [b] thienyl, naphthalene [2,3-b] thienyl, thianthrene group, furyl, pyranose, isobenzofuran-base, the chromene base, xanthyl Fei Evil thiophene base, the 2H-pyrrole radicals, pyrrole radicals, imidazole radicals, pyrazolyl, pyridine radicals, pyrazinyl, pyrimidine radicals, pyridazinyl, the indolizine base, isoindolyl, the 3H-indyl, indyl, the 1H-indazolyl, purine radicals, 4H-quinolizine base, isoquinolyl, quinolyl, phthalazinyl, the naphthyridines base, quinoxalinyl, quinazolyl, the cinnolines base, pteridine radicals, the 4aH-carbazyl, carbazyl, the B-carboline base, phenanthridinyl, acridinyl, uncle's pyridine base, the phenanthroline base, phenazinyl, the phenarsazine base, isothiazolyl, phenothiazinyl isoxazolyl, furazan base Fei oxazinyl, different Chromanyl, Chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, iso-dihydro-indole-group, the quinoline cyclic group of giving repeated exhortations, morpholinyl, thioxanthene ketone group etc.

As having substituent alkyl thiocarbonyl, for example can list methyl thiocarbonyl, propyl dithiocarbamate carbonyl, butyl thiocarbonyl, hexyl thiocarbonyl, octylsulfo carbonyl, decyl thiocarbonyl, octadecyl thiocarbonyl, trifluoromethyl thiocarbonyl etc.

As having substituent thiocarbonyl aryl, can list 1-naphthyl thiocarbonyl, 2-naphthyl thiocarbonyl, 4-methyl sulfane base phenyl thiocarbonyl, 4-phenyl sulfane base phenyl thiocarbonyl, 4-dimethylaminophenyl thiocarbonyl, 4-diethylamino phenyl thiocarbonyl, 2-chlorphenyl thiocarbonyl, 2-aminomethyl phenyl thiocarbonyl, 2-methoxyphenyl thiocarbonyl, 2-butoxy phenyl thiocarbonyl, 3-chlorphenyl thiocarbonyl, 3-trifluoromethyl thiocarbonyl, 3-cyano-phenyl thiocarbonyl, 3-nitrobenzophenone thiocarbonyl, 4-fluorophenyl thiocarbonyl, 4-cyano-phenyl thiocarbonyl, 4-methoxyphenyl thiocarbonyl etc.

As having substituent dialkyl amino carbonyl, can list dimethylamino carbonyl, diethylamino carbonyl, dipropyl amino carbonyl, dibutylamino carbonyl etc.

As having substituent dialkyl amido thiocarbonyl, can list dimethylamino thiocarbonyl, the amino thiocarbonyl of dipropyl, two butyl amido thio carbonyl etc.

As above-mentioned R, from the angle of high sensitivityization, more preferably do not have replacement or have substituent acyl group, preferred particularly do not have replacement or have substituent acetyl group, propiono, benzoyl, toluyl.

Substituting group when having substituting group as above-mentioned acyl group for example can list the group that following structural formula is represented, wherein, and preferred (d-1) any (d-4) and (d-5).

As the divalent organic group that above-mentioned A represents, can list and to have substituent carbon number and be 1～12 alkylidene, can have substituent ring caproic subunit, can have substituent alkynylene.

As the substituting group that can be directed into these groups; for example remove fluorine atom; the chlorine atom; bromine atoms; halogen atoms such as iodine atom; methoxyl; ethoxy; alkoxys such as tert-butoxy; phenoxy group; to aryloxy group such as toloxyls; methoxycarbonyl; butoxy carbonyl; alkoxy carbonyls such as phenyloxycarbonyl; acetoxyl group; propionyloxy; acyloxy such as benzoyloxy; acetyl group; benzoyl; isobutyryl; acryloyl group; methacryl; acyl groups such as methoxalyl base; methyl sulfane base; alkyl alkylthio bases such as tert-butyl group sulfane base; phenyl sulfane base; sulfur alkyl aryls such as p-methylphenyl sulfane base; methylamino; alkyl aminos such as cyclohexyl amino; dimethylamino; diethylamino; morpholinyl; dialkyl amidos such as piperidyl; phenyl amino; arylaminos such as p-methylphenyl amino; methyl; ethyl; the tert-butyl group; alkyl such as dodecyl; phenyl; p-methylphenyl; xylyl; cumenyl; naphthyl; anthryl; outside the aryl such as phenanthryl etc., also can list hydroxyl; carbonyl; formoxyl; sulfydryl; sulfo group; the pyrovinic acid base; p-toluenesulfonyl; amino; nitro; cyano group; trifluoromethyl; trichloromethyl; trimethyl silyl; phosphinico; phosphono; the trimethyl ammonium; the dimethyl sulfonium base; triphenyl benzoyl first base Phosphonium base etc.

Wherein, as above-mentioned A, from improve sensitivity, suppress heating through the time the painted angle that caused, the preferred alkylidene that does not have the alkylidene that replaces, replaced by alkyl (for example methyl, ethyl, the tert-butyl group, dodecyl), the alkylidene that is replaced by alkenyl (for example vinyl, allyl), the alkylidene that is replaced by aryl (for example phenyl, p-methylphenyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, styryl).

As the aryl that above-mentioned Ar represents, preferred carbon number is 6～30 aryl, also can have substituting group.

Particularly, Ar can list phenyl, xenyl, the 1-naphthyl, the 2-naphthyl, the 9-anthryl, the 9-phenanthryl, the 1-pyrenyl, 5-naphtho-naphthyl, the 1-indenyl, 2-base difficult to understand, the 9-fluorenyl, the terphenyl base, the connection tetraphenyl, o-tolyl, between tolyl, p-methylphenyl, xylyl, adjacent cumenyl, between cumenyl, to cumenyl, the sym-trimethyl benzene base, the pentalene base, binaphthyl, the trinaphthylene base, join four naphthyls, the heptalene base, diphenylene, benzo two indenyls, the fluoranthene base, the acenaphthylene base, aceanthrene thiazolinyl; Fu base, fluorenyl, anthryl, the di-anthryl, join three anthryls, join four anthryls, the anthraquinoline base, phenanthryl, the Sanya phenyl, pyrenyl, Qu Ji, the naphtho-naphthyl, seven days of the week thiazolinyl Pi base perylene base, connection pentaphene base, the pentacene base, four phenylenes, the sexiphenyl base, the hexacene base, the rubicene base, the coronene base, three naphthylenes, join seven phenyl, the heptacene base, the pyrrole anthryl, ovalene base etc.Wherein, from improve sensitivity, suppress heating through the time the painted angle that caused, preferably replace or do not have the phenyl of replacement.

When above-mentioned phenyl has substituting group; as its substituting group; fluorine atom is for example arranged; the chlorine atom; bromine atoms; halogen atoms such as iodine atom; methoxyl; ethoxy; alkoxys such as tert-butoxy; phenoxy group; to aryloxy group such as toloxyls; methyl sulfo-oxygen base; ethylenebis dithiocarbamate oxygen base; alkylthio oxygen bases such as t-butylthio oxygen base; phenyl sulfo-oxygen base; aryl sulfo-oxygen bases such as p-methylphenyl sulfo-oxygen base; methoxycarbonyl; butoxy carbonyl; alkoxy carbonyls such as phenyloxycarbonyl; acetoxyl group; propionyloxy; acyloxy such as benzoyloxy; acetyl group; benzoyl; isobutyryl; acryloyl group; methacryl; acyl groups such as methoxalyl base; methyl sulfane base; alkyl alkylthio bases such as tert-butyl group sulfane base; phenyl sulfane base; sulfur alkyl aryls such as p-methylphenyl sulfane base; methylamino; alkyl aminos such as cyclohexyl amino; dimethylamino; diethylamino; morpholinyl; dialkyl amidos such as piperidyl; phenyl amino; arylaminos such as p-methylphenyl amino; ethyl; the tert-butyl group; alkyl such as dodecyl, hydroxyl; carbonyl; formoxyl; sulfydryl; sulfo group; the pyrovinic acid base; p-toluenesulfonyl; amino; nitro; cyano group; trifluoromethyl; trichloromethyl; trimethyl silyl; phosphinico; phosphono; the trimethyl ammonium; the dimethyl sulfonium base; triphenyl benzoyl first base Phosphonium base etc.

In the general formula (III), when the structure of above-mentioned Ar and adjacent S formed " SAr " is the structure of following expression, preferred from the angle of sensitivity.

As the monovalence substituting group that above-mentioned X represents, can list and to have substituent alkyl; can have substituent aryl; can have substituent alkenyl; can have substituent alkynyl; can have substituent alkoxy; can have substituent aryloxy group; can have substituent alkylthio oxygen base; can have substituent aryl sulfo-oxygen base; can have substituent haloalkyl; on N, can have substituent amide group; can have substituent acyloxy; can have substituent alkyl alkylthio base; can have substituent sulfur alkyl aryl; can have substituent alkyl sulphinyl; can have substituent aryl sulfonyl kia; can have substituent alkyl sulphonyl; can have substituent aryl sulfonyl; can have substituent acyl group; can have substituent alkoxy carbonyl; can have substituent carbamyl; can have substituent sulfamoyl; can have substituent amino; can have substituent phosphinyl; can have substituent heterocyclic radical; halogen atom etc.

As having substituent alkyl; preferred carbon number is 1～30 alkyl, for example can list methyl; ethyl; propyl group; butyl; hexyl; octyl group; decyl; dodecyl; octadecyl; isopropyl; isobutyl; sec-butyl; the tert-butyl group; the 1-ethyl pentyl group; cyclopentyl; cyclohexyl; trifluoromethyl; the 2-ethylhexyl; phenacyl; 1-naphthoyl ylmethyl; 2-naphthoyl ylmethyl; 4-methyl sulfane base phenacyl; 4-phenyl sulfane base phenacyl; 4-dimethylamino phenacyl; 4-cyano group phenacyl; 4-methyl phenacyl; 2-methyl phenacyl; 3-fluorobenzene acyl methyl; 3-trifluoromethyl benzoyl methyl; 3-nitro phenacyl etc.

As having substituent aryl, preferred carbon number is 6～30 aryl, for example can list phenyl, xenyl, the 1-naphthyl, the 2-naphthyl, the 9-anthryl, the 9-phenanthryl, the 1-pyrenyl, 5-naphtho-naphthyl, the 1-indenyl, 2-base difficult to understand, the 9-fluorenyl, the terphenyl base, the connection tetraphenyl, o-tolyl, between tolyl, p-methylphenyl, xylyl, adjacent cumenyl, between cumenyl, to cumenyl, the sym-trimethyl benzene base, the pentalene base, binaphthyl, the trinaphthylene base, join four naphthyls, the heptalene base, diphenylene, benzo two indenyls, the fluoranthene base, the acenaphthylene base, aceanthrene thiazolinyl; Fu base, fluorenyl, anthryl, the di-anthryl, join three anthryls, join four anthryls, the anthraquinoline base, phenanthryl, the Sanya phenyl, pyrenyl, Qu Ji, the naphtho-naphthyl, seven days of the week thiazolinyl Pi base perylene base, connection pentaphene base, the pentacene base, four phenylenes, the sexiphenyl base, the hexacene base, the rubicene base, the coronene base, three naphthylenes, join seven phenyl, the heptacene base, the pyrrole anthryl, ovalene base etc.

As having substituent alkenyl, preferred carbon number is 2～10 alkenyl, for example can list vinyl, allyl, styryl etc.

As having substituent alkynyl, preferred carbon number is 2～10 alkynyl, for example can list ethinyl, propinyl, propargyl etc.

As having substituent alkoxy, preferred carbon number is 1～30 alkoxy, for example can list methoxyl, ethoxy, propyl group oxygen base, isopropyl oxygen base, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amyl group oxygen base, isopentyl oxygen base, own oxygen base, heptan the oxygen base, octyloxy, the 2-ethyl hexyl oxy, the last of the ten Heavenly stems oxygen base, dodecyloxy, octadecane oxygen base, the ethoxy carbonyl methyl, 2-ethyl hexyl oxy carbonyl methyl oxygen base, amino carbonyl methyl oxygen base, N, N-dibutylamino carbonyl methyl oxygen base, N-methylamino carbonyl methyl oxygen base, N-ethylamino carbonyl methyl oxygen base, N-octyl group amino carbonyl methyl oxygen base, N-methyl-N-benzylamino carbonyl methyl oxygen base, benzyl oxygen base, cyano methyl oxygen base etc.

As having substituent aryloxy group, preferred carbon number is 6～30 aryloxy group, for example can list phenoxy group, 1-naphthoxy, 2-naphthoxy, 2-chlorophenoxy, 2-methylphenoxy, 2-methoxyl phenoxy group, 2-phenoxy butoxy base, 3-chlorophenoxy, 3-4-trifluoromethylphenopendant, 3-cyano-benzene oxygen, 3-nitro-phenoxy, 4-fluorophenoxy, 4-cyano-benzene oxygen, 4-methoxyl phenoxy group, 4-dimethylamino phenoxyl, 4-methyl sulfane phenoxyl, 4-phenyl sulfane phenoxyl etc.

As having substituent alkylthio oxygen base, preferred carbon number is 1～30 thio alkoxy, for example can list methyl sulfo-oxygen base, ethylenebis dithiocarbamate oxygen base, propyl dithiocarbamate oxygen base, isopropylthio oxygen base, butyl sulfo-oxygen base, isobutyl sulfo-oxygen base, sec-butyl sulfo-oxygen base, t-butylthio oxygen base, amyl group sulfo-oxygen base, isopentyl sulfo-oxygen base, hexyl sulfo-oxygen base, heptyl sulfo-oxygen base, octylsulfo oxygen base, 2-ethylhexyl sulfo-oxygen base, decyl sulfo-oxygen base, dodecyl sulfo-oxygen base, octadecyl sulfo-oxygen base, dibenzylsulfide is for oxygen base etc.

As having substituent aryl sulfo-oxygen base, preferred carbon number is 6～30 aryl sulfo-oxygen base, for example can list phenyl sulfo-oxygen base, 1-naphthyl sulfo-oxygen base, 2-naphthyl sulfo-oxygen base, 2-chlorphenyl sulfo-oxygen base, 2-aminomethyl phenyl sulfo-oxygen base, 2-methoxyphenyl sulfo-oxygen base, 2-butoxy phenyl sulfo-oxygen base, 3-chlorphenyl sulfo-oxygen base, 3-trifluoromethyl sulfo-oxygen base, 3-cyano-phenyl sulfo-oxygen base, 3-nitrobenzophenone sulfo-oxygen base, 4-fluorophenyl sulfo-oxygen base, 4-cyano-phenyl sulfo-oxygen base, 4-methoxyphenyl sulfo-oxygen base, 4-dimethylaminophenyl sulfo-oxygen base, 4-methyl sulfane base phenyl sulfo-oxygen base, 4-phenyl sulfane base phenyl sulfo-oxygen base etc.

As having substituent acyloxy, preferred carbon number is 2～20 acyloxy, for example can list acetoxyl group, propionyloxy, butyryl acyloxy, penta acyloxy, trifluoromethyl ketonic oxygen base, benzoyloxy, 1-naphthyl carbonyl oxygen base, 2-naphthyl carbonyl oxygen base etc.

As having substituent alkyl alkylthio base; preferred carbon number is 1～20 alkyl alkylthio base, for example can list methyl sulfane base, ethyl sulfane base, propylthio alkyl, isopropyl sulfane base, butyl sulfane base, hexyl sulfane base, cyclohexyl sulfane base, octyl group sulfane base, 2-ethylhexyl sulfane base, capryl sulfane base, dodecane acyl group sulfane base, octadecanoyl sulfane base, cyano methyl sulfane base, methoxy sulfane base etc.

As having substituent sulfur alkyl aryl, preferred carbon number is 6～30 sulfur alkyl aryl, for example can list phenyl sulfane base, 1-naphthyl sulfane base, 2-naphthyl sulfane base, 2-chlorphenyl sulfane base, 2-aminomethyl phenyl sulfane base, 2-methoxyphenyl sulfane base, 2-butoxy phenyl sulfane base, 3-chlorphenyl sulfane base, 3-trifluoromethyl sulfane base, 3-cyano-phenyl sulfane base, 3-nitrobenzophenone sulfane base, 4-fluorophenyl sulfane base, 4-cyano-phenyl sulfane base, 4-methoxyphenyl sulfane base, 4-methyl sulfane base phenyl sulfane base, 4-phenyl sulfane base phenyl sulfane base, 4-dimethylaminophenyl sulfane base etc.

As having substituent alkyl sulphinyl; preferred carbon number is 1～20 alkyl sulphinyl, for example can list methylsulfinyl, ethyl sulfinyl, propyl group sulfinyl, isopropyl sulfinyl, butyl sulfinyl, hexyl sulfinyl, cyclohexyl sulfinyl, octyl group sulfinyl, 2-ethylhexyl sulfinyl, capryl sulfinyl, dodecane acyl group sulfinyl, octadecanoyl sulfinyl, cyano methyl sulfinyl, methoxy sulfinyl etc.

As having substituent aryl sulfonyl kia; preferred carbon number is 6～30 aryl sulfonyl kia, for example can list the phenyl sulfinyl; 1-naphthyl sulfinyl; 2-naphthyl sulfinyl; 2-chlorphenyl sulfinyl; 2-aminomethyl phenyl sulfinyl; 2-methoxyphenyl sulfinyl; 2-butoxy phenyl sulfinyl; 3-chlorphenyl sulfinyl; 3-trifluoromethyl sulfinyl; 3-cyano-phenyl sulfinyl; 3-nitrobenzophenone sulfinyl; 4-fluorophenyl sulfinyl; 4-cyano-phenyl sulfinyl; 4-methoxyphenyl sulfinyl; 4-methyl sulfane base phenyl sulfinyl; 4-phenyl sulfane base phenyl sulfinyl; 4-dimethylaminophenyl sulfinyl etc.

As having substituent alkyl sulphonyl; preferred carbon number is 1～20 alkyl sulphonyl, for example can list methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropyl sulfonyl, butyl sulfonyl, hexyl sulfonyl, cyclohexyl sulfonyl, octyl group sulfonyl, 2-ethylhexyl sulfonyl, capryl sulfonyl, dodecane acyl group sulfonyl, octadecanoyl sulfonyl, cyano methyl sulfonyl, methoxy sulfonyl etc.

As having substituent aryl sulfonyl; preferred carbon number is 6～30 aryl sulfonyl, for example can list phenyl sulfonyl; 1-naphthyl sulfonyl; 2-naphthyl sulfonyl; 2-chlorphenyl sulfonyl; 2-aminomethyl phenyl sulfonyl; 2-methoxyphenyl sulfonyl; 2-butoxy phenyl sulfonyl; 3-chlorphenyl sulfonyl; 3-trifluoromethyl sulfonyl; 3-cyano-phenyl sulfonyl; 3-nitrobenzophenone sulfonyl; 4-fluorophenyl sulfonyl; 4-cyano-phenyl sulfonyl; 4-methoxyphenyl sulfonyl; 4-methyl sulfane base phenyl sulfonyl; 4-phenyl sulfane base phenyl sulfonyl; 4-dimethylaminophenyl sulfonyl etc.

As having substituent acyl group; preferred carbon number is 2～20 acyl group, for example can list acetyl group; propiono; bytyry; the trifluoromethyl carbonyl; valeryl; benzoyl; 1-naphthoyl base; 2-naphthoyl base; 4-methyl sulfane base benzoyl; 4-phenyl sulfane base benzoyl; 4-dimethylamino benzoyl; 4-diethylamino benzoyl; the 2-chlorobenzene formacyl; the 2-methyl benzoyl; 2-methoxybenzoyl base; 2-butyl phenyl ether formoxyl; the 3-chlorobenzene formacyl; 3-trifluoromethyl benzoyl; 3-cyano group benzoyl; the 3-nitro benzoyl; the 4-fluoro benzoyl; 4-cyano group benzoyl; 4-methoxybenzoyl base etc.

As having substituent alkoxy carbonyl, preferred carbon number is 2～20 alkoxy carbonyl, for example can list methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl, hexyloxy carbonyl, carbonyl octyloxy, the last of the ten Heavenly stems oxygen base carbonyl, octadecane oxygen base carbonyl, phenyloxycarbonyl, trifluoromethyl oxygen base carbonyl, 1-naphthoxy carbonyl, 2-naphthoxy carbonyl, 4-methyl sulfane phenoxyl carbonyl, 4-phenyl sulfane phenoxyl carbonyl, 4-dimethylamino phenyloxycarbonyl, 4-diethylamino phenyloxycarbonyl, 2-chlorophenoxy carbonyl, 2-methylphenoxy carbonyl, 2-methoxyl phenyloxycarbonyl, 2-phenoxy butoxy base carbonyl, 3-chlorophenoxy carbonyl, 3-4-trifluoromethylphenopendant carbonyl, 3-cyano-benzene oxygen carbonyl, 3-nitro-phenoxy carbonyl, 4-fluorophenoxy carbonyl, 4-cyano-benzene oxygen carbonyl, 4-methoxyl phenyloxycarbonyl etc.

As having substituent carbamyl; preferred total carbon atom number is 1～30 carbamyl, for example can list N-methylamino formoxyl; N-ethylamino formoxyl; N-propyl group carbamyl; N-butyl carbamyl; N-hexyl carbamyl; N-cyclohexyl carboxyamide base; N-octyl group carbamyl; N-decyl carbamyl; N-octadecyl carbamyl; N-phenyl amino formoxyl; N-2-aminomethyl phenyl carbamyl; N-2-chlorphenyl carbamyl; N-2-isopropyl phenyl carbamyl; N-2-(2-ethylhexyl) phenyl amino formoxyl; N-3-chlorphenyl carbamyl; N-3-nitrobenzophenone carbamyl; N-3-cyano-phenyl carbamyl; N-4-methoxyphenyl carbamyl; N-4-cyano-phenyl carbamyl; N-4-methyl sulfane base phenyl amino formoxyl; N-4-phenyl sulfane base phenyl amino formoxyl; N-methyl-N-phenyl amino formoxyl; N; the N-formyl-dimethylamino; N; N-dibutylamino formoxyl; N; N-diphenyl amino formoxyl etc.

As having substituent sulfamoyl; preferred total carbon atom number is 0～30 sulfamoyl, for example can list sulfamoyl, N-alkylsulfamoyl group, N-ammonia aryl sulfonyl, N, N-dialkyl sulfamine, N, N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl etc.More specifically can list N-methyl sulfamoyl; N-ethyl sulfamoyl; N-propyl group sulfamoyl; N-butyl sulfamoyl; N-hexyl sulfamoyl; N-cyclohexyl sulfamoyl; N-octyl group sulfamoyl; N-2-ethylhexyl sulfamoyl; N-decyl sulfamoyl; N-octadecyl sulfamoyl; N-phenyl sulfamoyl base; N-2-aminomethyl phenyl sulfamoyl; N-2-chlorphenyl sulfamoyl; N-2-methoxyphenyl sulfamoyl; N-2-isopropyl phenyl sulfamoyl; N-3-chlorphenyl sulfamoyl; N-3-nitrobenzophenone sulfamoyl; N-3-cyano-phenyl sulfamoyl; N-4-methoxyphenyl sulfamoyl; N-4-cyano-phenyl sulfamoyl; N-4-dimethylaminophenyl sulfamoyl; N-4-methyl sulfane base phenyl sulfamoyl base; N-4-phenyl sulfane base phenyl sulfamoyl base; N-methyl-N-phenyl sulfamoyl base; N; N-dimethylamino sulfonyl; N; N-dibutylamine sulfonyl; N, N-diphenyl sulfamoyl etc.

As having substituent amino, preferred total carbon atom number is 0～50 amino, for example can list-NH ₂, N-alkyl amino, N-arylamino, N-acyl amino, N-sulfuryl amino, N, N-dialkyl amido, N, N-ammonia diaryl base, N-alkyl-N-arylamino, N, N-disulfonyl base amino etc.More specifically can list the N-methylamino; the N-ethylamino; N-propyl group amino; N-isopropyl amino; N-butyl amino; N-tert-butyl group amino; N-hexyl amino; N-cyclohexyl amino; N-octyl group amino; N-2-ethylhexyl amino; N-decyl amino; N-octadecyl amino; the N-benzylamino; the N-phenyl amino; N-2-aminomethyl phenyl amino; N-2-chlorphenyl amino; N-2-methoxyphenyl amino; N-2-isopropyl phenyl amino; N-2-(2-ethylhexyl) phenyl amino; N-3-chlorphenyl amino; N-3-nitrobenzophenone amino; N-3-cyano-phenyl amino; N-3-trifluoromethyl amino; N-4-methoxyphenyl amino; N-4-cyano-phenyl amino; N-4-trifluoromethyl amino; N-4-methyl sulfane base phenyl amino; N-4-phenyl sulfane base phenyl amino; N-4-dimethylaminophenyl amino; N-methyl-N-phenyl amino; N; the N-dimethylamino; N; the N-diethylamino; N; the N-dibutylamino; N; the N-diphenyl amino; N; N-diacetyl amino; N; N-dibenzoyl amino; N; N-(dibutyl carbonyl) amino; N; N-(dimethyl methyl acyl group) amino; N; N-(diethyl sulfonyl) amino; N; N-(dibutyl sulfonyl) amino; N; N-(diphenyl sulfonyl) amino; morpholinyl; 3, the 5-dimethylated morpholinyl; carbazyl etc.

As having substituent phosphinyl; preferred total carbon atom number is 2～50 phosphinyl; for example can list dimethyl oxygen phosphino-, diethyl phosphinyl, dipropyl phosphinyl, two phenenyl phosphinyl, dimethoxy phosphinyl, diethoxy phosphinyl, dibenzoyl phosphinyl, two (2; 4, the 6-trimethylphenyl) phosphinyl etc.

As having substituent heterocyclic radical, preferably contain the aromatic series or the aliphatics heterocycle of nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms.Thienyl is for example arranged, benzo [b] thienyl, naphthalene [2,3-b] thienyl, thianthrene group, furyl, pyranose, isobenzofuran-base, the chromene base, xanthyl Fei Evil thiophene base, the 2H-pyrrole radicals, pyrrole radicals, imidazole radicals, pyrazolyl, pyridine radicals, pyrazinyl, pyrimidine radicals, pyridazinyl, the indolizine base, isoindolyl, the 3H-indyl, indyl, the 1H-indazolyl, purine radicals, 4H-quinolizine base, isoquinolyl, quinolyl, phthalazinyl, the naphthyridines base, quinoxalinyl, quinazolyl, the cinnolines base, pteridine radicals, the 4aH-carbazyl, carbazyl, the B-carboline base, phenanthridinyl, acridinyl, uncle's pyridine base, the phenanthroline base, phenazinyl, the phenarsazine base, isothiazolyl, phenothiazinyl isoxazolyl, furazan base Fei oxazinyl, different Chromanyl, Chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, iso-dihydro-indole-group, the quinoline cyclic group of giving repeated exhortations, morpholinyl, thioxanthene ketone group etc.

As halogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom etc. are arranged.

As having substituent haloalkyl, can list a methyl fluoride, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, a bromomethyl, two bromomethyls, trisbromomethyl etc.

As on N, having substituent amide group, can list N, N-dimethylformamide base, N, N-diethylamide base etc.

In addition, above-mentioned have a substituent alkyl; can have substituent aryl; can have substituent alkenyl; can have substituent alkynyl; can have substituent alkoxy; can have substituent aryloxy group; can have substituent alkylthio oxygen base; can have substituent aryl sulfo-oxygen base; can have substituent acyloxy; can have substituent alkyl alkylthio base; can have substituent sulfur alkyl aryl; can have substituent alkyl sulphinyl; can have substituent aryl sulfonyl kia; can have substituent alkyl sulphonyl; can have substituent aryl sulfonyl; can have substituent acyl group; can have substituent alkoxy carbonyl; can have substituent carbamyl; can have substituent sulfamoyl; can have substituent amino; can have substituent heterocyclic radical also can further be replaced by other substituting groups.

As such substituting group; for example remove fluorine atom; the chlorine atom; bromine atoms; halogen atoms such as iodine atom; methoxyl; ethoxy; alkoxys such as tert-butoxy; phenoxy group; to aryloxy group such as toloxyls; methoxycarbonyl; butoxy carbonyl; alkoxy carbonyls such as phenyloxycarbonyl; acetoxyl group; propionyloxy; acyloxy such as benzoyloxy; acetyl group; benzoyl; isobutyryl; acryloyl group; methacryl; acyl groups such as methoxalyl base; methyl sulfane base; alkyl alkylthio bases such as tert-butyl group sulfane base; phenyl sulfane base; sulfur alkyl aryls such as p-methylphenyl sulfane base; methylamino; alkyl aminos such as cyclohexyl amino; dimethylamino; diethylamino; morpholinyl; dialkyl amidos such as piperidyl; phenyl amino; arylaminos such as p-methylphenyl amino; methyl; ethyl; the tert-butyl group; alkyl such as dodecyl; phenyl; p-methylphenyl; xylyl; cumenyl; naphthyl; anthryl; outside the aryl such as phenanthryl etc., also can list hydroxyl; carbonyl; formoxyl; sulfydryl; sulfo group; the pyrovinic acid base; p-toluenesulfonyl; amino; nitro; cyano group; trifluoromethyl; trichloromethyl; trimethyl silyl; phosphinico; phosphono; the trimethyl ammonium; the dimethyl sulfonium base; triphenyl benzoyl first base Phosphonium base etc.

Wherein, as X, from the viewpoint of solvent solubility with the absorption efficiency that improves the long wavelength zone, preferably can have substituent alkyl, can have substituent aryl, can have substituent alkenyl, can have substituent alkynyl, can have substituent alkoxy, can have substituent aryloxy group, can have substituent alkylthio oxygen base, can have substituent aryl sulfo-oxygen base, can have substituent haloalkyl, can have substituent amino, or on N, can have substituent amide group, wherein more preferably can have substituent alkyl.

In addition, the n in the general formula (III) represents 0～5 integer, from the viewpoint of synthetic complexity, is preferably 0～3 integer, 0～2 integer more preferably.

In the general formula (III), when having a plurality of X, a plurality of X can be identical also can be different.

The object lesson of the Photoepolymerizationinitiater initiater of above-mentioned general formula (III) expression below is shown.

The compound of general formula used in the present invention (III) expression has absorbing wavelength in the wavelength region may of 250nm～500nm.More preferably can list in the wavelength region may of 300nm～380nm and have absorbing wavelength person.The high person of absorbance at preferred especially 308nm place and 355nm place.

Photosensitive composition of the present invention can also and be that Photoepolymerizationinitiater initiater and oxime are Photoepolymerizationinitiater initiater conduct (D) Photoepolymerizationinitiater initiater the Photoepolymerizationinitiater initiater with removing lophine.As being that Photoepolymerizationinitiater initiater and oxime are the Photoepolymerizationinitiater initiater the Photoepolymerizationinitiater initiater except that lophine, so long as can cause, promote the polymeric compounds of above-mentioned (C) polymerizable compound then can use known in the past compound ad lib.For example can list organic halogenation compound, oxadiazole compound, carbonyls, ketal compound, benzoin compound, acridine compound, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, metallocene compound, organic boronic compound, disulfonic acid compound, salt compound, acylphosphanes (oxide) compound etc. particularly.

As their object lesson, can list if " Bull Chem.Soc.Japan " 42 such as woodss, 2924 (1969), United States Patent (USP) the 3rd, 905, No. 815 instructionss, Japanese Patent Publication 46-4605 communique, Japanese kokai publication sho 48-36281 communique, Japanese kokai publication sho 55-32070 communique, Japanese kokai publication sho 60-239736 communique, Japanese kokai publication sho 61-169835 communique, Japanese kokai publication sho 61-169837 communique, Japanese kokai publication sho 62-58241 communique, Japanese kokai publication sho 62-212401 communique, Japanese kokai publication sho 63-70243 communique, Japanese kokai publication sho 63-298339 communique, M.P.HuTT " Journal of Heterocyclic Chemistry " 1 (No3), (1970) "; the special fair 6-29285 communique of Japan; United States Patent (USP) the 3rd; 479; No. 185; United States Patent (USP) the 4th, 311, No. 783, United States Patent (USP) the 4th, 622, wait each instructions No. 286, Japanese kokai publication sho 62-143044 communique, Japanese kokai publication sho 62-150242 communique, Japanese kokai publication hei 9-188685 communique, Japanese kokai publication hei 9-188686 communique, Japanese kokai publication hei 9-188710 communique, TOHKEMY 2000-131837 communique, TOHKEMY 2002-107916 communique, No. 2764769 communique of patent, each communique such as TOHKEMY 2002-116539 communique, and Kunz, the organic borate of record among the Martin " Rad Tech ' 98.Pproceeding April19-22; 1998, Chicago " etc., Japanese kokai publication hei 6-157623 communique, Japanese kokai publication hei 6-175564 communique, Japanese kokai publication hei 6-175561 communique, Japanese kokai publication hei 6-175554 communique, Japanese kokai publication hei 6-175553 communique, Japanese kokai publication hei 9-188710 communique, Japanese kokai publication hei 6-348011 communique, Japanese kokai publication hei 7-128785 communique, Japanese kokai publication hei 7-140589 communique, Japanese kokai publication hei 7-306527 communique, Japanese kokai publication hei 7-292014 communique, J.C.S.Perkin II (1979) 1653-1660), J.C.S.Perkin II (1979) 156-162, Journal of Photopolymer Science and technology (1995) 202-232, TOHKEMY 2000-66385 communique, TOHKEMY 2000-80068 communique, the Photoepolymerizationinitiater initiater of putting down in writing in the Japanese Unexamined Patent Application Publication 2004-534797 communique etc. is as object lesson.

As (D) Photoepolymerizationinitiater initiater, when using the Photoepolymerizationinitiater initiater that under exposure wavelength, does not have absorption, preferably use under exposure wavelength, to have the compound of absorption as sensitizer.Be described below for sensitizer.

The content of the present invention used (D) Photoepolymerizationinitiater initiater is preferably the scope of 5 quality %～20 quality %, more preferably scope, the scope of 10 quality %～15 quality % more preferably of 5 quality %～15 quality % with respect to the total solid composition of photosensitive composition.

The preferred following mode of photosensitive composition of the present invention: (B) adhesive resin has above-mentioned (B-1) at least in molecule; As (C) polymerizable compound, contain at least a kind in above-mentioned (C1) multi-functional monomer, above-mentioned (C2) multi-functional monomer and the above-mentioned monomer M-1; As (D) Photoepolymerizationinitiater initiater, the ketoxime that contains above-mentioned general formula (III) expression is a Photoepolymerizationinitiater initiater.

＜(E) solvent 〉

Photosensitive composition of the present invention contains (E) solvent, can use (E) solvent to be prepared.In addition, above-mentioned pigment dispensing composition also uses (E) solvent to be prepared.

As (E) solvent, can list:

The ester class, ethyl acetate for example, acetate-positive butyl ester, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, the ethoxyacetic acid methyl esters, the ethoxyacetic acid ethyl ester, the ethoxyacetic acid butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate and 3-oxygen base methyl propionate, 3-oxygen base alkyl propionates classes such as 3-oxygen base ethyl propionate (3-methoxypropionic acid methyl esters for example, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters and 3-ethoxyl ethyl propionate etc.), 2-oxygen base methyl propionate, 2-oxygen base ethyl propionate, 2-oxygen base alkyl propionates classes such as 2-oxygen base propyl propionate (2-methoxypropionic acid methyl esters for example, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxygen base-2 Methylpropionic acid methyl esters, 2-oxygen base-2 Methylpropionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl esters and 2-ethoxy-2 Methylpropionic acid ethyl ester etc.), methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, 1,3 butylene glycol diacetate esters etc.;

Ethers, for example diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, TC, the diethylene glycol single-butyl ether, methyl proxitol, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, tripropylene glycol list n-butyl ether, propylene glycol phenyl ether, methylcellosolve acetate, ethyl cellosolve acetate, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, the propylene glycol n-propyl ether acetic acid esters, propylene-glycol diacetate, the propylene glycol n-butyl ether acetic acid esters, propylene glycol phenyl ether acetic acid ester, the DPGME acetic acid esters, dipropylene glycol n-propyl ether acetic acid esters, dipropylene glycol n-butyl ether acetic acid esters, tripropylene glycol methyl ether acetic acid esters etc.;

Alkoxyalkyl acetate esters, for example 3-methoxyl butylacetic acid ester, 4-methoxyl butylacetic acid ester, 2-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 2-ethoxy butylacetic acid ester, 4-ethoxy butylacetic acid ester, 2-methoxyl amyl group acetic acid esters, 3-methoxyl amyl group acetic acid esters, 4-methoxyl amyl group acetic acid esters, 2-methyl-3-methoxyl amyl group acetic acid esters, 3-methyl-3-methoxyl amyl group acetic acid esters, 3-methyl-4-methoxyl amyl group acetic acid esters etc.;

Ketone, for example acetone, MEK, cyclohexanone, 2-heptanone, 3-heptanone etc.;

Alcohols, for example ethanol, isopropyl alcohol etc.;

Aromatic hydrocarbon basedly for example can list toluene, dimethylbenzene etc.

Wherein, 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, methyl proxitol, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester etc.

(E) solvent can also be used in combination more than 2 kinds except can using separately.

Can also contain other compositions such as (F) sensitizer, surfactant, heat-curing resin in the photosensitive composition of the present invention as required.

＜(F) sensitizer 〉

The preferred compound that has absorption under exposure wavelength that uses is as sensitizer, to improve the efficiency of initiation of (D) Photoepolymerizationinitiater initiater in the photosensitive composition of the present invention.

This sensitizer promotes the free-radical generating reaction of (D) Photoepolymerizationinitiater initiater composition and the polyreaction of the polymerizable compound that is caused thus by the exposure of absorbable wavelength.

As such sensitizer, can list known beam split sensitizing coloring matter or dyestuff or absorbing light and with interactional dyestuff of Photoepolymerizationinitiater initiater or pigment.

As can be used for preferred beam split sensitizing coloring matter of sensitizer of the present invention or dyestuff, can list the polynuclear aromatic same clan (pyrene perylene for example, benzophenanthrene), xanthene class (fluorescein for example, eosin, erythrosine, rhodamine B, rose-red), cyanine class (sulphur carbon cyanines for example, oxygen carbon cyanines), part cyanines class (part cyanines for example, carbon part cyanines), thiazide (thionine for example, methylene blue, toluidine blue), acridine (acridine orange for example, chloroflavin, acriflavine), phthalocyanines (phthalocyanine for example, metal phthalocyanine), porphyrin class (tetraphenylporphyrin for example, central metal replaces porphyrin), chlorophyll class (chlorophyll for example, chlorophyllin, central metal replaces chlorophyll), metal complex, anthraquinone class (for example anthraquinone), class in side's acid (for example in side's acid (squarylium)), carbonyls, ketal compound, the benzoin compound, the acridine compound, the organic peroxy compound, azo-compound, coumarin compound, triazo-compound, metallocene compound, the organic boronic compound, disulfonic acid compound, preferred ethylamino benzophenone or thioxanthones and mercaptan compound.

Mercaptan compound is many not to be absorbed under exposure wavelength, further improves initiating agent to the sensitivity of active radioactive ray or suppress the effects such as polymerization obstruction of the polymerizable compound that oxygen produced thereby have to play a role as chain-transferring agent.

As mercaptan compound, can list the two thiopropionates (BDTP) of ethylene glycol bis thiopropionate (EGTP), butylene glycol, trimethylolpropane tris thiopropionate (TMTP), pentaerythrite tetrathio propionic ester (PETP) and wait simple function mercaptan compounds such as each multi-functional thiol's compound, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β mercaptonaphthalene, N-phenyl-mercaptobenzimidazole.

Particularly from ageing stability, deliquescent viewpoint solvent, the mercaptan compound of preferred simple function.

The content of mercaptan compound is from the viewpoint of the curing rate that balance determined that improves polymerization growth rate and chain transfer in the photosensitive composition of the present invention, is the scope of 0.5～10 quality %, the scope of 0.5～5 quality % more preferably with respect to the quality optimization of the total solid composition of photosensitive polymer combination.

(surfactant)

Photosensitive composition of the present invention can contain surfactant.

When increasing pigment concentration,, therefore be easy to take place the thickness inequality after photosensitive composition layer (dyed layer is filmed) forms when photosensitive composition coating or transfer printing are on substrate because the thixotropy of coating fluid generally can increase.In addition, when utilizing the slot coated method to form photosensitive composition layer (dyed layer is filmed), importantly before drying the photosensitive composition layer form usefulness the coating fluid levelling, form filming of uniform thickness.Therefore, preferably in above-mentioned photosensitive composition, contain suitable surfactant.As above-mentioned surfactant, can list in TOHKEMY 2003-337424 communique, the Japanese kokai publication hei 11-133600 communique disclosed surfactant as preferred surfactants.

As the surfactant that is used to improve coating, can add nonionic is that surfactant, fluorine are that surfactant, silicon are surfactant etc.

As nonionic is surfactant, and nonionics such as preference such as polyoxyethylene glycol class, polyoxy propandiols, polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, polyxyethylated ester class, polyoxypropylene alkyl ether, polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, single glycerine alkyl esters are surfactant.

Polyether polyols classes such as polyoxyethylene glycol, polyoxy propylene glycol are arranged particularly; Polyoxyalkylene alkyl classes such as polyoxyethylene laurel ether, polyoxypropylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polystyrene-basedization of polyoxyethylene ether, polyoxyethylene tribenzyl phenyl ether, polystyrene-basedization of polyoxyethylene-propylene ether, polyoxyethylene nonylplenyl ether; Nonionics such as polyoxyalkylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters class are surfactant.

Their object lesson for example has ADEKA PLURONIC series, ADEKANOL series, (above be trade name to TETRONIC series, ADEKA Co., Ltd. (ADEKA Corporation) system), EMULGEN series, (above be trade name to RHEODOL series, Kao Corp (KaoCorporation) system), ELEMINOL series, NONIPOL series, OCTAPOL series, DODEKAPOL series, NEWPOL series (above is trade name, Sanyo Chemical Industries Co., Ltd. (Sanyo Chemical Industries Ltd.) system), PIONIN series (trade name, (the Takemoto Oil﹠amp of Zhu Ben's Oil Corporation; Fat Co., Ltd.) system), NISSAN NONION series (trade name, NOF Corp (NOF Corporation) system) etc.Can suitably use these commercially available products.Preferred HLB value is 8～20, more preferably 10～17.

As fluorine is surfactant, the compound that can preferably use endways, any position at least in main chain and the side chain has fluoroalkyl or fluorine alkylidene.

As concrete commercially available product, MEGAFAC F142D is for example arranged, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F183, MEGAFAC F780, MEGAFAC F781, MEGAFAC F782, MEGAFAC F784, MEGAFAC F552, MEGAFAC F554, MEGAFAC R30, (above be trade name to MEGAFAC R08, Dainippon Ink Chemicals (DIC Corporation) system), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, (above be trade name to FLUORAD FC-431, Sumitomo 3M Co., Ltd. system), SURFLON S-112, SURFLON S-113, SURFLONS-131, SURFLON S-141, SURFLON S-145, SURFLON S-382, SURFLONSC-101, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, (above be trade name to SURFLON SC-106, (the Asahi Glass Co. of Asahi Glass Co., Ltd, Ltd.) system), EFTOP EF351, EFTOP 352, EFTOP 801, EFTOP802 (above is trade name, JEMCO Co., Ltd. (JEMCO Inc.) system) etc.

As silicon is surfactant, for example can list TORAY SILICONE DC3PA, TORAY SILICONE DC7PA, TORAY SILICONE SH11PA, TORAYSILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONESH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH-190, TORAYSILICONE SH-193, TORAY SILICONE SZ-6032, TORAY SILICONESF-8428, TORAY SILICONE DC-57, (above be trade name to TORAY SILICONE DC-190, (the Dow Corning Toray Co. of Dow Corning Toray Silicone Co., Ltd., Ltd.) system), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above is trade name, Momentive Performance Materials Inc. system) etc.

Wherein, as preferred surfactants of the present invention, MEGAFAC F780, MEGAFACF781, MEGAFAC F782, MEGAFAC F784, MEGAFAC F552 and MEGAFACF554 (above is Dainippon Ink Chemicals's system) are arranged.

These surfactants are to be preferably below 5 mass parts with respect to photosensitive composition 100 mass parts, more preferably below 2 mass parts, more preferably the amount below 0.5 mass parts is used.When the amount of surfactant surpassed 5 mass parts, striped when being easy to be coated with drying or wildness, flatness were easy to variation.

(heat-curing resin)

Photosensitive composition of the present invention can contain heat-curing resins such as epoxy resin, oxetane resin as required.

As epoxy resin, bisphenol type epoxy compound, cresols phenolic varnish type epoxy compound, biphenyl type epoxy compound, alicyclic epoxy compound etc. are arranged.

For example, as the bisphenol type epoxy compound, except EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, (above be trade name to YDF-170 etc., Dongdu changes into (Tohto Kasei Co., Ltd.) system), DENACOL EX-1101, EX-1102, (above be trade name to EX-1103 etc., NagaseChemiteX Corporation system), PLACCEL GL-61, GL-62, G101, (above be trade name to G102, Daicel chemistry (Daicel Chemical Industries Ltd.) system) outside, also can list and Bisphenol F type epoxy compound like these compounds, bisphenol S type epoxy compound.In addition, can also use epoxy acrylates such as Ebecryl 3700,3701,600 (above be trade name, Daicel-CytecCompany Ltd. system).

As cresols phenolic varnish type epoxy compound, (above is trade name can to list EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc., Dongdu system of changing into), DENACOL EM-125 etc. (abovely is trade name, Nagase ChemiteXCorporation system), as the biphenyl type epoxy compound, can list 3,5,3 ', 5 '-tetramethyl-4,4 '-diglycidyl biphenyl etc.

As the alicyclic epoxy compound, can list CELLOXIDE 2021,2081,2083,2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above is Daicel chemistry (Daicel Chemical Industries Ltd.) system), SANTOHTO ST-3000, ST-4000, ST-5080, ST-5100 etc. (above is trade name, Dongdu system of changing into) etc.Can also use in addition as EPOTOHTO YH-434, the YH-434L of amine type epoxy resin, in the skeleton of bisphenol A type epoxy resin modification the glycidyl esters etc. of dimer acid.

In these epoxy resin, preferred phenolic varnish type epoxy compound, alicyclic epoxy compound, preferred especially epoxide equivalent is 180～250.As such material, can list EPICLONN-660, N-670, N-680, N-690, YDCN-704L and (abovely be trade name, Dainippon Ink Chemicals's system), EHPE3150 (trade name, Daicel chemistry (Daicel Chemical Industries Ltd.) system).

As oxetane resin, can use ArON OXETANE OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (above be trade name, the synthetic system in East Asia).

In addition, oxetane resin can use separately, perhaps also can mix use with acrylic acid series copolymer, epoxy resin or maleimide resin.Particularly by with epoxy resin and when using, from the heat of utilizing the ultraviolet laser exposure to be produced cause reactive high, with the viewpoint of the adaptation of substrate preferably.

The content in photosensitive composition as epoxy resin of the present invention and oxetane resin, total solid composition with respect to photosensitive composition is preferably 0.5～15 quality %, from take into account to the dissolubility of alkali and with the viewpoint of the adaptation of substrate, be preferably 1～10 quality %.

(organic carboxyl acid)

For the alkali dissolution that promotes uncured portion, when further improving the development of photosensitive composition, can add organic carboxyl acid, preferred molecular weight is the low-molecular-weight organic carboxyl acid below 1000.For example can list formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, aliphatics monocarboxylic acid such as sad particularly; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatics tricarboxylic acids such as the third three acid, aconitic acid, norcamphor three acid; Benzoic acid, methyl benzoic acid, cumfrey, 2,3-mesitylenic acid, 3, aromatic series monocarboxylic acids such as 5-mesitylenic acid; Aromatic series poly carboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, phenoxyacetic acid, methoxybenzene ethoxyacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, acetate cinnamylidene ester, coumaric acid, umbellic acid.

(silane coupling agent)

In the photosensitive composition of the present invention,, can use silane coupling agent (silane coupling agent) from the viewpoint of the adaptation of further raising and substrate.

Silane coupling agent is as the material that can preferably have alkoxysilyl with the hydrolization group of inorganic material chemical bonding.In addition; preferably have and organic resin between interact or form key and show the group of compatibility; as such group; preferably have (methyl) acryloyl group, phenyl, sulfydryl, glycidyl, oxetanyl, wherein preferably have (methyl) acryloyl group or glycidyl.

Promptly; as the silane coupling agent that uses among the present invention; be preferably compound, can list (methyl) acryloyl group-trimethoxy silane compound, glycidyl-trimethoxy silane compound of following structure etc. particularly with alkoxysilyl and (methyl) acryloyl group or epoxy radicals.

Addition when using silane coupling agent in the total solid composition in the used photosensitive composition of the present invention, is preferably the scope of 0.2 quality %～5.0 quality %, 0.5 quality %～3.0 quality % more preferably.

(polymerization inhibitor)

Among the present invention, for stop in the manufacturing of photosensitive composition or preserve in polymerizable compound unwanted thermal polymerization takes place, preferably add a spot of hot polymerization inhibitor.

As spendable hot polymerization inhibitor among the present invention, can list p-dihydroxy-benzene, p methoxy phenol, two-tert-butyl group-paracresol, pyrogallol, tert-butyl catechol, benzo quinone, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-the inferior cerium salt of di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), N-nitroso-phenyl hydramine, phenoxazine, phenothiazine etc.

The addition of hot polymerization inhibitor is preferably 0.01 quality %～5 quality % with respect to photosensitive composition.

In addition, for the caused polymerization of anti-block suppresses, can also add senior derivative of fatty acid such as mountain Yu acid or mountain Yu acid amides etc. as required, make its surperficial uneven distribution in the dry run after coating at photographic layer.The addition of advanced higher fatty acid derivative is preferably the 0.5 quality %～10 quality % of photosensitive composition.

(plastifier)

In addition, also can add inorganic filler or plastifier etc. for the rerum natura that improves photosensitive composition among the present invention.

As plastifier; dioctyl phthalic ester, two (dodecyl) phthalic ester, triethylene glycol dicaprylate, DMEP, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine etc. are for example arranged, its with respect to (C) polymerizable compound and (B) gross mass of adhesive resin can add below the 10 quality %.

Photosensitive composition of the present invention can utilize known in the past exposure method to be cured, and wherein, utilized the exposure of ultraviolet light to be cured, also to show the high adaptation to substrate with high sensitivity.As the exposure method of ultraviolet light, can be in laser explosure method and close induction type (proximity) exposure method any, from suppressing the viewpoint of surperficial reticulation, preferred laser explosure method.During the colored pattern that photosensitive composition of the present invention can be preferred for color filter forms.

" pattern formation method, color filter and manufacture method thereof "

Photosensitive composition of the present invention and pattern formation method preferably are applicable to the liquid crystal indicator color filter.Below, enumerate liquid crystal indicator and the pattern formation method of having used photosensitive composition of the present invention is described, but the present invention is not limited to the method with the pattern formation method in the manufacturing method of color filter.

Pattern formation method of the present invention comprises following operation: photosensitive composition of the present invention is applied on the substrate, thereby the dyed layer that forms dyed layer forms operation; Utilize the ultraviolet laser of pattern sample to expose to above-mentioned dyed layer, thereby form the exposure process of sub-image; With, the dyed layer that is formed with above-mentioned sub-image is developed, thereby form the developing procedure of pattern.In addition, also can design operation (prebake conditions (pre-bake) operation) that above-mentioned dyed layer is toasted and the operation (roasting procedure) that the above-mentioned dyed layer after developing is toasted as required.Sometimes these operations are called in the lump pattern and form operation.

(dyed layer formation operation)

Form in the operation at dyed layer of the present invention, photosensitive composition of the present invention is applied on the substrate, thereby forms dyed layer.As substrate, for example can list alkali-free glass, soda-lime glass, pyrex, the quartz glass that in liquid crystal indicator etc., uses and on them, adhere to nesa coating and the components of photo-electric conversion substrate that uses in the substrate that obtains, solid-state imager etc.In addition, can also use plastic base.Use these substrates, ground such as preferred clathrate form black matrix (blackmatrix), form colored pattern in the blank parts of grid.

On these substrates in order to improve with the driving fit of the layer on top, to prevent the planarization of material diffusion or substrate surface, also undercoat can be set as required, from the angle of further performance effect of the present invention, preferable substrate is large-scale (about 1 length of side is more than the 1m).

As the method that on substrate, forms dyed layer, can preferably use the method for bestowing of slot coated (slit coating), ink-jet method (inkjetting), rotary coating (spin coating), curtain coating coating (cast coating), roller coat (roll coating), silk screen print method various coatings such as (screen printing) etc.Wherein, from the preferred slot coated of the viewpoint of precision and speed.

In addition, can also use and will be in advance be imparted into the adhering molding transfer that forms on the interim supporter method to the substrate by the above-mentioned method of bestowing.

About printing transferring method, among the present invention, also can preferably use the middle method for making of putting down in writing in paragraph [0096]～[0108] of paragraph [0023], [0036]～[0051] or the TOHKEMY 2006-47592 communique of TOHKEMY 2006-23696 communique.

Bed thickness (for example being coated with thick) about dyed layer of the present invention, in order to obtain sufficient Color reproduction zone and to obtain sufficient panel luminance, preferably the mode that reaches 0.5 μ m～3.0 μ m according to dried thickness forms, and more preferably reaches 1.5 μ m～2.5 μ m.

(exposure process)

In exposure process of the present invention, utilize the ultraviolet laser of pattern sample to expose to above-mentioned dyed layer, thereby form sub-image.Consider by exposure process of the present invention, in the pattern-like exposure area of photosensitive composition, the initiation kind that utilization is produced by (D) Photoepolymerizationinitiater initiater, cause and promote the polymerization curing reaction of (C) polymerizable compound, the heat of utilizing the ultraviolet laser exposure to be produced simultaneously, (B) molecular memory of adhesive resin allyl, N position-substituted maleimide amido or cyclic imide base generation thermal response, cause and promote curing reaction, light takes place by the exposure area, hot dual cure forms the pattern that is made of consolidation zone and uncured zone.

As the exciting media of laser, crystallization, glass, liquid, pigment, gas etc. are arranged, can use from what these media sent known ultraviolet lights such as Solid State Laser, liquid laser, gas laser, semiconductor laser are had the laser of vibration wavelength.Wherein, from the viewpoint of the power and the vibration wavelength of laser, preferred Solid State Laser, gas laser.

Exposure wavelength as the ultraviolet laser that uses among the present invention, from wavelength photoreceptor and the good angle of sensitivity that meets photosensitive composition, be preferably the scope of 300nm～380nm, more preferably 310nm～360nm scope, be preferably 355nm wavelength laser exposure method especially.

Can preferably use the 3rd higher hamonic wave (355nm), excimer laser one XeCl (308nm), the XeF (353nm) of the Nd:YAG laser of big, the less expensive Solid State Laser of power particularly especially.

In addition, as the exposure that is exposed thing (pattern), be 1mJ/cm ²～100mJ/cm ²Scope, 1mJ/cm more preferably ²～50mJ/cm ²Scope.When exposure during in this scope, the angle of the throughput rate that forms from pattern is preferred.

The ultraviolet laser that uses among the present invention is preferably the pulse laser that vibrates from the viewpoint of throughput rate under the frequency of 20Hz～2000Hz.

Be not particularly limited as spendable exposure device among the present invention, can use EGIS (trade name as commercially available product, (the V Technology Co. of V Technology Co., Ltd., Ltd.) make) or DF2200G (trade name, big Japanese Screen Co., Ltd. (Dainippon Screen MFG.Co., Ltd.) system etc.Also preferably use the device except that above-mentioned.

The depth of parallelism of the light of ultraviolet laser is good, can not use mask to carry out pattern exposure when exposure, but pattern form is subjected to exporting the shape of light, the influence of distribution (profile) (mask).Therefore, use mask pattern to be exposed because the rectilinearity of pattern increases, therefore more preferably.

(developing procedure)

In developing procedure of the present invention, the dyed layer that has formed above-mentioned sub-image is developed, thereby form pattern.Utilize the exposure area of ultraviolet laser to be solidified into pattern-like, carry out the alkali development treatment by development treatment, thereby can with in above-mentioned exposure process not illuminated portion (uncured portion) be dissolved in the aqueous alkali and remove, only the residual light part of having solidified forms pattern thus.

As developer solution, use organic base developer solution or inorganic base developer solution or its mixed liquor.

As the alkaline agent that uses in the developer solution, for example can list NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicylo-organic basic compounds such as [5.4.0]-7-hendecene preferred uses that with pure water these alkali compounds to be diluted to concentration is 0.001～10 quality %, is preferably alkaline aqueous solution that 0.01～1 quality % obtains as developer solution.In addition, when using the developer solution that constitutes by such alkaline aqueous solution, generally after development, wash (flushing) with pure water.

As development temperature, be preferably 20 ℃～35 ℃, more preferably 23 ℃～30 ℃.Development time is preferably 30 seconds～and 120 seconds, more preferably 40 seconds～90 seconds.Wherein, about the preferred compositions of development temperature and development time, for example can list temperature be carry out under 25 ℃ 50 seconds～100 seconds, be to carry out under 30 ℃ 40 seconds～80 seconds in temperature.

In addition, flushing is pressed and to be preferably 0.01MPa～0.5MPa, more preferably 0.05MPa～0.3MPa, 0.1MPa～0.3MPa more preferably.By selecting these conditions, the shape of pattern at random can be designed to rectangle or suitable taper.

(roasting procedure)

Among the present invention,, the roasting procedure that the above-mentioned dyed layer after developing is toasted is set preferably in order to make the completion of cure of photosensitive composition.The method of toasting can be undertaken by following manner: use heating plate (hot plate) or heating arrangements such as convective oven (convection oven) (heated air circulation type dryer), high frequency heating machine that the substrate with pattern after developing, washing is carried out continous way or step heating.

As the condition of baking, temperature is preferably 150 ℃～260 ℃, more preferably 180 ℃～260 ℃, most preferably is 200 ℃～240 ℃.Stoving time is preferably 10 minutes～and 150 minutes, more preferably 20 minutes～120 minutes, most preferably be 20 minutes～90 minutes.

In addition, when forming the colored pattern of RGB 3 tones, light shield layer etc., a plurality of tones, can only repeat the circulation of formation, exposure, development and the baking of dyed layer according to required tone number; Also can be after each tone ground carry out formation, exposure and the development of dyed layer, last all tone ground toasts.Thus, make the color filter that possesses the colored pixels that constitutes by required tone.

(other operations)

Among the present invention, before exposure process, wait the dyed layer drying that forms, also the operation of carrying out prebake conditions can be set in order to make by coating.The prebake conditions temperature of dyed layer is preferably 60 ℃～140 ℃, more preferably 80 ℃～120 ℃.The prebake conditions time is preferably 30 seconds～and 300 seconds, more preferably 80 seconds～200 seconds.

" liquid crystal indicator "

Color filter of the present invention preferably is suitable for the making of liquid crystal indicator, has used the liquid crystal indicator of the color filter of making by pattern formation method of the present invention can show high-grade image.

The definition of display device or the illustrative examples of each display device are as being recorded in " Electricity デ イ ス プ レ イ デ バ イ ス (assistant The clear husband of wood work, (the strain) Gong Ye Tone meeting of looking into (Kogyo Chosakai PublishingInc.) 1990 Nian development are capable) ", " デ イ ス プ レ イ デ バ イ ス (it is capable that she blows Cis chapter work, industry figure Books (strain) (Sangyo Tosho), 1989 Nian development) " etc.In addition, liquid crystal indicator for example is recorded in " inferior generation liquid crystal デ イ ス プ レ イ Ji Intraoperative (interior field Long man Knitting collection, (strain) Gong Ye Tone look into can 1994 Nian development capable) ".The present invention's liquid crystal indicator applicatory is not particularly limited, for example applicable to the liquid crystal indicator of the variety of way of record in above-mentioned " inferior generation liquid crystal デ イ ス プ レ イ Ji Intraoperative ".

Liquid crystal indicator is with especially effective especially to the liquid crystal indicator of colored TFT (thin film transistor (TFT)) mode in the color filter.The liquid crystal indicator of colored TFT mode for example is recorded in " カ ラ one TFT liquid crystal デ イ ス プ レ イ (upright altogether (strain) (the Kyoritsu Shuppan Co., Ltd.), 1996 Nian development are capable) that publish ".Liquid crystal indicator, STN (super-twist nematic), TN (twisted nematic), VA (vertical orientating type), OCS (On Chip Spacer), FFS (fringe field switching type) and R-OCB (catoptrics compensated bend type) etc. that the present invention also enlarges applicable to IPS transverse electric field type of drive, MVA angle of visibilities such as pixel partitioning scheme such as (multizone vertical orientating types) such as (switch types in the face).For example be recorded in " EL, PDP, the up-to-date Move of LCD デ イ ス プ レ イ-Ji Intraoperative と city Games are to-(East レ リ サ one チ セ Application タ one (Toray ResearchCenter, Inc.) Tone to look into Yan Jiu Bu Door 2001 Nian development capable) " the 43rd page for its mode.

Liquid crystal indicator is made of various parts such as electrode base board, polarizing coating, phase retardation film, (backlight) backlight, sept (spacer), visual field diaphragm except color filter.Color filter for liquid display element of the present invention is also applicable to the liquid crystal indicator that is made of these well-known components.

It is capable that these parts for example are recorded in " ' 94 liquid crystal デ イ ス プ レ イ Zhou side material ケ ミ カ Le ズ city's Games (Island Itou Kentaro (strain) シ one エ system シ one (CMC Publishing) 1994 Nian development) ", " 2003 Ye Jing Off Even city Games present situation と

Look forward to (last volume) (it is capable that the good lucky キ メ ラ of (strain) Fuji Gross of table grinds (Fuji Chimera Research Institute Inc.) 2003 Nian development) ".

About backlight, be recorded in SID meeting Digest 1380 (2005) (A.Konnoet.al), monthly magazine デ イ ス プ レ イ in Dec, 2005 number 18～24 ペ, one ジ (the Island health is abundant), monthly magazine デ イ ス プ レ イ in Dec, 2005 number 25～30 ペ, one ジ (Yagi spark gap grand bright) etc.

To be used for liquid crystal indicator by the color filter that pattern formation method of the present invention is made, with the three-wavelength pipe combination of known cold-cathode tube in the past the time, can realize high-contrast, led light source (RGB-LED) by making red, green, blue can provide the high Color reproduction of brightness height and excitation good liquid crystal indicator as backlight in addition.

[embodiment]

Below, more specifically describe the present invention by embodiment, but the present invention is only otherwise break away from its purport, is not limited to following embodiment.Wherein, short of special qualification, " % " and " part " is quality standard.

By following method, synthesize example compound 1-1, the 1-2, the 1-3,31,35 and 39 that in (B) adhesive resin item, enumerate.

(synthesis example 1: example compound 1-1's is synthetic)

In the there-necked flask of the 200mL capacity that possesses the stirring rod, backflow cooling tube and the thermometer that have agitator, add 1-methoxyl-2-propyl alcohol 54g, under stream of nitrogen gas, be heated to 70 ℃.Use ram pump (plunger pump) with 2.5 hours times in there-necked flask, drip in 1-methoxyl-2-propyl alcohol 54g be dissolved with ALMA 10.07g, methacrylic acid 1.93g, as 2 of polymerization initiator, the solution of two (2, the 4-methyl pentane nitrile) 0.185g of 2 '-azo.After dripping end, stirred 2 hours down at 70 ℃ again.Heating is put in the 1L water after finishing, once more precipitation.With carrying out vacuum drying after the precipitate filtration, obtain the adhesive resin of 9g (yield is 75%).

As the mensuration sample of weight-average molecular weight, with the adhesive resin 0.01g that the weighing of 10mL graduated cylinder obtains, add the tetrahydrofuran of about 8mL, at room temperature after the dissolving, making total amount is 10mL.Use gel permeation chromatography (GPC) to measure this solution.The weight-average molecular weight of example compound 1-1 (ALMA/methacrylic acid copolymer, mol ratio=80/20) is 35000.

In addition, synthetic method according to above-mentioned example compound 1-1, synthetic example compound 1-2 (ALMA/methacrylic acid copolymer, mol ratio=50/50, weight-average molecular weight is 35000) and example compound 1-3 (ALMA/methacrylic acid copolymer, mol ratio=40/60, weight-average molecular weight are 35000).

(synthesis example 2: example compound 31 synthetic)

In the flask that possesses cooling tube, stirring machine, add 2,2 '-azobis isobutyronitrile, 2 mass parts and propylene glycol monomethyl ether 200 mass parts, then add N-phenylmaleimide 51.9 mass parts, ALMA 62 mass parts, methacrylic acid 16.8 mass parts and as 2 of molecular weight regulator, 4-diphenyl-4-methyl-1-pentene (NOF Corp's system trade name, NOFMER MSD) 3 mass parts are carried out nitrogen replacement.Slowly stir afterwards, and make the temperature of reaction solution rise to 80 ℃, keep this temperature to carry out polymerization in 5 hours, thereby obtain the solution (solid component concentration=20.0 quality %) of adhesive resin.Using the weight-average molecular weight of the example compound 31 of GPC mensuration is 35000.

(synthesis example 3: example compound 35 synthetic)

In the flask that possesses cooling tube, stirring machine, add 2,2 '-azobis isobutyronitrile, 2 mass parts and propylene glycol monomethyl ether 200 mass parts, then add cyclohexyl maleimide 124.6 mass parts, methacrylic acid 25.2 mass parts and as 2 of molecular weight regulator, 4-diphenyl-4-methyl-1-pentene (NOF Corp's system trade name, NOFMER MSD) 3 mass parts are carried out nitrogen replacement.Slowly stir afterwards, and make the temperature of reaction solution rise to 80 ℃, keep this temperature to carry out polymerization in 5 hours, thereby obtain the solution (solid component concentration=20.0 quality %) of adhesive resin.Using the weight-average molecular weight of the example compound 35 of GPC mensuration is 20000.

(synthesis example 4: example compound 36 synthetic)

Add 2 in the flask that possesses cooling tube, stirring machine, 2 '-azobis isobutyronitrile, 2 mass parts and propylene glycol monomethyl ether 200 mass parts then add N-CH ₂-Ph maleimide 111.0 mass parts, methacrylic acid 34.4 mass parts and as 2 of molecular weight regulator, 4-diphenyl-4-methyl-1-pentene (NOF Corp's system trade name, NOFMER MSD) 3 mass parts are carried out nitrogen replacement.Slowly stir afterwards, and make the temperature of reaction solution rise to 80 ℃, keep this temperature to carry out polymerization in 5 hours, thereby obtain the solution (solid component concentration=20.0 quality %) of adhesive resin.Using the weight-average molecular weight of the example compound 36 of GPC mensuration is 18000.

(synthesis example 5: example compound 39 synthetic)

Method (Kato, S., Sato according to Kato etc., K., Maeda, D., Nomura, M.ColloidsSurfaces A:Physiochem.Eng.Aspects, 1999,153,127 (1999)) synthesize the compound that following structural formula is represented, then by the synthetic example compound 39 of the method (Okazaki, E.Proceedings of the Radtech Europe2001) of this compound and metering system acid-utilising Okazaki.Using the weight-average molecular weight of the example compound 39 of GPC mensuration is 20000.

(preparation of the dispersion liquid of viridine green halogenated phthalocyanines zinc)

-halogenated phthalocyanines zinc pigment synthetic-

With benzene dicarbonitrile, zinc chloride is that raw material is made Phthalocyanine Zinc.

Halogenation is in 3.1 parts of 40 ℃ of following mix sulphur acyl chlorides, 3.7 parts of anhydrous Aluminum chlorides, 0.46 part in sodium chloride, 1 part of Phthalocyanine Zinc, and 2.2 parts of dripping bromine are carried out then.Reacted 15 hours down at 80 ℃, afterwards reaction mixture is dropped in the water, the thick pigment of part bromination Phthalocyanine Zinc is separated out.With this water-based slurry filtration, carry out 80 ℃ hot wash, dry under 90 ℃, obtain the refining thick pigment of part bromination Phthalocyanine Zinc of 2.6 parts of processes.

1.6 parts of 7 parts in sodium chloride, diethylene glycols, the dimethylbenzene of 1 part of the thick pigment of this part bromination Phthalocyanine Zinc, pulverizing are added in two wrist type kneaders for 0.09 part, descended mixing 6 hours at 100 ℃.100 parts in water putting into 80 ℃ is taken out in mixing back, stirs filter after 1 hour, hot wash, drying, obtain the part bromination Phthalocyanine Zinc pigment of pulverizing.

The part bromination Phthalocyanine Zinc pigment that obtains by the content of halogen analysis that utilizes quality analysis as can be known, average group becomes ZnPcBr ₁₀Cl ₄H ₂(PC; Phthalocyanine), on average contain 10 bromines in 1 molecule.

In addition, utilizing the mean value of the primary particle size of transmission electron microscope (the system JEM-2010 of Jeol Ltd.) mensuration is 0.065 μ m.

(the Aimex Co. of Aimex Co., Ltd. that diameter is a 0.5mm zirconia bead is being housed, Ltd.) add 78 parts of 14.9 parts of part bromination Phthalocyanine Zinc pigment (being called PG58) obtaining in above-mentioned, 7.1 parts of BYK corporate system acrylic acid series spreading agents " BYK-2001 ", propylene glycol 1-monomethyl ether 2-acetic acid esters (below be called PGMEA) in Zhi the high speed dispersor " TSC-6H " (trade name), change stirring 8 hours with per minute 2000, the dispersion liquid of the halogenated phthalocyanines zinc pigment (being called viridine green PG58) of preparation part bromination.

(preparation of the dispersion liquid of yellow uitramarine PY150)

-resin (i-1) synthetic-

Mix caprylic acid 6.4g, 6-caprolactone 200g, metatitanic acid (IV) four butyric ester 5g, be cooled to room temperature after 8 hours, obtain vibrin (i-1) in heating under 160 ℃.Synthetic route below is shown.

-resin (J-1) synthetic-

(trade name, SP-018, number-average molecular weight are 1,800 to the mix polyethylene imines, Japanese catalyzer (Nippon Shokubai Co., Ltd.) system) 10g and above-mentioned vibrin (i-1) 100g, 120 ℃ of heating 3 hours down, obtain intermediate (J-1B).Afterwards, put and be chilled to 65 ℃, slowly add the PGMEA 200g that contains succinic anhydride 3.8g, stirred 2 hours.Afterwards, add PGMEA, obtain the PGMEA 10 quality % solution of resin (J-1).Resin (J-1) has the side chain in vibrin (i-1) source and the carboxylic acid in succinic anhydride source.Synthetic route below is shown.

Utilize ball mill (zirconia bead 0.3mm) to mix C.I. pigment yellow 150 (PY150) 15 parts of (mean grain size is 60nm), 7.5 parts of above-mentioned resins (J-1), the PGMEA77.5 part 3 hours of disperseing, the dispersion liquid of preparation yellow uitramarine PY150 as pigment.

(embodiment 1)

(preparation of photosensitive composition)

Be prepared as follows dispersible pigment dispersion 1.Promptly, is 3 according to following composition, use homogenizer with rotating speed, mixed in 3 hours 000r.p.m. stir, the preparation mixed solution, then with the bead dispersion machine ULTRAAPEX MILL (trade name of having used 0.1mm φ zirconia bead, longevity industrial group (KotobukiIndustries Co., Ltd.) system) dispersion treatment 8 hours.

C.I. pigment blue 15: 6 11.8 parts

C.I. pigment Violet 23 is 1.0 parts

24.0 parts of Disperbyk161 (BYK corporate system, 30% solution)

63.2 parts of PGMEA

The composition of forming below further adding in the dispersible pigment dispersion 1 that obtains mixes, and preparation blue cast (B) is used photosensitive composition.

1 39.20 parts of dispersible pigment dispersions

16.40 parts of the 20%PGMEA solution of adhesive resin: example compound 1-1

4.57 parts of polymerizable compound: M-510 (the multi-functional monomer that contains carboxyl)

(Toagosei Co., Ltd's system, ARONIX M-510, acid number are 100mgKOH/g)

Photoepolymerizationinitiater initiater: 2.74 parts of compd As (following structure)

Sensitizer: 0.55 part of simple function mercaptan compound SH-1 (following structure)

0.60 part of epoxy compound: EHPE3150 (Daicel KCC system)

35.51 parts of the mixed solutions of solvent: PGMEA and 3-ethoxyethyl group propionic ester (=80/20[mass ratio])

Polymerization inhibitor: 0.01 part of p methoxy phenol

0.40 part of closing force correctives: KBM-503 (KCC of SHIN-ETSU HANTOTAI system)

Surfactant: 0.02 part of MEGAFAC F-780 (Dainippon Ink Chemicals's system)

Compd A

SH-1

(formation of pattern)

About the formation of pattern, short of special qualification is then implemented following operation and is carried out.

Use slit coater (Hirata Spinning Ltd. (Hirata Corporation), HC-6000) photosensitive composition that will above obtain is applied to alkali-free glass substrate (Corning company, 1737, on the surface of 550mm * 660mm), carry out 120 seconds prebake conditions then in 90 ℃ cleaning oven, forming thickness is the dyed layer of 2.0 μ m.

Then, use EGIS (the 3rd higher hamonic wave (355nm) of V Technology Co., Ltd., YAG laser, pulse width are 6ns), through having 20 microns wide live widths and interval (Line﹠amp as laser explosure device; Space) photomask (photomask) also makes the surface of the dyed layer on the substrate and the gap of photomask (slit) is 200 μ m, and (exposure is 20mJ/cm to carry out 20 times ²) about 1mJ/cm ²Pulse irradiation (frequency is 50Hz).

Afterwards, use developing apparatus (High-Technologies company of Hitachi (HitachiHigh-Technologies Corporation) system) to this substrate, with potassium hydroxide is developer solution CDK-1 ((the Fuji film Electronics Materials Co. of film Electronics Materials Co., Ltd. of Fuji, Ltd.) (dilution has the solution of 1 mass parts CDK-1,99 mass parts pure water to 1.0% developer solution system), 25 ℃), will wash to press and be set at 0.20MPa, developed 50 seconds, air-dry after washing with pure water.Afterwards, in 220 ℃ cleaning oven, carry out 30 minutes baking, on substrate, form blue line pattern.

The line pattern that forms is carried out following evaluation.Show the result in table 2.

(evaluation of live width sensitivity)

Utilize optical microscope (200 times) to observe formed line pattern, live width is carried out evaluation of measuring.

-evaluation criterion-

More than the A:30 μ m

More than the B:27 μ m and less than 30 μ m

More than the C:25 μ m and less than 27 μ m

D: less than 25 μ m

E: do not form pattern or peel off, can't estimate.

(linear evaluation)

Utilize optical microscope (200 times) to observe formed line pattern, the rectilinearity of visual valuation live width (unstable degree).

-evaluation criterion-

A: do not have shakiness, also do not have fragmentation, lines straight.

B: there is shakiness several positions, but lines are straight substantially.

C: shakiness is big, the lines shakiness about live width ± 2 μ m takes place.

D: shakiness is big, the lines shakiness about live width ± 5 μ m takes place.

E: do not form pattern or peel off, can't estimate.

(stable on heating evaluation)

In 240 ℃ cleaning oven the substrate that has formed line pattern is appended baking 60 minutes, (Otsuka Electronics Co., Ltd.) system spectrophotometer MCPD-2000 measures aberration (the Δ E that appends the baking front and back in Shi Yong Otsuka Electronics Co., Ltd. ^*Ab).Here, Δ E ^*Ab is meant L ^*a ^*b ^*The aberration of chromatic diagram.Use Δ E ^*The value of ab is estimated thermotolerance according to following evaluation criterion.

-evaluation criterion-

5: Δ E ^*Ab is more than 0 and less than 1.0

4.5: Δ E ^*Ab is more than 1.0 and less than 2.0

4: Δ E ^*Ab is more than 2.0 and less than 3.0

3.5: Δ E ^*Ab is more than 3.0 and less than 3.5

3: Δ E ^*Ab is more than 3.5 and less than 4.0

2.5: Δ E ^*Ab is more than 4.0 and less than 5.0

2: Δ E ^*Ab is more than 5.0

1: peel off and Δ E ^*Ab is more than 5.0

(evaluation of development)

Use spin coater that photosensitive composition is applied on the surface of above-mentioned alkali-free glass substrate, make dry film thickness reach 2.0 μ m,, form uniform dyed layer 120 ℃ of following prebake conditions 2 minutes.Then used the pulse irradiation of laser explosure device as mentioned above.

Then, use shower nozzle that pure water is sprayed, after making dyed layer surface on the substrate wetting equably, use KOH be developer solution (with KOH, contain the solution that obtains after 100 times of non-ionic surfactant, trade name: CDK-1, film Electronics Materials Co., Ltd. of Fuji system dilutions) under 24 ℃ with flat burner pressure as 0.04MPa, every 5 seconds ground carry out shower and develop, washed for 20 seconds with flowing water afterwards, use air knife to carry out drying then, obtain line pattern.

When above-mentioned line pattern forms, be performed as follows the evaluation of development.That is, develop, measure and remove the needed time from substrate uncured since ground prolongation in per 5 seconds in 10 seconds.

(evaluation of reticulation)

In the formation of above-mentioned pattern, use that to have 20 microns wide and 200 microns wide live widths and masks at interval, to make the dyed layer surface on the substrate and the gap (slit) of mask be that 200 μ m ground expose.Utilize optical microscope (200 times) to observe the line pattern of 20 microns of the formed live widths in baking back, back and 200 microns, visual valuation reticulation.

-evaluation criterion-

A:200 micron, 20 microns all do not have reticulation, smooth.

Do not have reticulation during the B:200 micron, but reticulation has slightly taken place 20 microns the time.

Do not have reticulation during the C:200 micron, but reticulation has taken place 20 microns the time tempestuously.

Reticulation has slightly taken place during the D:200 micron, and reticulation has taken place 20 microns the time tempestuously.

The E:200 micron, reticulation has all taken place 20 microns the time tempestuously.

(comprehensive evaluation)

Synthetically estimate live width sensitivity, rectilinearity, thermotolerance, development and reticulation according to following evaluation criterion.

-evaluation criterion-

5: very excellent.

4.5: excellence.

4: use no problem level down usually.

3.5: though poor performance is no problem level.

3: common inadequate spendable level.

2.5: be lower than common spendable permission level, existing problems.

2: performance is insufficient, can't use.

1: the level that can't estimate.

(embodiment 2～23, comparative example 1～6)

Except change as shown in table 1 in the preparation of the photosensitive composition of embodiment 1 used each material, similarly prepare each photosensitive composition with the preparation of the photosensitive composition of embodiment 1.As the colorant of red color tone (R) usefulness, use C.I. paratonere 254.As the colorant of green hue (G) usefulness, with the C.I. pigment green 36: the mass ratio of C.I. pigment yellow 150 (C.I. pigment green 36/C.I. pigment yellow 150)=70/30 mixes and uses the former and the latter.

Use each photosensitive composition, similarly form the line pattern of embodiment 2～23 and comparative example 1～6 with the formation of pattern among the embodiment 1.The line pattern that use obtains carries out evaluation similarly to Example 1.The results are shown in table 2.

In addition, among the embodiment 15～17, in the evaluation of the formation of pattern and development and reticulation, replace laser explosure to carry out the close induction type exposure.The condition of close induction type exposure is as described below.Promptly, utilization has the type that closely the connects exposure machine (High-Technologies of Hitachi corporate system) of ultrahigh pressure mercury lamp vertically to hold up the state of substrate and mask (the quartzy exposed mask with picture pattern), with dyed layer surface on the substrate and the distance setting between the mask is 200 μ m, with exposure 20mJ/cm ²Carry out pattern exposure.

(embodiment 24)

(preparation of photosensitive composition)

Mix following composition, the preparation photosensitive composition.

32.68 parts of the dispersion liquids of above-mentioned viridine green PG58

14.56 parts of the dispersion liquids of above-mentioned yellow uitramarine PY150

0.176 part of adhesive resin: example compound 1-1

5.52 parts of polymerizable compound: TO-2349 (the multi-functional monomer that contains carboxyl)

(Toagosei Co., Ltd's system, ARONIX TO-2349, acid number are 67mgKOH/g)

Lophine is a Photoepolymerizationinitiater initiater: 1.115 parts of HABI-1311 (following structure)

(DKSH Japan system)

Photoepolymerizationinitiater initiater: 1.246 parts of IRGACURE OXE-01

(Ciba Specialty Chemicals corporate system)

Photoepolymerizationinitiater initiater: 0.036 part of KAYACURE DETX-S

(Nippon Kayaku K. K's system)

Sensitizer: 0.161 part of simple function mercaptan compound SH-1

Solvent: 24.60 parts of 3-ethoxyethyl group propionic esters

Solvent: 12.89 parts of propylene glycol monomethyl ether

Polymerization inhibitor: 0.003 part of p methoxy phenol

Surfactant: 0.0146 part of MEGAFAC F-554 (Dainippon Ink Chemicals's system)

HABI-1311

(formation of pattern)

Utilizing slit mouth mould is that 100mm/s, coating slit are that 100 μ m, coating flow velocity are that the condition of 1.3ml/s is applied to alkali-free glass substrate (on the surface of Corning company, 1737,550mm * 660mm) with the above-mentioned photosensitive composition that obtains with the coating speed, use the drying under reduced pressure chamber to carry out vacuum drying then and be 0.5Torr until arriving pressure, dry 120 seconds (prebake conditions) in 80 ℃ baking oven obtains the coated film that thickness is 2.0 μ m then.Afterwards, seeing through the photomask with 20 microns wide live widths and interval uses ultrahigh pressure mercury lamp with 20mJ/cm ²(illumination is 35mW/cm ²) Gap200 μ m carries out proximity printing, 1% aqueous solution of alkaline developer CDK-1 (film Electronics Materials Co., Ltd. of Fuji system) was scattered 40 seconds with the shower shape and then pure water was scattered 60 seconds with the shower shape, to the coated film wash-out developer after the exposure.Then, handled above-mentioned coated film through exposure and development treatment 40 minutes (then toast), on glass substrate, form line pattern with 230 ℃ baking oven for heating.

Afterwards, carry out similarly to Example 1 evaluation for formed line pattern.The results are shown in table 2.

(embodiment 25)

Except being that Photoepolymerizationinitiater initiater changes over the HABI-1311A (following structure) from HABI-1311, similarly prepare photosensitive composition with the preparation of the photosensitive composition of embodiment 24 with the lophine in the preparation of the photosensitive composition of embodiment 24.Afterwards, form line pattern and estimating similarly to Example 24.The results are shown in table 2.

HABI-1311A

(embodiment 26)

Except the polymerizable compound in the preparation of the photosensitive composition of embodiment 24 is changed into M-520 (Toagosei Co., Ltd's system from TO-2349, acid number is 30.0mgKOH/g, contain the multi-functional monomer of carboxyl) outside, similarly prepare photosensitive composition with the preparation of the photosensitive composition of embodiment 24.Afterwards, form line pattern and estimating similarly to Example 24.The results are shown in table 2.

Table 1

In the table 1, M-510 is that the system ARONIX M-510 of Toagosei Co., Ltd, M-520 are the system ARONIX M-520 of Toagosei Co., Ltd.M-1 and M-2 are object lesson M-1 and the M-2 that enumerates in the project of the multi-functional monomer that contains carboxyl.M-5 is the potpourri of (n=2/n=3/n=4)=60/30/10 in the compound represented of following structural formula.M-6 is the potpourri of (n=2/n=3/n=4)=85/15/5 in the compound represented of following structural formula.

In the table 1, DPHA is a dipentaerythritol acrylate, uses the commodity DPHA by name of Japanese chemical drug system.

CGI242 is that oxime is Photoepolymerizationinitiater initiater (a Ciba Specialty Chemicals corporate system).

" B-CIM " is that Photoepolymerizationinitiater initiater B-CIM and sensitizing coloring matter EAB (B-CIM: EAB=2: 1[mass ratio]) (being hodogaya chemical industry system) replace compd A for utilizing lophine.

" triazine system " for triazine be the adjacent bromo-of Photoepolymerizationinitiater initiater, 4-[to N, two (ethoxy carbonyl) aminophenyls of N-]-2, two (the trichloromethyl)-s-triazines of 6-.

Compd B is the compound that following structural formula is represented.

Compd B

In the table 1, comparative compound 1 is the multipolymer (the copolymerization mol ratio is 80/20, weight-average molecular weight be 35000) of n propyl methacrylate and methacrylic acid for the multipolymer of benzyl methacrylate and methacrylic acid (the copolymerization mol ratio is 80/20, weight-average molecular weight be 35000), comparative compound 2.

[table 2]

As shown in Table 2, used the live width sensitivity height, rectilinearity, thermotolerance of the embodiment 1～26 of photosensitive composition of the present invention and development excellent and suppressed the generation of reticulation.

Claims (10)

1. photosensitive composition, it contains (A) colorant, (B) adhesive resin, (C) polymerizable compound, (D) Photoepolymerizationinitiater initiater and (E) solvent at least, wherein,

The content of described (A) colorant is counted 15 quality %～60 quality % with respect to the solid constituent of photosensitive composition with mass fraction;

Described (B) adhesive resin has the structural unit, (B-2) that are selected from (B-1) following general formula (I) expression and has the structural unit of N position-substituted maleimide amido and (B-3) at least a kind of structural unit in the structural unit of following general formula (II) expression and have the structural unit of acidic-group in molecule;

At least a kind in described (C) polymerizable compound is the multi-functional monomer that contains carboxyl, and at least a kind in described (D) Photoepolymerizationinitiater initiater is that Photoepolymerizationinitiater initiater or oxime are Photoepolymerizationinitiater initiater for lophine;

In the general formula (I), R ¹¹～R ¹⁵Represent hydrogen atom, halogen atom, cyano group, alkyl or aryl independently of one another, R ¹⁶Expression hydrogen atom or methyl;

In the general formula (II), R ²¹Expression hydrogen atom or methyl, R ²²The expression carbon number is 1～6 alkylidene, R ²³And R ²⁴Represent that independently of one another hydrogen atom or carbon number are alkyl, the R below 4 ²³And R ²⁴Bonding forms carbocyclic ring mutually.

2. photosensitive composition according to claim 1, wherein, described oxime is that Photoepolymerizationinitiater initiater is that the ketoxime that following general formula (III) is represented is a Photoepolymerizationinitiater initiater;

In the general formula (III), R and X represent that independently of one another monovalence substituting group, A represent that divalent organic group, Ar represent that aryl, n are 0～5 integer, and when X exists when a plurality of, a plurality of X represent the monovalence substituting group independently of one another, and they can be the same or different.

3. photosensitive composition according to claim 1, wherein, the described acid number that contains the multi-functional monomer of carboxyl is 80mgKOH/g～200mgKOH/g.

4. photosensitive composition according to claim 1, it further contains (F) sensitizer, and at least a kind in described (F) sensitizer is the simple function mercaptan compound.

5. pattern formation method, it comprises following operation:

Each described photosensitive composition of claim 1～4 is applied on the substrate, thereby the dyed layer that forms dyed layer forms operation;

Utilize the ultraviolet laser of pattern sample to expose to described dyed layer, thereby form the exposure process of sub-image; With

The described dyed layer that is formed with sub-image is developed, thus the developing procedure of formation pattern.

6. pattern formation method according to claim 5, wherein, the exposure wavelength of described ultraviolet laser is the scope of 300nm～380nm.

7. pattern formation method according to claim 5, wherein, the pulse laser of described ultraviolet laser under the frequency of 20Hz～2000Hz, vibrating.

8. manufacturing method of color filter, it has the operation that forms pattern by the described pattern of claim 5 formation method on substrate.

9. color filter, it is for making by the described manufacture method of claim 8.

10. display device, it possesses the described color filter of claim 9.