CN101526761B

CN101526761B - Image forming method, color filter and display apparatus

Info

Publication number: CN101526761B
Application number: CN2009101185786A
Authority: CN
Inventors: 伊藤维成; 增田敏幸
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2008-03-07
Filing date: 2009-03-04
Publication date: 2013-05-08
Anticipated expiration: 2029-03-04
Also published as: JP5008590B2; KR20090096327A; JP2009216779A; CN101526761A

Abstract

The invention provides an image forming method, comprising an image forming procedure which exposes a light-sensitive resin layer formed on a substrate and develops with an aqueous alkali to form an image; a first cleaning procedure which substitutes the aqueous alkali retaining on the substrate formed with the image for cleaning; and a second cleaning procedure spraying the pure water to the cleaned image forming face to remove residues with the water pressure higher than the cleaning water pressure.

Description

Image forming method and color filter and display device

Technical field

The color filter and the display device that the present invention relates to the photo-sensitive resin after exposure is developed with aqueous slkali and form the image forming method of image and use this image forming method to form.

Background technology

In recent years, be used for the color filter of liquid crystal indicator etc. so that the Pigments resist-coating is grown up centered by the method for substrate.But, in the method, owing to using method of spin coating etc., so have the loss of Pigments resist many, also be difficult to control problem for the condition that evenly is coated with.As Qi Xie Decision means, proposed to use the method for the photosensitive transfer printing material with thermoplastic resin.

In the method for using photosensitive transfer printing material, owing to will be in advance evenly coating photo-sensitive resin (containing pigment and photoresist) transfer printing (laminated) on the temporary supporting body on desirable substrate, so can be as rotary coating, and loss photoresist in a large number not also can be formed uniformly thickness.In the method for using this photosensitive transfer printing material, by thermoplastic resin further is set on the temporary supporting body, photo-sensitive resin is followed be present in concavo-convex on substrate, thereby photo-sensitive resin can be kept certain by the thickness on substrate.At this moment, before the development of photo-sensitive resin, must remove thermoplastic resin, take the method (following sometimes this operation is called " PD operation ") of processing etc. with developer solutions such as 1% triethanolamine aqueous solution.

In addition, after removing thermoplastic resin, the non-exposure section (non-image section) of removing photo-sensitive resin in order to develop obviously changes pattern, further uses the development treatment (following sometimes this operation is called " CD operation ") of alkaline developer.As this alkaline developer, the alkaline developer (for example, referring to patent documentation 1) that contains carbonate and anionic surfactant is for example disclosed.

Also proposed following method: after photo-sensitive resin was developed, in photo-sensitive resin, contained composition residued on substrate as the development residue sometimes.Therefore, in order to remove this development residue, after developing procedure, use clean-out system (contain surfactant remove as the residual film of the development of principal ingredient use liquid), remove residue (below, sometimes this operation is called " SD operation ") by cleaning with the rotary brush wiping in this liquid.Thus, the development residue of the color filter of gained significantly reduces, and has improved the quality of color filter.

Recently, consider from the viewpoint that reduces costs, disperse resist to obtain the autofrettage (below, sometimes will use the coating of slit-shaped nozzle to be called " slot coated method ") of color filter of the saving fluidization of Pigments resist with slit-shaped nozzle coating pigment.Black pattern with or a part of material of using etc. of sept have problems such as easily producing striped with the slot coated method.Therefore, known have a following method: above-mentioned material is set, with the method for slot coated method setting material in addition on substrate with transfer printing.Thus, can throughput rate make well color filter.

[patent documentation 1] Japanese kokai publication hei 05-204164 communique

By importing the SD operation, although can significantly reduce the generation of development residue, substrate is tending towards maximizing in recent years, and is accompanied by the maximization of substrate as mentioned above, and the axial length of rotary brush also has the tendency of increase.Therefore, the weak easy residue of part of contact brush is removed insufficient, and the contact that brush might occur is uneven.Therefore, in the cleaning after development, need the at present higher brush management of ratio of precision.

Cleaning after development has also proposed the method for removing residue with high pressure jetting system injection waters such as UHV (ultra-high voltage) micro ejectors (high super pressure micro jet) except carrying out with above-mentioned rotary brush.For example, can be by at the amplitude direction of substrate a plurality of nozzles side by side, the inject high pressure pure water is removed residue, carries out thus removing of residue.But, at this moment, sometimes press unequal meeting because of the injection of each nozzle and cause producing the striated inequality on substrate.

In addition, form with transfer printing the material that black pattern or sept are used etc. as mentioned above, when forming material beyond it with the slot coated method, if residual development residue in the non-pixel region on the substrate that has formed image by transfer printing etc. can produce coating defects sometimes when being coated with subsequently.And then following problems is arranged: when forming sept, sept is uneven to be increased, and demonstration inequality that might be when making display device is relevant.

Summary of the invention

The present invention obtains in view of foregoing.Based on above-mentioned situation, need following image forming method, be about to develop when forming image, Yi Bian suppress the generation of development residue after the photo-sensitive resin exposure, inhibition development on one side waits the generation of the inequality after alkali treatment, thereby can form high-quality image (comprising color filter).In addition, need to reduce development residue and uneven high-quality color filter and display device.

the present invention has obtained following understanding: when the residue after developing is removed, carry out in advance following operation before with high-pressure injection device high-pressure injection pure water: lower than the hydraulic pressure that is produced by the high-pressure injection device, (for example water temperature is 5 ℃～40 ℃ namely to be not suitable for low-pressure that residue removes, the nozzle ejection angle is 0 °～180 °, and the distance of injection nozzle and real estate when being 50mm～250mm nozzle ejection press for 0.5MPa following) under, wash etc. with pure water stream and replace the aqueous slkali that residues on substrate, can reduce the generation of incidental inequality the process till removing to residue after photo-sensitive resin is developed, the present invention is based on above-mentioned cognition and obtains.

For the concrete means that reach above-mentioned problem as described below.

＜1〉a kind of image forming method, it has: image forms operation, and the photo-sensitive resin exposure that is formed at substrate is rear with the aqueous slkali development, forms image; The 1st matting residues in the aqueous slkali of the described image forming surface of the substrate that is formed with image with pure water displacement, clean with this; With the 2nd matting, the image forming surface of the described substrate of the high pressure of the hydraulic pressure with than described clean the time after the described cleaning further sprays pure water and removes residue, cleans with this.

＜2〉as above-mentioned＜1〉described image forming method, it is characterized in that, described photo-sensitive resin contains colorant, is colored the picture pattern that forms after painted as described image, forms with this color filter that is made of described picture pattern.

＜3〉as above-mentioned＜1〉or above-mentioned＜2 described image forming method, it is characterized in that, described image forms operation and comprises and use the transfer printing process that forms photo-sensitive resin in the photosensitive transfer printing material that has at least photo-sensitive resin on temporary supporting body transfer printing on described substrate, develops with aqueous slkali after transfer printing is formed at photo-sensitive resin exposure on substrate.

＜4〉in above-mentioned＜1 〉～＜3 in the described image forming method of any one, the aqueous slkali that photo-sensitive resin is developed preferably contains at least a kind in carbonate at least a kind and anionic surfactant.Carbonate contains at least a kind in sodium salt and sylvite, and the content sum of sodion and potassium ion is preferably 60 quality %～100 quality % with respect to the total cation in carbonate.

＜5〉in above-mentioned＜1 〉～＜4 in the described image forming method of any one, in the 1st matting, preferably take the nozzle ejection pressure below 0.5MPa (water temperature as 5 ℃～40 ℃, nozzle ejection angle as 0 °～180 °, injection nozzle and the distance of real estate clean as the pressure feed pure water of 50mm～250mm).

＜6〉in addition, in above-mentioned＜1 〉～＜5 in the described image forming method of any one, in the 2nd matting, preferably take the nozzle ejection pressure as more than 2MPa (water temperature as 5 ℃～40 ℃, nozzle ejection angle as 35 °～165 °, injection nozzle and the distance of real estate clean as the pressure injection pure water of 50mm～150mm).

＜7〉in above-mentioned＜1 〉～＜6 in the described image forming method of any one, in the 2nd matting, preferably the normal direction at the image forming surface of aforesaid substrate becomes with the angle that the injection direction of pure water forms ± cleans under the condition of 0 °～20 °.

＜8〉and then, in above-mentioned＜1 〉～＜7 in the described image forming method of any one in, following proposal more preferably: in the process of the supply of the pure water in carrying out the 1st matting, when the distance of injection nozzle and real estate is 50mm～250mm, nozzle ejection is pressed as below 0.5MPa, this moment, water temperature was 5 ℃～40 ℃, and the nozzle ejection angle is 0 °～180 °; In the process of the injection of the pure water in carrying out the 2nd matting, when the distance of injection nozzle and real estate was 50mm～150mm, nozzle ejection was pressed and is 3MPa～24MPa, and this moment, water temperature was 5 °～40 ℃, and the nozzle ejection angle is 35 °～165 °.

＜9〉a kind of color filter, it is to use above-mentioned＜2 〉～above-mentioned＜8〉the described image forming method formation of middle any one.

＜10〉a kind of display device, it has above-mentioned＜9〉described color filter.

According to the present invention, photo-sensitive resin is developed after exposure and when forming image, suppressing on one side the generation of development residue, suppress the generation of inequality developments grade alkali treatment after on one side, can provide to form the high-quality image image forming method of (comprising color filter).

In addition, according to the present invention, can provide and reduce development residue and uneven high-quality color filter and display device.

In the present invention, when particularly forming photo-sensitive resin with photosensitive transfer printing material by transfer printing, the raising of the crudy after realizing developing (residue or inequalities in the non-pixel section that reduces that being developed on substrate remove etc.).In addition, even the precision of the rotary brush when not strict control is used for cleaning also can obtain high-quality image (comprising color filter).

Embodiment

Below, describe image forming method of the present invention in detail, also color filter of the present invention and display device with this color filter are elaborated by this explanation.

＜image forming method 〉

Image forming method of the present invention arranges following operation and consists of: image forms operation, and the photo-sensitive resin exposure that is formed at substrate is rear with the aqueous slkali development, forms image; The 1st matting residues in the aqueous slkali of the described image forming surface of the substrate that is formed with image with pure water displacement, clean with this; With the 2nd matting, the image forming surface of the substrate of the high pressure of the hydraulic pressure with than described clean the time after the described cleaning further sprays pure water and removes residue, cleans with this.Can also have other operations as required.

In the present invention, photo-sensitive resin after exposure is developed with aqueous slkali and after forming image, to the substrate high-pressure injection pure water that is formed with image with the development residue of removing, clean image forming surface before, wash the aqueous slkali of the image forming surface that residues in substrate after development by using in advance pure water stream, be replaced into pure water (being to clean the two-stage), when removing residue with the high-pressure injection device afterwards, can be in the situation that keep the generation that the residue removability prevents from pressing because of injection uneven easily generation inequality.Thus, the residue of non-image section and the high-quality image (containing color filter) of the inequality in image can be reduced.

Need to prove the cleaning fluid of the residue (above-mentioned SD operation) after in the present invention, said aqueous slkali comprises be used to the alkaline developer of removing thermoplastic resin (above-mentioned PD operation), is used for removing the alkaline developer of photo-sensitive resin (above-mentioned CD operation) and is used for removing development.

Below, describe each operation that consists of image forming method of the present invention in detail.

[image formation operation]

Image forms in operation, develops to form image with aqueous slkali (the following developer solution that sometimes also simply is called) after the photo-sensitive resin that is formed at substrate is exposed.In this operation, after the photo-sensitive resin that will be formed at substrate as described below exposes, develop and remove the zone that is not exposed curing, desirable exposing patterns is obviously changed.

Develop to use aqueous slkali as developer solution, can be undertaken by impregnated in method in aqueous slkali or the spraying type treatment trough of spray aqueous slkali.Particularly preferably use the method that the spraying type treatment trough of a large amount of spray spouts is set above the conveying mechanism of conveying substrate.When using the spraying type treatment trough, photo-sensitive resin in short-term equably can develop.

As the nozzle of spraying type treatment trough, can enumerate flat burner, conic nozzle, indirect injection etc.Particularly by using the platypelloid type nozzle, effectively remove unexposed photoresist with the impulsive force energy demoulding ground of spray.

Usually be preferably scope near room temperature to 40 ℃ as the temperature of the aqueous slkali of developer solution.In addition, development herein is the development treatment photo-sensitive resin, but when using following photosensitive transfer printing material, also thermoplastic resin, middle layer and photo-sensitive resin once can be developed.The layer that when developing uneven and photo-sensitive resin development in order to reduce, developer solution causes is deteriorated, and after first thermoplastic resin and middle layer were removed in dissolving, the development of carrying out photo-sensitive resin was desirable.When carrying out the development of photo-sensitive resin after the development in thermoplastic resin and middle layer, preferably select the developer solution that does not make photo-sensitive resin deteriorated for the developer solution of removing thermoplastic resin and middle layer.Can consider thermoplastic resin and middle layer, select developer solution with the difference of the dissolution velocity of photo-sensitive resin, perhaps appropriate combination liquid temperature, spraying are pressed, the development treatment conditions such as pressure during wiping carry out the method.

Preferably contain at least a kind of carbonate and anionic surfactant at least a kind as being used for the develop aqueous slkali of developer solution of (CD operation) of photo-sensitive resin.

Above-mentioned carbonate preferably contains sodium salt and/or sylvite.Carbonate is sodium salt and/or sylvite, the damping fluid under the pH zone that can obtain at needs.In addition, can obtain low residue effect when the development of photo-sensitive resin.As the kation of carbonate, can contain other kations except sodion and potassium ion.As other kations, can enumerate lithium ion, alkaline-earth metal ion, ammonium ion.When containing as mentioned above the kation except sodion and potassium ion in carbonate, the content sum of sodion and potassium ion is preferably 60 quality %～100 quality % with respect to the total cation in carbonate, is more preferably 90 quality %～100 quality %.Carbonate is not only to contain for example lithium salts or ammonium salt, and when also containing sodium salt and/or sylvite, the good cushion effect under the pH zone that can obtain at needs can also obtain good low residue effect.

The concentration of the carbonate when photo-sensitive resin is developed (following sometimes be referred to as " concentration during development ") is preferably 0.04 mole/kg～0.5 mole/kg, is more preferably 0.06 mole/kg～0.5 mole/kg, most preferably is 0.08～0.4 mole/kg.During the development of carbonate concentration be 0.04 mole/when kg was above, low residue was respond well, be 0.5 mole/when kg is following, can be suppressed near the residual residual film in edge of image (for example colored pixels of color filter).

For developer solution, make the dope body according to the use state, in advance it is carried storage, it is desirable suitably being diluted on cost during use.From the point of view, state that consider to produce developer solution (followingly is called " concentration during preservation " with the concentration of the developer solution of this state sometimes.) time, during the preservation of carbonate, concentration is preferably 0.1 mole/kg～1.0 mole/kg.During the preservation of carbonate concentration be 0.1 mole/when kg is above, can obtain the low residue effect of non-image section and near the residual film inhibition image, simultaneously also favourable aspect cost, during the preservation of carbonate concentration be 1.0 moles/when kg is following, can suppresses Lose and send generation precipitate when preserving.Therefore, for developer solution, during preservation relative concentration concentration when developing be preferably 2～6 times, more preferably be 3～6 times, most preferably be 4～5 times.

During as the development of developer solution, the pH of concentration, be preferably pH9.3～10.9, is more preferably pH9.5～10.7, most preferably is pH9.7～10.6.PH is 9.3 when above, can accelerate developing powder, and throughput rate is good, in addition, can also obtain good cushion effect.In addition, pH is 10.9 when following, can obtain good residue removability, in addition, can also obtain good cushion effect.

As above-mentioned anionic surfactant, for example preferably enumerate naphthalene sulfonic acid derivant salt, polyoxyethylene naphthyl ether sulfate.

As above-mentioned naphthalene sulfonic acid derivant salt, preferably from the salt of naphthalene sulfonic acids and have at least a kind that selects the salt of alkyl naphthalene sulfonic acid of at least 1 alkyl.As the alkyl of alkyl naphthalene sulfonic acid, preferably can have carbon number and be 1～6 substituent alkyl, more preferably isopropyl, butyl, isobutyl, more preferably butyl.Replacement radix as the alkyl of alkyl naphthalene sulfonic acid is preferably 1～6, is more preferably 1～3.As the concrete example of naphthalene sulfonic acid derivant, can enumerate naphthalene sulfonic acids, dibutyl naphthalene sulfonic acid, dibutyl naphthalene sulfonic acids, tributyl naphthalene sulfonic acids.

Above-mentioned naphthalene sulfonic acid derivant salt can use separately respectively a kind, and also two or more kinds may be used, but preferred also with more than 2 kinds.In addition, as naphthalene sulfonic acid derivant salt, particular certain cancers and/or sylvite.

Developer solution can contain with glassware for drinking water has blended organic solvent as other compositions.

As with glassware for drinking water, the organic solvent of miscibility being arranged, for example can enumerate methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, diacetone alcohol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl-n-butyl ether, benzylalcohol, acetone, MEK, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, 1-METHYLPYRROLIDONE.There is the concentration of organic solvent in developer solution of miscibility to be generally 0.1 quality %～40 quality % with glassware for drinking water.

In addition, when using photosensitive transfer printing material, the alkali treatment (PD operation) that can be provided for as required developing before above-mentioned CD operation and remove thermoplastic resin and middle layer.

The solution that preferably contains alkanolamine as the aqueous slkali of the developer solution that is used for the PD operation particularly preferably contains the solution of triethanolamine and/or diethanolamine.

And then, when using photosensitive transfer printing material in image formation operation of the present invention, after the development (CD operation) of above-mentioned photo-sensitive resin, can further be provided for carrying out the alkali treatment (SD operation) that residue is removed.Usually use in the aqueous slkali of this moment and contain surfactant as the alkaline cleaner that is used for removing the development residue of principal ingredient.

Alkaline cleaner as being used for removing the development residue preferably contains the alkaline solution that is selected from least a surfactant in alkynes class surfactant, alkyl ether surfactant, phenoxy group oxygen base alkylene base class surfactant, naphthalene class surfactant.

Image of the present invention forms in operation, before above-mentioned development, the exposure process that the photo-sensitive resin on substrate is exposed into desirable pattern-like can be set.Below, exposure process is described.

In exposure process, be pattern-like (pattern exposure) with the photo-sensitive resin that is formed on substrate via the mask exposure of stipulating.The light source that is used for pattern exposure is selected according to the photonasty of photo-sensitive resin.For example, can use the known light sources such as ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp, argon laser.As described in Japanese kokai publication hei 6-59119 communique, the transmittance that may be used the above wavelength region may of 400nm is the optical filter below 2% etc.Exposure during pattern exposure is preferably 200mJ/cm ²Following scope is more preferably 150mJ/cm ²Following scope, preferred scope is 100mJ/cm ²～40mJ/cm ²Particularly exposure is 150mJ/cm ²When following, be desirable aspect shortening the productive temp time (tact time).

Image of the present invention forms in operation, and the operation that forms as being exposed the photo-sensitive resin of object can be set before above-mentioned exposure process.In this operation, can with coating be used to form photo-sensitive resin coating fluid method or use the photosensitive transfer printing material that has photo-sensitive resin on the temporary supporting body to come any method in the method for transfer printing to form photo-sensitive resin through exposure imaging.In image forming method of the present invention, consider for the minimizing effect that improves the development residue and the effect of the generation of image inequality when preventing from carrying out high-pressure injection is effective aspect, the preferred situation that adopts the transfer printing process with photosensitive transfer printing material transfer printing formation photo-sensitive resin to carry out.

Photosensitive transfer printing material and to be used to form the details of each composition of coating fluid of photo-sensitive resin as described below.

Carry out in the situation that utilize transfer printing, fit (laminated) in real estate by the surface that for example makes on the temporary supporting body photo-sensitive resin that stacks gradually the photosensitive transfer printing material that thermoplastic resin, middle layer, photo-sensitive resin form from this temporary supporting side, strip the temporary supporting body, thereby can transfer printing form photo-sensitive resin on substrate.At this moment; usually after removing the protective film that sets in advance for the photo-sensitive resin of protecting photosensitive transfer printing material; the surface of the photo-sensitive resin removing and expose is coincided with real estate pressurize, heat, thus photosensitive transfer printing material is fitted in real estate.Can use the known laminating machinees such as laminating machine, vacuum laminator and surface trimming laminating machine (Auto-cutlaminator) in applying.The surface trimming laminating machine can further be boosted productivity.

After stripping the temporary supporting body it being fitted, mask and thermoplastic resin and middle layer via regulation arrange exposure process same as described above, thus the photo-sensitive resin exposure are pattern-like.

Image of the present invention forms in operation, as image, forming 1 look or the colored pattern more than 2 looks (for example colored pixels) that is colored as RGB etc. on substrate, can form the color filter that is made of this picture pattern thus.That is, at this moment, image forming method of the present invention can be as the manufacture method of the color filter of making color filter.

When making color filter, the colored pixels such as RGB can form by the transfer printing that forms photo-sensitive resin with above-mentioned photosensitive transfer printing material transfer printing.Wherein, the viewpoint of the coating defects when preventing to be coated with considers, after preferably using photosensitive transfer printing material to form the light-shielding pattern of black matrix" etc., the operation through form photo-sensitive resin by coating forms.At this moment, the side that is formed with the light-shielding patterns such as black matrix" on substrate, the photo-sensitive resin that is used to form colored pixels from the coating of the top of above-mentioned light-shielding pattern forms the coating fluid of use, develops, exposes, and forms thus colored pixels.When for example forming the colored pixels of red (R), green (G), blue (B), for example at first be coated with the coating fluid that is used to form red pixel, and after making its drying, carry out pattern exposure, development and heat treated, form red pixel, then similarly form green pixel, blue pixel.Next, the substrate that will be formed with light-shielding pattern and all colored pixels (being RGB herein) heats again, can obtain color filter thus.

In addition, use photosensitive transfer printing material further to be formed for remaining the spacer material of predetermined distance with color filter with the distance of the substrate of its subtend configuration on the color filter that forms.

In such scheme, can be coated with coating fluid with known rubbing method, such as enumerating method of spin coating, rolling method, ink-jet method, slot coated method, slit rotary process etc.In above-mentioned rubbing method, from reducing the viewpoint of fluid loss, preferably use the rubbing method of slot coated device.As the method, can be referring to the method for the use slit-shaped nozzle of record in the paragraph [0023] of TOHKEMY 2006-23696 communique.The thickness of the light-shielding pattern on the bed thickness counterpart substrate of the photo-sensitive resin that forms with rubbing method is set.

[the 1st matting]

In image forming method of the present invention, carry out following the 2nd matting that residue removes with the high-pressure injection device before, following the 1st matting is set, namely residue in the pure water displacement aqueous slkali that above-mentioned image forms the image forming surface of the substrate that forms image in operation, clean (following also referred to as washing drip washing) with this.Cleaning in the 1st matting is as following the 2nd matting, pure water is supplied in to be not suitable for removing the pressure that residues in the residue on substrate after development the image forming surface of substrate carries out.

If remove residue with the high-pressure injection device under the state of the composition of residual alkali solution on substrate, easily produce uneven, so by remaining in aqueous slkali on substrate with pure water washing drip washing at least, can prevent when guaranteeing the residue removability due to the residual inequality that causes of aqueous slkali after developing.

Method as washing drip washing, so long as the low-pressure that is not suitable for removing the residue on substrate, preferably take the nozzle ejection pressure below 0.5MPa (this moment water temperature as 5 ℃～40 ℃, nozzle ejection angle as 0 °～180 °, injection nozzle and the distance of real estate as the pressure of 50mm～250mm) is supplied to pure water the method for the image forming surface of substrate, just can be not particularly limited.Particularly, can enumerate pure water is sprayed to the method for substrate or substrate is immersed in method pure water etc. from spray spout or gap nozzle.In the present invention, preferably use the method for the spraying type treatment trough that a large amount of spray spouts are set on the conveying mechanism of conveying substrate.

Nozzle for spray can be selected arbitrarily in not producing uneven scope, but from preventing the nozzle form of the preferred energy wide-angle of uneven viewpoint ground ejection.In order to make water be dispersed throughout equably the integral body of real estate, the injection nozzle that preferably spreads to spray with the fan type can separately or be arranged a plurality of these injection nozzles and clean on fan-shaped dispersal direction.

[the 2nd matting]

The image forming surface of the substrate of the 2nd matting after to be the high pressure of the hydraulic pressure with than the cleaning in the 1st matting the time finish to clean in above-mentioned the 1st matting further sprays pure water and removes residue, cleans with this.

In injection pure water in this operation, as long as be the pressure higher than the hydraulic pressure in the 1st matting, but considering needs and can spray to remove the pressure that residues in the residue on substrate in this operation, for example preferably when water temperature be that 5 ℃～40 ℃, nozzle ejection angle are the distance of 35 °～165 ° and injection nozzle and real estate when being 50mm～150mm, press in nozzle ejection and spray pure water for the image forming surface to substrate under the pressure more than 2MPa.The defective etc. of pixel never occurs, the viewpoint that can remove residue is considered, more preferably nozzle ejection is pressed and is 2MPa～34MPa, is particularly preferably 3MPa～24MPa.

As the high-pressure injection device, preferred UHV (ultra-high voltage) micro ejector.The UHV (ultra-high voltage) micro ejector refers to that the voltage that applies on real estate is generally 20kgf/cm ²～350kgf/cm ²(1.9～34.3MPa), be preferably 30kgf/cm ²～250kgf/cm ²(3.9kgf/cm ²～24.5MPa) thrower.Exert pressure and select according to the shape of nozzle, in the present invention preferred opal type nozzle (section is the concavees lens shape).

The jet angle of UHV (ultra-high voltage) micro ejector is the parameter of considerable influence washing effect, to the jet angle on the surface of photo-sensitive resin during for vertical (90 °) residue to remove effect the strongest.On the other hand, for the removing of non-exposure section, only the residue effect of removing is by force inadequate, must remove composition not from substrate with the water slug of machinery.For this reason, the injection direction of pure water is that vertical (90 °) are best with respect to substrate, but can be also ± 0～20 ° of left and right with the normal direction of substrate and the formed angle initialization of injection direction of pure water, the direct of travel of substrate from pure water the place ahead of water spot spray or rearward spray.

Embodiment as economy, in fact adopt continuous washing, but this moment is in order to make water spread all over equably at the Width of photo-sensitive resin, the following method of preferred employing is carried out continuous washing and is processed, the injection nozzle that namely sprays in order to the expansion of fan type separately or arrange a plurality of nozzles on fan type dispersal direction, at the injection direction with respect to this sector shape be on the direction at right angle on one side constant speed move the photoresist spout part by water on one side.The high-pressure injection device that can obtain above-mentioned injection pressure, angle of attack, dispersion of flow shape etc., effect of the present invention can be enumerated the superhigh pressure jetting precision cleaning AF of system series (Asahi Sunac (strain) system).Wherein, be used for the injection of relatively high pressure, AF5400S or AF6200SW are fit to, and are used for the injection of relatively low pressure, and AF2800II is fit to.So long as have the device of above-mentioned injection seal pressurization, angle of attack and dispersion of flow shape etc., just this instrument kind is not limited, can be suitable for the cleaning means as this operation.

in the present invention, from keeping the removability of development residue on one side, inequality after suppressing on one side to develop occurs, form the viewpoint of high-quality image (containing color filter), preferred following situation: (water temperature is 5 ℃～40 ℃ at injection nozzle in the supply of the pure water in above-mentioned the 1st matting, the nozzle ejection angle is 0 °～180 °) and the distance of real estate when being 50mm～250mm nozzle ejection press as carrying out under the following pressure of 0.5MPa, (water temperature is 5 ℃～40 ℃ to injection pure water in above-mentioned the 2nd matting at injection nozzle, the nozzle ejection angle is 35 °～165 °) and the distance of real estate when being 50mm～150mm nozzle ejection press as under the pressure of 3MPa～24MPa and carry out.

As image forming method of the present invention, can after forming operation and matting, above-mentioned image carry out as required post-exposure or rear roasting (heat treated).Operation till being transferred to rear roasting can be referring to paragraph [0067]～[0069] of TOHKEMY 2005-3861 communique, record [0072]～[0074] as preference.

As the image that is formed by image forming method of the present invention, can enumerate the light-shielding pattern such as colored pattern (such as colored pixels), black matrix" of red (R), green (G) and blue (B) etc. and light spacer etc.But, in the present invention, be not limited thereto.

(photosensitive transfer printing material)

Next, schematic illustration is used to form the photosensitive transfer printing material of photo-sensitive resin.

Photosensitive transfer printing material preferably sets gradually thermoplastic resin, middle layer and photo-sensitive resin from this temporary supporting side and the transfer materials that obtains on the temporary supporting body.The Production Example of photosensitive transfer printing material is carried out as the operation of record in paragraph [0064]～[0066] that TOHKEMY 2005-3861 communique can be set.

-temporary supporting body-

As the temporary supporting body of photosensitive transfer printing material, even preferably have pliability, the temporary supporting body of remarkable distortion, contraction or elongation does not occur under pressurization or pressurization and heating yet.As the example of this temporary supporting body, can enumerate pet film, cellulose triacetate film, plasticon, polycarbonate film etc., wherein biaxial stretch-formed pet film particularly preferably.

-thermoplastic resin-

Thermoplastic resin in photosensitive transfer printing material has resiliency, make exist on the surface as the substrate of transfer printing body can follow when concavo-convex concavo-convex.

As the composition that consists of this thermoplastic resin, the polymer of putting down in writing in preferred Japanese kokai publication hei 5-72724 communique is particularly preferably approximately to select the polymer below 80 ℃ from the softening point that obtains with dimension card ViCat method (the polymkeric substance softening point measurement method of particularly carrying out with U.S. material test method(s) ASTMD ASTMD1235).

particularly, can enumerate tygon, the polyolefin such as polypropylene, ethene and vinyl-acetic ester or its saponified etc. ethylene copolymer, ethene and acrylate or it is saponified, Polyvinylchloride, vinyl chloride and vinyl-acetic ester and saponified etc. vinyl chloride copolymer thereof, Vingon, metachloroethylene copolymer, polystyrene, styrene and (methyl) acrylate or its saponified etc. styrol copolymer, polyvinyl toluene, vinyltoluene and (methyl) acrylate or its saponified etc. vinyl toluene copolymer, poly-(methyl) acrylate, (methyl) acrylate copolymers such as (methyl) butyl acrylate and vinyl-acetic ester, vinyl-acetic ester multipolymer nylon, copolymer nylon, N-alkoxy methyl nylon, the organic polymers such as polyamide such as N-dimethylamino nylon.

-middle layer-

During for the coating that prevents a plurality of coating layers and the purpose of mixing of the composition the during preservation after coating, the middle layer is set in photosensitive transfer printing material preferably.As the middle layer, the oxygen separation layer with oxygen isolation features of putting down in writing as " separating layer " in preferred Japanese kokai publication hei 5-72724 communique.At this moment, the sensitivity during exposure improves, and the time load of exposure machine reduces, and throughput rate improves.

As above-mentioned oxygen separation layer, preferred demonstration is hanged down oxygen permeability, is dispersed or dissolved in the oxygen separation layer in water or aqueous alkali, can suitably select from known oxygen separation layer.In above-mentioned oxygen separation layer, particularly preferably combination contains the layer of polyvinyl alcohol (PVA) and polyvinylpyrrolidone.

-photo-sensitive resin-

When photo-sensitive resin required the light-proofness of black matrix" etc., the layer that can form with the coloured composition put down in writing in the light sensitive black resin bed put down in writing in TOHKEMY 2005-3861 communique or TOHKEMY 2004-240039 communique etc. was identically formed.In addition, when forming the colored pattern (such as the colored pixels that consists of color filter etc.) of red (R), green (G), blue (B) etc., can be identically formed with the layer that the photosensitive composition put down in writing in TOHKEMY 2006-23696 communique forms.

The photo-sensitive resin that is used to form the colored pattern of RGB etc. can form by coating on the temporary supporting body coating fluid of use etc. and form corresponding to the photo-sensitive resin of red (R), green (G) and blue desirable form and aspect such as (B).Be used for the modulation photo-sensitive resin form use coating fluid colorant as shown below.About coating process as mentioned above.

Colorant is selected pigment, dyestuff etc. arbitrarily according to the form and aspect of the colored pixels such as RGB.As colorant, can use redness, green, blueness, yellow, purple, magenta, glaucous known pigment and dyestuff.as preference, can enumerate Victoria blue BO (C.I.42595), auramine (C.I.41000), Monolight yellow GT (C.I. pigment Yellow 12), permanent yellow GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), forever consolidate pink FBB (C.I. pigment red 146), Clariant type paratonere (Hostaperm red) ESB (C.I. pigment violet 1 9), Permanent ruby FBH (C.I. paratonere 11), Faster pink B spra (C.I. pigment red 81), and Monastral Fast Blue (C.I. pigment blue 15).In addition, as the pigment that is particularly suitable for forming color filter, can enumerate C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 168, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. pigment red 21 5, C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment blue 15: 1, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 64, C.I. pigment yellow 13 9, C.I. pigment yellow 83, C.I. pigment Violet 23 etc.

Above-mentioned pigment and dyestuff preferably have pigment and the dyestuff of the following mean grain size of 5 μ m usually, are preferably below 1 μ m.When forming color filter, preferred mean grain size is below 0.5 μ m.

-protective film-

Pollution or damage when preserving in order to exempt from preferably arrange thinner protective film on the photo-sensitive resin on the temporary supporting body.Protective film can be by forming with the same or similar material of temporary supporting body, but use can be easily from the material of photo-sensitive resin separation.

As the material for the protection of film, for example silicon paper, polyolefin piece or teflon plate are fit to.

(substrate)

As substrate, be not particularly limited, can select from glass plate, resin film-making or the known base material such as film, resin-coated paper according to desirable.Wherein, the substrate of preferably clear is such as enumerating the known glass plates such as the soda-lime glass plate that has the monox tunicle on the surface, low-expansion glass, alkali-free glass, quartz glass plate or plastic sheeting etc.

Aforesaid substrate can make connecting airtight well between photosensitive polymer combination or photosensitive transfer printing material by implementing in advance coupling processing.As coupling processing, the method for putting down in writing in preferred TOHKEMY 2000-39033 communique.

In addition, the thickness as substrate is not particularly limited, but common preferred 700 μ m～1200 μ m, particularly preferably 500 μ m～1100 μ m.

＜color filter 〉

Color filter of the present invention is that the image forming method by the invention described above forms, and has the picture pattern that is colored, and can on this picture pattern, sept be set.Because color filter of the present invention forms by image forming method of the present invention, as mentioned above, carrying out for 2 stages cleans, the 1st matting with the aqueous slkali on pure water displacement substrate namely is set in advance, so have the high-quality of the inequality that reduced in the image or the height inequality in picture element flaw and sept before the 2nd matting of high-pressure injection pure water.

＜display device 〉

Display device of the present invention has the color filter of the invention described above, in addition is not particularly limited, and comprises the display device such as liquid crystal indicator, plasma scope display device, EL display device, CRT display device etc.

About the definition of display device and the explanation of each display device, such as being documented in " electronic console equipment (the clear husband's work of assistant 々 wood, the meeting of (strain) census of manufacturing, nineteen ninety distribution) ", " display apparatus (she blows along chapter work, industry books (strain) and puts down into distribution in the first year) " etc.

In display device of the present invention, liquid crystal indicator particularly preferably.About liquid crystal indicator, for example be documented in " inferior generation LCD Technology (Uchida Tatsuo edits, the meeting of (strain) census of manufacturing, 1994 the distribution) " in.Liquid crystal indicator is not particularly limited, and for example can use the liquid crystal indicator of the variety of way of record in above-mentioned " inferior generation LCD Technology ".The present invention is in above-mentioned display device, particularly the liquid crystal indicator of colored TFT mode is effective.Liquid crystal indicator about colored TFT mode for example is documented in " in color TFT-LCD display (vertical publication (strain) altogether, distribution in 1996).And then the pixel partitioning scheme such as transverse electric field type of drive, MVA that also can use IPS etc. etc. has enlarged the liquid crystal indicator of angle of visibility.About aforesaid way, for example be documented in " the up-to-date trend in EL, PDP, LCD display technology technology and market (eastern beautiful research centre investigation department, calendar year 2001 distribution) " 43 pages.

Liquid crystal indicator also is made of various parts such as electrode base board, polarization film, phase-contrast film, backlight, sept, view angle compensation films except being made of color filter.For above-mentioned parts, for example be documented in " market of ' 94 liquid crystal display periphery material chemical productss (island Itou Kentaro, (strain) CMC, distribution in 1994) ", " present situation in 2003 liquid crystal connection markets and prospect (last volume) in the future (show good Ji, (strain) Chimera of Fuji always grind, distribution in 2003) ".

display device of the present invention can adopt ECB (Electrically ControlledBirefringence), TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optically CompensatoryBend), STN (Supper Twisted Nematic), VA (Vertically Aligned), HAN (Hybrid Aligned Nematic), GH (Guest Host) and so on various display modes.

Display device of the present invention has color filter of the present invention, thereby can prevent that the demonstration when carrying in televisor, watch-dog is uneven, can broad color reproduction zone and the high-contrast of performance, also can be preferred for notebook computer with in the display device of the large picture such as display and televisor watch-dog etc.

[embodiment]

Below, be described more specifically the present invention by embodiment, but only otherwise exceed its purport, the present invention just is not limited to following examples.Need to prove, as long as no special record, " part " expression quality criteria.

(embodiment 1)

[making of color filter]

＜1. the modulation of photonasty heavy colour composition 〉

The modulation of-carbon black dispersion liquid (K-1)-

Use refiner under the condition of 3000rpm, following each composition to be stirred 1 hour.The mixed solution of gained is implemented 8 hours loose processing of differential with the pearl dispersion machine that uses 0.3mm zirconium pearl (trade name: DISPERMAT, GETZMANN society system), obtain carbon black dispersion liquid (K-1).

＜form

Carbon black (Color black FW2, Degussa society system) ... 26.7 part

Spreading agent (Disparlon DA7500 acid number 26 amine values 40, nanmu originally change into (strain) system)

3.3 part

Methacrylic acid benzyl ester/methacrylic acid (=72/28[mol ratio]) multipolymer (50 quality % solution of molecular weight 30,000, propylene glycol monomethyl ether) ... 10 parts

Propylene glycol monomethyl ether ... 60 parts

Use the carbon black dispersion liquid (K-1) of gained, with the formula modulation photonasty heavy colour composition CK-1 of following table 1.The unit of the numerical value in table 1 is " part ".

[table 1]

The details of each composition in above-mentioned table 1 is as described below.

Resin solution C-2: methacrylic acid benzyl ester/methacrylic acid (=85/15 mol ratio) multipolymer (50 quality % solution of Mw10000, propylene glycol monomethyl ether)

UV curable resin C-3: trade name " Cyclomer P ACA-250 " contest road chemical industry (strain) system (acrylic copolymer, the propylene glycol monomethyl ether solution (solid constituent: 50 quality %)) that have alicyclic ring, COOH base and acryloyl group on side chain

Polymerizable compound C-5: trade name " TO-1382 " East Asia synthetic (strain) system

(take the part with the end OH base of dipentaerythritol five acrylate be substituted by the COOH base have 5 officials can the monomer of acryloyl group as major component.)

Initiating agent C-7: trade name " OXE-02 " Ciba society system

Surfactant C-8: large Japanese ink chemical industry (strain) system of trade name " MEGAFAC R30 "

Solvent: PGMEA=propylene glycol monomethyl ether

EEP=3-ethoxyethyl group propionic ester

＜2. utilize coating and the formation black matrix" 〉

The formation of-photonasty heavy colour composition layer-

Use slot coated device (model HC6000, Hirata Spinning Ltd.'s system), the photonasty heavy colour composition CK-1 of gained is coated on glass substrate (healthy and free from worry society MILLENNIUM thickness processed is 0.7mm), regulate interval, spray volume between slit and glass substrate, making the thickness after rear roasting is 1.2 μ m, is coated with second with coating speed 120mm/.

-preroast, exposure-

Then, use hot plate, after carrying out the heating (preroast processings) of 120 seconds under 90 ℃, use Millar spray regime exposure machine (model MPA-8000, society of Canon Co., Ltd system) is with 100mJ/cm ²Expose.

-develop-

Then, spray is installed with is decided to be 0.20MPa, developed 60 seconds with 1.0% developer solution (1 part of CDK-1 and 99 parts of liquid that the pure water dilution obtains, 25 ℃) of potassium hydroxide class developer solution CDK-1 (Fuji's electronic material (strain) system).Then, with the pure water of 25 ℃ of platypelloid type nozzle (110 ° of pressure 0.05MPa, jet angles) sprays 20 seconds, pixel from from this nozzle to the colour filtering chip basic board that leaves real estate 150mm forms top blast and send, and the mode of washing with pure water stream is replaced developer solution and the cleaning fluid on colour filtering chip basic board.Then, use UHV (ultra-high voltage) micro ejector (injection precise purging system AF series A F6200SW (Asahi sunac (strain) system)), under the pressure of 4MPa, the distance high-voltage of the pure water of 25 ℃ from the real estate 100mm that leaves colour filtering chip basic board sprayed 15 seconds, remove the residue that the pixel that remains in colour filtering chip basic board forms face, obtain black matrix pattern.

-roasting-

Then, with calcination process after the cleaning oven of 220 ℃ 40 minutes, the thickness that forms opening that colored pixels forms the zone and be 90 μ m * 200 μ m, black matrix" was that the live width of 1.2 μ m, black matrix" is the about clathrate black matrix substrate of 25 μ m.Use X-Rite 361T (V) (SAKATA INXENG (strain) system), measure the optical concentration (OD) of the black matrix" that forms, result is 4.2.

＜3. the modulation of photosensitive coloring composition 〉

The modulation of-3-1. red (R) use photosensitive coloring composition CR-1-

Use refiner under the condition of 3000rPm, each composition of following composition to be stirred 1 hour.With the mixed solution of gained with use 0.3mm zirconium pearl pearl dispersion machine (trade name: DISPERMAT, GETZMANN society system) implement 4 hours loose processing of differential, obtain redness (R) with dispersion liquid (R-1).

＜form

Paratonere 254 (mean grain size under SEM observes is 43nm) ... 11 parts

Paratonere 177 (the mean grain size 58nm under SEM observes) ... 4 parts

Following dispersion resin A-3 ... 5 parts

Spreading agent (trade name: Disperbyk-161, BYK society system)

(30% solution of propylene glycol monomethyl ether) ... 3 parts

Alkali soluble resin: methacrylic acid benzyl ester/methacrylic acid copolymer

(=75/25[mol ratio] multipolymer, molecular weight 30,000, propylene glycol monomethyl ether solution (solid constituent: 50 quality %)) ... 9 parts

Solvent B: propylene glycol monomethyl ether ... 68 parts

Use the redness (R) of gained with dispersion liquid (R-1), modulate the redness (R) of following composition and use photosensitive coloring composition CR-1.

＜form

Above-mentioned redness (R) dispersion liquid (R-1) ... 100 parts

Epoxy resin (trade name: EHPE3150, contest road chemical industry society system) ... 2 parts

Polymerizable compound: dipentaerythritol five or six acrylate ... 8 parts

Polymerization initiator: 4-(o-bromo-p-N, N-two (ethoxy carbonyl methyl) amino-phenyl)-2,6-two (trichloromethyl)-S-triazine ... 1 part

Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1 ... 1 part

Polymerization initiator: diethyl thioxanthone ... 0.5 part

Polymerization inhibitor: p-metoxyphenol ... 0.001 part

Fluorine class surfactant (trade name: Megafac R30, large Japanese ink chemical industry society system) ... 0.01 part

Non-ionics (trade name: Tetronic R150, ADEKA society system) ... 0.2 part

Solvent: propylene glycol n-butyl ether acetic acid esters ... 30 parts

Solvent: propylene glycol monomethyl ether ... 100 parts

The modulation of-3-2. green (G) use photosensitive coloring composition CG-1-

Use refiner under the condition of 3000rPm, each composition of following composition to be stirred 1 hour.The mixed solution of gained is implemented 8 hours loose processing of differential with the pearl dispersion machine that uses 0.3mm zirconium pearl (trade name: DISPERMAT, GETZMANN society system), obtain green (G) with dispersion liquid (G-1).

Pigment green 36 (the mean grain size 47nm under SEM observes) ... 11 parts

Pigment yellow 150 (the mean grain size 39nm under SEM observes) ... 7 parts

Following dispersion resin A-3 ... 5 parts

Spreading agent (trade name: Disperbyk-161, BYK society system, 30% solution) ... 3 parts

Alkali soluble resin: methacrylic acid benzyl ester/methacrylic acid copolymer

(=85/15[mol ratio] polymkeric substance, molecular weight 30,000, propylene glycol monomethyl ether solution (solid constituent: 50 quality %)) ... 11 parts

Solvent: propylene glycol monomethyl ether ... 70 parts

Use the green (G) of gained to use photosensitive coloring composition CG-1 with the green (G) of the following composition of dispersion liquid (G-1) modulation.

Above-mentioned green (G) dispersion liquid (G-1) ... 100 parts

Epoxy resin: (trade name) EHPE3150 (contest road chemical industry society system) ... 2 parts

Polymerizable compound: dipentaerythritol five or six acrylate ... 8 parts

Polymerizable compound: four (epoxy acrylate) of pentaerythrite ... 2 parts

The two trihalomethyl groups of polymerization initiator: 1,3--5-benzo tetrahydrofuran triazine ... 2 parts

Polymerization initiator: diethyl thioxanthone ... 0.5 part

Polymerization inhibitor: p methoxy phenol ... 0.001 part

Fluorine class surfactant (trade name: Megafac R08, large Japanese ink chemical industry society system) ... 0.02 part

Non-ionics (trade name: Emulgen A-60, Hua Wangshe system) ... 0.5 part

Solvent: propylene glycol monomethyl ether ... 120 parts

Solvent: propylene glycol n-propyl ether acetic acid esters ... 30 parts

The modulation of-3-3. blue (B) use photosensitive coloring composition CB-1-

Use refiner under the condition of 3000rPm, each composition of following composition to be stirred 1 hour.The mixed solution of gained is implemented 4 hours loose processing of differential with the pearl dispersion machine that uses 0.3mm zirconium pearl (trade name: DISPERMAT, GETZMANN society system), obtain blueness (B) with dispersion liquid (B-1).

＜form

Pigment blue 15: 6 (mean grain size under SEM observes is 55nm ... 14 parts

Pigment Violet 23 (mean grain size under SEM observes is 61nm) ... 1 part

Following dispersion resin A-3 ... 5 parts

Alkali soluble resin: methacrylic acid benzyl ester/methacrylic acid copolymer ... 4 parts

(=80/20[mol ratio] multipolymer, molecular weight 30,000, propylene glycol monomethyl ether solution (solid constituent: 50 quality %))

Solvent: propylene glycol monomethyl ether ... 73 parts

Use the blueness (B) of gained with dispersion liquid (B-1), modulate the blueness (B) of following composition and use photosensitive coloring composition CB-1.

＜form

Above-mentioned blueness (B) dispersion liquid (B-1) ... 100 parts

Alkali soluble resin: methacrylic acid benzyl ester/methacrylic acid copolymer ... 7 parts

Epoxy resin: Celloxide 2080 (trade names; Contest road chemical industry society system) ... 2 parts

UV curable resin: Cyclomer PACA-250 (trade name; Contest road chemical industry society system)

(have alicyclic ring, COOH base, and acrylic copolymer, the propylene glycol monomethyl ether solution (solid constituent: 50 quality %) of acryloyl group on side chain ... 4 parts

Polymerizable compound: dipentaerythritol five or six acrylate ... 12 parts

Polymerization initiator: 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-1-(adjacent acetyl group oximido) ethyl ketone ... 3 parts

Polymerization inhibitor: p methoxy phenol ... 0.001 part

Non-ionics (trade name: EmulgenA-60, Hua Wangshe system) ... 1.0 part

Solvent: 3-ethoxyl ethyl propionate ... 20 parts

Solvent: propylene glycol monomethyl ether ... 150 parts

＜4. dispersion resin A-3's is synthetic 〉

(1. chain-transferring agent A3's is synthetic)

Make 7.83 parts of dipentaerythritols six (3-mercaptopropionic acid ester) (DPMP; Sakai chemical industry (strain) system) (following compound (33)) and the 4.55 parts following compound (m-6) that has adsorption site and have a carbon-to-carbon double bond is dissolved in 28.90 parts of propylene glycol monomethyl ether, flows down at nitrogen and is heated to 70 ℃.Add wherein 0.04 part 2, two (2,4-dimethyl-penten acyl group) (the pure pharmaceutical worker's industry of V-65 and light (strain) systems) of 2 '-azo group heated 3 hours.And then, add 0.04 part of V-65, flow down at nitrogen, make its reaction 3 hours under 70 ℃.Till being cooled to room temperature, obtain thus 30% solution of mercaptan compound shown below (chain-transferring agent A3).

(1/3.5 adds adult)

(2. dispersion resin A-3's is synthetic)

The mixed solution of 30% solution of 4.99 parts of chain-transferring agent A3 that obtain as mentioned above, 19.0 parts of methyl methacrylates, 1.0 parts of methacrylic acids and 4.66 parts of propylene glycol monomethyl ether is flowed down at nitrogen be heated to 90 ℃.Stir this mixed solution on one side, on one side splashed into 2 through 2.5 hours, the mixed solution that 0.139 part of the two isobutyric acid dimethyl ester (the pure pharmaceutical worker's industry of V-601 and light (strain) system) of 2 '-azo group, 5.36 parts of propylene glycol monomethyl ether and propylene glycol monomethyl ether are 9.40 parts.After splashing into end, making its reaction after 2.5 hours under 90 ℃, drop into 0.046 part 2, the mixed solution of the two isobutyric acid dimethyl esters of 2 '-azo group and 4.00 parts of propylene glycol monomethyl ether further makes its reaction 2 hours.Add 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether in reactant liquor, be cooled to room temperature, obtain thus the solution (specific dispersion resin as 30 quality %, propylene glycol monomethyl ether as 21 quality %, propylene glycol monomethyl ether as 49 quality %) of specific dispersion resin A-3 (take the weight-average molecular weight of polystyrene conversion as 24000).

The acid number of this specific dispersion resin A-3 is 48mg/g.The structure of dispersion resin A-3 as shown below.

The making of＜color filter 〉

The formation of-photosensitive coloring composition layer-

The redness (R) of gained is formed the face side with the black matrix" that photosensitive coloring composition CR-1 is coated on above-mentioned black matrix substrate.Particularly, identical with the situation that forms photonasty heavy colour composition layer, regulate interval, spray volume between slit and black matrix substrate, the bed thickness that makes the photosensitive coloring composition layer after rear roasting is about 2.1 μ m, is coated with second take coating speed as 120mm/.

-preroast, exposure-

Then, use hot plate, after carrying out the heating (preroast processings) of 120 seconds under 100 ℃, use Millar ink-jetting style exposure machine (model MPA-8000, Canon Co., Ltd's system) is with 90mJ/cm ²Expose.In addition, set mask pattern and exposure machine, making the coincidence (exposure coincidence amount) of exposing patterns and black matrix" is 8.0 μ m.

-develop, roasting-

Then, spray is installed with is decided to be 0.2MPa, with lower the development 45 seconds of 1.0 quality % developer solutions (1 part of CDK-1,99 parts of liquid that the pure water dilution obtains, 25 ℃) of potassium hydroxide class developer solution CDK-1 (Fuji's electronic material (strain) system).Then, with the pure water of 25 ℃ of platypelloid type nozzle (pressure is that 0.05MPa, jet angle are 110 °) sprays 20 seconds, the pixel formation face of the colour filtering chip basic board from this nozzle to distance real estate 150mm blows, with developer solution and the cleaning fluid on pure water stream filter wash color chips displacement substrate.Then, use UHV (ultra-high voltage) micro ejector (injection precise purging system AF series, AF6200SW (Asahi sunac (strain) system)), spray the pure water 15 seconds of 25 ℃ from the distance high-voltage of the real estate 100mm that leaves colour filtering chip basic board under the pressure of 4MPa, remove the residue that the pixel that remains in colour filtering chip basic board forms face.Then, with roasting after the peace and quiet baking oven of 220 ℃ 30 minutes, form the red pixel after thermal treatment finishes.

Then, except redness (R) is replaced with green (G) with photosensitive coloring composition CG-1 with photosensitive coloring composition CR-1, carry out successively in the same manner formation, preroast, exposure, development and the roasting of above-mentioned photosensitive coloring composition layer, form green pixel.And then except redness (R) is replaced with blueness (B) with photosensitive coloring composition CB-1 with photosensitive coloring composition CR-1, operation in the same manner forms blue pixel, obtains the color filter that is formed by the RGB3 look.

Next, further form the transparency electrode of ITO (Indium Tin Oxide) with sputter on red pixel, green pixel and the blue pixel of the color filter of gained and black matrix".Below, be referred to as " colour filtering chip basic board ".

[making of sept]

＜sept the making of photosensitive transfer film 〉

Be the upper thermoplastic resin coating fluid that is formed by following formula A that is coated with of pet film temporary supporting body (PET temporary supporting body) of 75 μ m at thickness, make its drying, forming dry bed thickness is the thermoplastic resin of 16.5 μ m.

(the thermoplastic resin formula A of coating fluid)

Methyl methacrylate/acrylic acid 2-Octyl Nitrite/methacrylic acid benzyl ester/methacrylic acid (=55/11.7/4.5/28.8[mol ratio], weight-average molecular weight 90,000) multipolymer ... 25.0 part

Styrene/acrylic (=63/37[mol ratio], weight-average molecular weight 8,000) multipolymer ... 58.4 part

Two (4-(methacryl polyethoxy) phenyl) propane of 2,2-... 39.0 part

Following surfactant 1 ... 10.0 part

Methyl alcohol ... 90.0 part

The 1-methoxy-2-propanol ... 51.0 part

Methyl ethyl ketone ... 700 parts

* surfactant 1

Following works 1 ... 30%

Methyl ethyl ketone ... 70%

Works 1

(n＝6、x＝55、y＝5、

Mw＝33940、Mw/Mn＝2.55

PO: epoxypropane, EO: oxirane)

Then, coating by the middle layer coating fluid that following formula B forms, makes its drying on the thermoplastic resin that forms, and stacked dry bed thickness is the middle layer of 1.5 μ m.

(the middle layer formula B of coating fluid)

Polyvinyl alcohol (PVA) ... 3.22 part

(PVA-205, saponification rate 80%, (strain) Kuraray system)

Polyvinyl pyrrolidone ... 1.49 part

(PVP K-30, ISPJAPAN (strain) system)

Methyl alcohol ... 42.3 part

Distilled water ... 524 parts

Then, further coating by the photo-sensitive resin coating fluid that the formula C1 shown in following table 2 forms, makes its drying on the middle layer that forms, and stacked dry bed thickness is the photo-sensitive resin of 4.1 μ m.

[table 2]

The photo-sensitive resin formula of coating fluid	C1
		Pigment	60
1-methoxyl-2-propyl-acetic acid ester	452
		MEK	285
Methyl alcohol	0.035
		Bonding agent-1	92
DPHA liquid	91
		Two (the trichloromethyl)-6-[4-(N, N-di ethoxy carbonyl methyl) of 2,4--3-bromophenyl]-s-triazine	2.1
Hydroquinone monomethylether	0.035
		Surfactant 2	0.83
The colour killing dyestuff	17
		Meter	1000

Need to prove, the details that each in the described formula of above-mentioned table 2 forms is as follows.

* pigment

30% methyl isobutyl ketone dispersion of silicon dioxide gel (trade name: MIBK-ST, daily output chemical industry (strain) system)

* bonding agent 1

Methacrylic acid/allyl methacrylate copolymer (=20/80[mol ratio], quality mean molecular weight 36000)

* DPHA liquid (polymerizable monomer)

Dipentaerythritol acrylate ... 76 parts

(trade name: KAYARAD DPHA, Japanese chemical drug (strain) system)

Propylene glycol monomethyl ether ... 24 parts

* colour killing dyestuff

Victoria blue BO H-M (hodogaya chemical (strain) system)

* surfactant 2

C ₆F ₁₃CH ₂CH ₂OCOCH=CH ₂(40 parts) and H (O (CH ₃) CHCH ₂) ₇OCOCH=CH ₂(55 parts) and H (OCH ₂CH ₂) ₇OCOCH=CH ₂Multipolymer (the weight-average molecular weight: 30,000) of (5 parts) ... 30 parts

Methyl ethyl ketone ... 70 parts

As previously discussed, after consisting of the stepped construction (the total bed thickness of 3 layers is 22.1 μ m) of PET temporary supporting body/thermoplastic resin/middle layer/photo-sensitive resin, further heating the thickness that pressurizes as cover film on the surface of photo-sensitive resin is the polypropylene made membrane of 12 μ m, fit, make the sept photosensitive transfer film.

The making of＜sept 〉

The sept cover film of photosensitive transfer film of peeling off gained, the surface of the photo-sensitive resin that will expose overlaps on the ITO film of the film formed colour filtering chip basic board of sputtering ITO of above-mentioned making, use laminating machine LamiCII type ((strain) イ of Hitachi Application ダストリイズ system), under line pressure 100N/cm, the pressurized, heated condition of 130 ℃ to make its applying in transmission speed 2m/ minute.Then, PET temporary supporting body is being removed with peeling off at the interface of thermoplastic resin, with photo-sensitive resin transfer printing together with thermoplastic resin and middle layer.

Then, use has the proximity type exposure machine (development of (strain) large Japanese section) of ultrahigh pressure mercury lamp, mask (the quartzy exposed mask with picture pattern) with so that the colour filtering chip basic board almost parallel that the relative mode of this mask and thermoplastic resin configures under the state that stands vertically, distance between the surface of the side that contacts with the middle layer of mask face and photo-sensitive resin is set as 40 μ m, is 60mJ/cm via mask from the thermoplastic resin side take exposure ²Approach exposure.

Then, triethanolamine class developer solution (is contained 30% triethanolamine, the liquid that trade name: T-PD2 (with Fujiphoto (strain) system) dilution 12 times (ratio of 1 part of T-PD2 and 11 parts of pure water is mixed) is obtained with pure water) under 30 ℃, flat burner sprays and presses as spray under the condition of 0.04MPa developed 50 seconds, removes thermoplastic resin and middle layer (PD operation).Then, after blow air is broken liquid above this glass substrate, spray pure water with spray thrower and carried out pure water drip washing in 10 seconds, blow air reduces the hydrops on substrate.

Then, use sodium carbonate class developer solution (sodium carbonate, 5% nekal, anionic surfactant, defoamer, and the stabilizing agent that contain sodium bicarbonate, 0.47 mol/L of 0.38 mol/L; The liquid that trade name: T-CD1 (Fujiphoto (strain) system) is obtained with 10 times of pure water dilutions) under 29 ℃, the platypelloid type nozzle ejection presses as spray under the condition of 0.15MPa developed 30 seconds, obtains the pattern image (CD operation) of sept.

Then, use (contains non-ionics defoamer stabilizing agent with clean-out system; Trade name: T-SD3 (Fujiphoto (strain) system)) liquid that obtains with 10 times of pure water dilutions, press as spray under the condition of 0.02MPa sprayed 20 seconds at 33 ℃, platypelloid type nozzle ejection, the residue of the periphery of the pattern image that forms is removed (SD operation).

After the end residue is removed, the pure water of 25 ℃ are sprayed 20 seconds with platypelloid type nozzle (110 ° of pressure 0.05MPa, jet angles), pixel from from this nozzle to the colour filtering chip basic board that leaves real estate 150mm forms top blast and send, and replaces with the developer solution on stream filter wash color chips substrate and the mode of cleaning fluid with pure water.Then, use UHV (ultra-high voltage) micro ejector (injection precise purging system AF series A F6200SW (Asahi sunac (strain) system)), under the pressure of 8MPa, the pure water of 25 ℃ was sprayed for 15 seconds from the distance high-voltage of the real estate 100mm that leaves colour filtering chip basic board, remove the residue on the pixel formation face that remains in colour filtering chip basic board, obtain spacer patterns.

Then, the colour filtering chip basic board that is provided with spacer patterns is carried out 30 minutes heat treated (rear roasting) under 230 ℃, form sept.

[making of liquid crystal indicator]

Use has formed the colour filtering chip basic board of sept, on the position of the black matrix" housing that the mode that is equivalent to surround around the pixel groups of color filter arranges, be coated with the sealant of ultraviolet curable resin by the divider mode, drip MVA pattern liquid crystal, after fitting with counter substrate, the substrate of fitting is carried out the UV irradiation, and then thermal treatment makes sealant cures.Paste the polaroid HLC2-2518 that Japanese San-ritz Co., Ltd. makes on the two sides of the liquid crystal cells that obtains like this, then, consist of the backlight of cold-cathode tube, be disposed at the back side one side of the liquid crystal cells that is provided with polarization plates, make liquid crystal indicator.

(embodiment 2)

In " making of sept " of embodiment 1, when the liquid that use obtains 10 times of T-SD3 dilutions with pure water carries out removing of residue, use has the rotary brush of nylon hair, the wiping spacer patterns carries out residue and removes, in addition, operate in the same manner with embodiment 1, form sept, further make liquid crystal indicator.

(comparative example 1)

In " making of sept " of embodiment 1, the liquid that use obtains 10 times of T-SD3 dilutions with pure water is removed the residue of pattern image periphery, after this EO without developer solution and cleaning fluid on pure water displacement substrate, but utilize the high-pressure injection pure water to remove residue on colour filtering chip basic board, in addition, make in the same manner with embodiment 1, form sept, further make liquid crystal indicator.

(comparative example 2)

In " making of sept " of embodiment 2, after end is used and with pure water, 10 times of liquid that obtain of T-SD3 dilution is removed residue, without developer solution and the cleaning fluid on pure water displacement substrate, but high-pressure injection pure water, remove the residue on colour filtering chip basic board, in addition, operate in the same manner with embodiment 2, form sept, further make liquid crystal indicator.

(estimating 1)

In the making of the sept in above-described embodiment and comparative example, the development inequality that produces when developing is observed in visual check, and a situation arises, use simultaneously the residue of observation by light microscope sept periphery, a situation arises for the defective of pixel (damaged or uneven), estimate according to following metewand.

Evaluation result is shown in following table 3.

＜metewand 〉

A: have no the generation of residue, picture element flaw fully.

B: the generation of slight visible residue, picture element flaw.

C: slightly see the generation of residue, picture element flaw.

D: the more generation of seeing residue, picture element flaw.

E: in the generation of the place of arrival of pixel visible residue, picture element flaw.

[table 3]

	Develop uneven (1)	Develop uneven (2)	The development residue	Picture element flaw
					Embodiment 1	-	A	B	B
Embodiment 2	B	A	A	B
					Comparative example 1	-	D	B	C
Comparative example 2	C	C	B	C

Develop uneven (1): be considered to the strip that causes with brush uneven

Develop uneven (2): be considered to the twill-like inequality that high-pressure injection causes

As shown in Table 3 above, before spraying pure water by the high-pressure injection device, the developer solution on substrate and clean-out system are replaced in the embodiment of pure water, inequality and development residue, picture element flaw can suppress to develop.And in comparative example, particularly observe the inequality that generation causes with high-pressure injection, also poor aspect picture element flaw.

(estimating 2)

Use the liquid crystal indicator of making in embodiment 1～2 and comparative example 1～2, relatively come the liquid crystal indicator of Evaluation operation example with the liquid crystal indicator of comparative example, confirm to show good display characteristic.

Its integral body of the disclosure of Japanese publication 2008-057730 adds in this instructions by reference.

In record all documents, patented claim and technical specification in this manual, add each document, patented claim and technical specification to be and add in this instructions by reference to the situation equal extent of record respectively particularly by reference.

Claims

1. image forming method, it has:

Image forms operation, and the photo-sensitive resin exposure that is formed at substrate is rear with the aqueous slkali development, forms image;

The 1st matting, press as below 0.5MPa in nozzle ejection, residue in the aqueous slkali of the described image forming surface of the substrate that is formed with image with the pure water displacement, clean with this, at this moment, the distance of injection nozzle and real estate is that 50mm～250mm, water temperature are 5 ℃～40 ℃; With

The 2nd matting, the image forming surface of the described substrate take the nozzle ejection pressure as 3MPa～24MPa after the described cleaning further sprays pure water and removes residue, clean with this, at this moment, the distance of injection nozzle and real estate is that 50mm～150mm, water temperature are 5 ℃～40 ℃.

2. image forming method as claimed in claim 1, wherein, described photo-sensitive resin contains colorant, as described image, forms the picture pattern after painted, forms with this color filter that is made of described picture pattern.

3. image forming method as claimed in claim 1, wherein, described image forms operation and comprises that following use forms the transfer printing process of photo-sensitive resin in the photosensitive transfer printing material that has at least photo-sensitive resin on temporary supporting body transfer printing on described substrate, develop the photo-sensitive resin exposure that transfer printing is formed on substrate afterwards with aqueous slkali.

4. image forming method as claimed in claim 1, wherein, the aqueous slkali that described photo-sensitive resin is developed contains at least a kind in carbonate at least a kind and anionic surfactant.

5. image forming method as claimed in claim 4, wherein, described carbonate contains at least a kind in sodium salt and sylvite, and the content sum of sodion and potassium ion is 60 quality %～100 quality % with respect to the total cation in carbonate.

6. image forming method as claimed in claim 1 wherein, in described the 2nd matting, becomes with the formed angle of the injection direction of pure water in the normal direction of the image forming surface of described substrate ± cleans under the condition of 0 °～20 °.