CN102471625A

CN102471625A - Ink, reverse printing process, liquid crystal color filter, and process for production of liquid crystal color filter

Info

Publication number: CN102471625A
Application number: CN2010800341576A
Authority: CN
Inventors: 岩本雅子; 近藤康彦; 真木贵史; 汤川光好; 小林博; 葭田荣治; 斋藤文宏
Original assignee: Sumitomo Rubber Industries Ltd; Tokyo Printing Ink Mfg Co Ltd
Current assignee: Sumitomo Rubber Industries Ltd; Tokyo Printing Ink Mfg Co Ltd
Priority date: 2009-11-06
Filing date: 2010-10-28
Publication date: 2012-05-23
Anticipated expiration: 2030-10-28
Also published as: KR20120093136A; CN102471625B; KR101606235B1

Abstract

Provided is an ink for use in a reverse printing process which comprises transferring an ink layer lying on a silicone blanket to an intaglio printing plate and then printing the thus-formed prescribed ink pattern on a substrate. An ink comprising a binder resin, a coloring matter, and a solvent, wherein the solvent contains 5 to 50% by mass (relative to the total amount of the solvent) of a low-tension solvent that has a boiling point of 50 to 150 DEG C and a surface tension (at 25 DEG C) of 12 to 21mN/m and 0.01 to 10% by mass (relative to the total amount of the ink) of a fluorine-containing surfactant that exhibits a solubility (at 23 DEG C) of 10g/100g or less in the low-tension solvent.

Description

The method of manufacture of printing ink, reversal printing method, liquid crystal color filter and liquid crystal color filter

Technical field

The present invention relates to a kind of printing ink that is used for the reversal printing method, use the method for manufacture of reversal printing method, liquid crystal color filter and the liquid crystal color filter of this printing ink.

Background technology

The liquid crystal color filter that LCD (Liquid Crystal Display, liquid-crystal display) possesses substrate and on this substrate, forms.Liquid crystal color filter comprises color filter layer, black matrix layer etc.Liquid crystal color filter obtains through the fine pattern that on almost whole of substrate, forms colored ink and black ink.In the past, adopted the formation method of so-called photolithography as liquid crystal color filter.

But in recent years, the intaglio offset print process replaces photolithography and popularizes and come.Compare with photolithography, the intaglio offset print process can reduce the waste of process number and materials used, also can reduce consumed energy.Its result can form ink logo at short notice expeditiously.

In the intaglio offset print process, for example, printing ink is filled in the recess of intaglio plate, makes printing ink in the recess be transferred to the surface of printing blanket.Then, will be transferred to substrate (being printed thing) surface again attached to the lip-deep printing ink of printing blanket.So just on substrate surface, form the ink logo of regulation.

Yet, in the intaglio offset print process, because printing ink is by 2 transfer printings, thereby printing ink all can takes place during each transfer printing and separate.The printing ink separation is meant that printing ink is separated into part that is transferred on the transfer printing target compound and the phenomenon of staying the part on the transfer printing source.Therefore, finally be transferred to and have big concavo-convex of difference of height in the ink logo on the substrate surface as separating traces and residual.Its result, there is the big tendency of thickness deviation in the ink logo that forms on the substrate surface.

So, in order to make the color depth homogeneous that reaches in each pixel between each pixel, the print process of the liquid crystal color filter of homogeneous thickness is arranged as forming requirement, replace the intaglio offset print process, developed reversal printing method (patent documentation 1～3).

In the reversal printing method, for example through inking is gone up and on the printing rubber blanket surface, seamlessly formed ink lay (whole ink lay) to roughly whole of printing rubber blanket.Then, this ink lay is contacted with the intaglio plate surface of the recess with predetermined pattern, be transferred to the part beyond the upper recess of intaglio plate surface.Like this, optionally with ink lay from the printing rubber blanket surface removal, on the printing rubber blanket surface, form the corresponding ink logo of pattern with the intaglio plate recess.And this ink logo is transferred on the substrate surface.So just form the ink logo of regulation at substrate surface.

In the reversal printing method, be 1 time during from the printing rubber blanket surface transfer to substrate surface for forming the required printing ink transfer printing number of times of ink logo.Therefore, compare with the intaglio offset print process, the reversal printing method can be dwindled the concavo-convex difference of height that remains in the ink logo surface.Its result can dwindle the thickness deviation of ink logo.

As printing rubber blanket, its surface is widely used by the silicon blanket that Zylox forms at least.The silicon blanket is excellent because of the printing ink release, thereby can improve the transfer printing property of printing ink from its surface to substrate surface.

Yet the printing ink wettability of silicon blanket surface is low.Therefore, on printing rubber blanket, form in the process of ink lay, when printing ink was applied on the silicon blanket surface, the printing ink that coats was prone to by the offset plate exclusion.Its result promptly enables to form the ink lay of homogeneous thickness, but because the repulsion of printing ink, exists ink lay problems such as irregular, pin hole to occur.

Therefore, to have discussed in order obtaining the silicon blanket is had concurrently the printing ink of appropriate wettability and release and the boiling point of contained solvent in ink surface tension, the printing ink and printing ink to have been adjusted swelling rate of Zylox etc.

In addition, also expect such effect, promptly; Printing rubber blanket is through reducing ink surface tension; By so-called from the levelling effect, ink lay is dry to the ink logo that is transferred to substrate surface from forming in the silicon blanket surface, during the solidified, the further homogenization of ink logo thickness.

In order to reduce ink surface tension, can consider to use separately as n-hexane, Virahol, contain the low solvent (following claim sometimes " low-tension solvent ") of surface tension such as fluorous solvent or with other solvents and usefulness.Also can consider in printing ink to add tensio-active agents such as silicon class tensio-active agent, fluorochemical surfactant (referring to patent documentation 5～6 etc.).

Patent documentation

Patent documentation 1: the spy opens flat 11-58921 communique

Patent documentation 2: the spy opens flat 11-198337 communique

Patent documentation 3: the spy opens the 2000-289320 communique

Patent documentation 4: the spy opens the 2006-111725 communique

Patent documentation 5: the spy opens the 2005-126608 communique

Patent documentation 6: the spy opens the 2005-128346 communique

Summary of the invention

Yet general low-tension solvent is because polarity is low, thereby low to the solvability of the high polar binder resin that uses in the printing ink.Therefore, use the low-tension solvent separately or when the system middle and high concentration with other solvents and usefulness uses the low-tension solvent, have the situation that can not make the binder resin excellent dissolution.Its result, solid substances such as binder resin are separated out as foreign matter in printing ink easily.

And, because the cause of the foreign matter of separating out has the problem that lengthwise streaking on whole the ink lay that is formed at silicon blanket (silicone blanket) surface, occurs.And because the cause of this lengthwise streaking, also have the problem that the shape of ink logo gets muddled.

In the reversal printing method; In order on the silicon blanket surface, to form whole ink lay; For example, can use the slit mouth mould coating machine (slit die coater) etc. of band slit, said slit have with the corresponding width of this ink lay width and with the corresponding interval of this ink film thickness.

The limit makes the silicon blanket rotate with certain speed, and the printing ink of specified amount is supplied with on the limit continuously to the silicon blanket surface through the slit of slit mouth mould coating machine.Thus, on the surface of silicon blanket, form have with the corresponding width of slit width and with whole ink lay of the corresponding thickness of slit separation.

Yet if having foreign matter to separate out in the printing ink, slit can partly be stopped up by foreign matter.Therefore, the supply meeting of printing ink is hindered in the subregion of the width of slit.Its result in the ink lay that is formed at the silicon blanket surface, can produce lengthwise streaking with the corresponding position of being stopped up by foreign matter of part.In addition, because the ink film thickness deviation that lengthwise streaking causes etc., the shape of ink logo can get muddled.

In addition, shown in patent documentation 4 example, the most boiling point of low-tension solvent is low or flash-point is low.Therefore, when in printing ink, adding the low-tension solvent, the anxiety of the safety issue of appearance is arranged also.

In addition, low-boiling low-tension solvent volatilizees from printing ink easily.Therefore, for example, when forming ink lay, also exist to occur lengthwise streaking, irregular etc. easily, or cause the disorderly problem of ink logo shape because of lengthwise streaking, spot etc. easily with slit mouth mould coating machine etc.

Promptly; When use contains the printing ink of low, the volatile low-tension solvent of boiling point; Even not having foreign matter during ink formulation separates out; Forming in the process of ink lay with slit mouth mould coating machine etc. times without number, cause ink setting and aggegation along with the volatilization of low-tension solvent, solid substance such as binder resin is separated out as foreign matter easily in the printing ink.And because slit is partly stopped up by foreign matter, the supply of printing ink is hindered in the subregion of the width of slit.Its result in the ink lay that is formed at the silicon blanket surface, can produce lengthwise streaking with the corresponding position of being stopped up by foreign matter of part.

In addition, do not separate out and follow foreign matter to separate out the lengthwise streaking of generation, the rising of ink viscosity is also arranged and cause ink lay irregular anxiety to occur even there is foreign matter.In addition, because this irregular ink film thickness deviation that causes etc., can the getting muddled in shape etc. of ink logo.

And,, also can suppress the generation of aforementioned variety of issue even it is proportional then to reduce containing of low-tension solvent if contain tensio-active agent in the solvent.

As tensio-active agent, to compare with silicon class tensio-active agent, fluorochemical surfactant is excellent on this aspect of effect that reduces ink surface tension.

Yet; Research according to the present inventor; It is difficult that the printing ink that will contain fluorochemical surfactant is coated on the silicon blanket surface equably, on the silicon blanket surface, forms the ink lay of no lengthwise streaking, irregular, pin hole etc., uniform in thickness and is not easy.

Main purpose of the present invention provide a kind of to the silicon blanket surface have appropriate wettability and release concurrently, be not prone to safety issue and lengthwise streaking, the printing ink that is used for the reversal printing method of problem such as irregular and use the reversal printing method of this printing ink.

In addition, other purposes of the present invention provide a kind of have no irregular and pinprick etc., the color filter layer of uniform in thickness and the liquid crystal color filter and the method for manufacture thereof of black matrix layer.

The reversal printing method of the present invention that is used to achieve the above object is that a kind of ink lay that is used for the silicon blanket is transferred to intaglio plate, will be printed onto the printing ink of the reversal printing method that is printed on the body by this ink logo that is transferred to the regulation that the ink lay on the intaglio plate constitutes with printing ink; It is characterized in that; The said printing ink that is used for the reversal printing method contains binder resin, tinting material and solvent; Said solvent contains with the ratio of 5～50 quality % that are equivalent to said solvent total amount and has 50 ℃～the low-tension solvent of 150 ℃ of boiling points and 12mN/m～21mN/m surface tension (25 ℃), and contains the fluorochemical surfactant of solubleness (23 ℃) below 10g/100g to said low-tension solvent with the ratio of 0.01～10 quality % of the said total ink that is equivalent to be used for the reversal printing method.

According to the present invention, containing of low-tension solvent is proportional little, particularly, it is controlled at 5～50 quality % that are equivalent to the solvent total amount.Thus, reversal printing method of the present invention can have the wettability and the release of appropriateness to the silicon blanket surface concurrently with printing ink.Its result can suppress the generation of safety issue and lengthwise streaking, problem such as irregular.

Among the present invention; As notion more specifically, it can be the reversal printing method that comprises following operation that the ink logo of the regulation that the ink lay of silicon blanket is transferred on the intaglio plate, will be made up of the said ink lay that is transferred on this intaglio plate is printed onto the reversal printing method that is printed on the body: make the ink lay that on almost whole of silicon blanket surface, forms and surface have the operation that contacts with the said surface of the version of the corresponding recess of ink logo of regulation; Said ink lay beyond the said recess is transferred on the said surface of said version, removes from the said surface selectivity ground of said silicon blanket thus, thereby form on the said surface of said silicon blanket and the operation of the corresponding ink logo of said recess; After forming said ink logo, said ink logo is printed onto the operation that is printed the surface.In addition, surface tension (25 ℃) and the surface tension synonym in the time of 25 ℃.

In addition, the boiling point of low-tension solvent is 50 ℃～150 ℃.Therefore,, use binder resin is had excellent deliquescent solvent, can prevent conscientiously that lengthwise streaking and inhomogenous generation and consequent ink logo shape are disorderly as the solvent beyond the low-tension solvent.

As stated, reversal printing method of the present invention with printing ink in, mainly be that low-tension solvent equal solvent is working to keep the wettability of printing ink to the silicon blanket surface.

On the other hand, fluorochemical surfactant self is good not as solvent and silicon class tensio-active agent to the wettability of silicon blanket surface.And, in the past, generally used in the fluorochemical surfactant those tensio-active agents to the favorable solubility of low-tension solvent in the printing ink etc.This is because thus, fluorochemical surfactant is dispersed in the printing ink equably, the homogeneity of raising printing ink.

Yet,, have solvent the good wettability of silicon blanket to be received the anxiety of fluorochemical surfactant obstruction if fluorochemical surfactant is dispersed in the printing ink equably.Thus, the tendency that exists printing ink integral body that the wettability of silicon blanket surface is reduced on the contrary.

In addition, fluorochemical surfactant shown in its name, with the interface of silicon blanket or substrate, or, reduce the surface tension of printing ink through the activity that improves printing ink on the surface of ink lay or ink logo (the printing ink liquid level is promptly with the interface of air).Therefore, as just do not make the fluorochemical surfactant segregation at the interface, it is dispersed on the printing ink equably, even then add fluorochemical surfactant, the surface tension of printing ink is fully reduced.Its result, aforementioned also insufficient from levelling effect etc.

Therefore, only in printing ink, use fluorochemical surfactant, be difficult to form in the silicon blanket surface have homogeneous thickness, the ink lay of even pin hole etc. invariably.In addition, owing to can not make ink film thickness homogenization and the cause that can not obtain fully, can not form ink logo at substrate surface with homogeneous thickness from levelling effect etc.

For this reason; Reversal printing method of the present invention with printing ink in; As previously mentioned; Said solvent contains fluorochemical surfactant to be equivalent to said reversal printing method with the ratio of 0.01～10 quality % of the total amount of printing ink, said fluorochemical surfactant to the solubleness (23 ℃) of said low-tension solvent below 10g/100g.

Because fluorochemical surfactant below 10g/100g, thereby can not make fluorochemical surfactant be dispersed in the printing ink equably to the solubleness (23 ℃) of said low-tension solvent, but makes its segregation in printing ink.

Therefore, printing ink is just arranged by solvent the wettability of silicon blanket surface.So, though contain fluorochemical surfactant, but still can suppress the reduction of the whole wettability of printing ink.Its result can make printing ink keep well the silicon blanket surface is had concurrently the wettability of appropriateness and the state of release.

In addition, as previously mentioned, fluorochemical surfactant is low to the wettability of silicon blanket, and therefore, segregation is in away from the ink lay of silicon blanket surface and the near surface of ink logo.In addition, after ink logo was transferred to substrate surface, segregation was in the near surface away from the ink logo of substrate surface.

Therefore,, can reduce the surface tension of printing ink well, manifest effectively from levelling effect etc. through the fluorochemical surfactant of segregation.Its result not only can make the ink film thickness homogenization, and can form the ink logo with homogeneous thickness at substrate surface.

Here, fluorochemical surfactant to the solubleness (23 ℃) of low-tension solvent when being meant fluorochemical surfactant below the 10g/100g at 23 ℃ to the solubleness of low-tension solvent 100g below 10g.

In addition, reversal printing method of the present invention with printing ink in, said low-tension solvent preferably has the fluorochemical surfactant of the surface tension (25 ℃) of 12mN/m～18mN/m.

Fluorine-containing solvent does not have flash-point basically, is flame retardant resistance.Therefore, can give printing ink with flame retardant resistance.Its result can further improve security.

In addition, the surface tension (25 ℃) that contains fluorous solvent is 12mN/m～18mN/m.Therefore, through regulating the whole surface tension of printing ink, can give printing ink well with wettability and release to the appropriateness of silicon blanket surface.

In addition, reversal printing method of the present invention with printing ink in, the said fluorous solvent that contains is preferably hydrogen fluorine ethers and/or hydro fluorocarbons.

In addition, reversal printing method of the present invention with printing ink in, said fluorochemical surfactant preferably has 6000～80000 weight-average molecular weight Mw.

In addition, reversal printing method of the present invention with printing ink in, said fluorine surfactant is preferably nonionic class tensio-active agent.

In addition, reversal printing method of the present invention preferably has surface tension (25 ℃) and the following viscosity (25 ℃) of 5mPaS below the 22m/Nm with printing ink.

In addition; The ink lay that reversal printing method of the present invention has the silicon blanket is transferred to the operation on the intaglio plate and is being printed the operation of printing the ink logo of the regulation that is made up of the said ink lay that is transferred on this intaglio plate on the body; It is characterized in that said ink lay forms with printing ink with reversal printing method of the present invention.

According to reversal printing method of the present invention, use printing ink of the present invention and adopt the reversal printing method, can form have homogeneous thickness, the ink lay of even pinprick etc. invariably.Therefore, adopt reversal printing method of the present invention, can obtain having thickness evenly, the liquid crystal color filter of color filter layer and the black matrix layer etc. of even pinprick etc. invariably.

Promptly; Liquid crystal color filter of the present invention has the liquid crystal color filter of transparency carrier, color filter layer and black matrix layer; It is characterized in that; Said color filter layer and said black matrix layer are formed on the said transparency carrier, and said color filter layer and/or said black matrix layer form through reversal printing method of the present invention.

In addition, the method for manufacture of liquid crystal color filter of the present invention has the operation that on transparency carrier, forms color filter layer and/or black matrix layer, it is characterized in that, forms said color filter layer and/or said black matrix layer through the described reversal printing method of claim 7.

According to the present invention, can provide a kind of to the silicon blanket surface have concurrently appropriateness wettability and release, be not prone to safety issue and lengthwise streaking, problem such as irregular the reversal printing method with printing ink and the reversal printing method of using this printing ink.

In addition, a kind of possess no irregular and pinprick etc., the color filter layer of uniform in thickness and the liquid crystal color filter and the method for manufacture thereof of black matrix layer can also be provided.

Description of drawings

Fig. 1 (a)～(c) is for to illustrate the synoptic diagram as the reversal printing method of an embodiment of the present invention by process sequence, and Fig. 1 (a) is the painting process of printing ink, and Fig. 1 (b) is the operation of removing of printing ink, and Fig. 1 (c) is a printing process.

Fig. 2 is the significant points expansion sectional drawing as the liquid crystal color filter of an embodiment of the present invention.

Embodiment

< printing ink >

Printing ink of the present invention is to be employed printing ink in the reversal printing method of printing rubber blanket with the silicon blanket, contains binder resin, tinting material and solvent.

As binder resin, for example can be vibrin, vinyl resin, TKK 021, polyvinyl butyral acetal, polyester-melamine resin, melamine resin, epoxy-melamine resin, resol, polyimide resin, epoxy resin etc.These resins can use separately or share more than 2 kinds.

Wherein, especially consider the weather resistance that improves liquid crystal color filter that LCD uses etc.,, preferably have the binder resin of thermoset, ultra-violet solidified, light solidified etc. as binder resin.Particularly, preferred polyester-melamine resin, epoxy-melamine resin, vinyl resin, especially preferred polyester-melamine resin.

The molecular weight of used binder resin is for example preferably more than 1000, especially preferably more than 5000, and preferably below 40000, especially below 20000.

The molecular weight of binder resin can use the weight-average molecular weight Mw that is converted into polystyrene standard that for example records through gel permeation chromatography (GPC) method to represent.The molecular weight of binder resin can be done suitable setting according to rerum naturas such as desired viscosity of printing ink and thixotroping viscosity in above-mentioned scope.

The addition of binder resin and the molecular weight of binder resin are same, can set according to rerum naturas such as desired viscosity of printing ink and thixotroping viscosity are suitable.For example, the addition of binder resin preferably accounts for more than the 3 quality % of total ink, especially preferably more than 5 quality %, and preferably below 25 quality %, especially preferably below 20 quality %.

As tinting material, can be various pigment, dyestuff.Especially ought be under the situation of the liquid crystal color filter used of LCD, consider to form ink logo with excellent chemical-resistant, thermotolerance, weathering resistance, photostabilization etc., as tinting material, preferred organic type of pigment and mineral-type pigment.

When printing ink that printing ink is used for the color filter layer that forms liquid crystal color filter,, can be the corresponding to pigment of tone with each color filter layer of red (R), green (G) and blue (B) as pigment.

Pigment is used in formation as the red color filter layer, for example can be diketopyrrolopyrroles pigment, quinacridine ketone pigment (for example, dimethylquinacridone, dichloro quinacridone etc.), anthraquinone class pigment etc.

Pigment is used in formation as the green color filter layer, for example can be cupric bromide phthalocyanine (C.I. pigment green 36), chlorinated copper phthalocyanine halogenated phthalocyanines classes such as (C.I. pigment Green 7s etc.) pigment etc.

Pigment is used in formation as blue color filter layer, for example can be phthalocyanine pigment etc.

These redness, green and blue pigments can use separately or share more than 2 kinds by the tone of color filter layer of all kinds.

In addition; When printing ink that printing ink is used for the black matrix layer that forms liquid crystal color filter; As pigment, for example can be that carbon black, titanium are black, red stone, ferric sulfate, chromic oxide, cupric oxide, composite oxides (Cr-Co-Fe class, Cr-Co-Mn-Fe class, Cr-Cu class, Cr-Cu-Mn class etc.) etc.

The particle diameter of pigment can be considered the thixotroping viscosity of printing ink, the smoothness of the patterned surfaces after the printing etc. and set arbitrarily.For example, the particle diameter of pigment is preferably median size at 1nm～100nm.

The pigment of median size below 1nm is difficult for obtaining, and coherency is high.The anxiety that therefore, dispersiveness reduction in printing ink is arranged.In addition, not only there is the anxiety that reduces the patterned surfaces smoothness in the pigment that surpasses 100 μ m, and when being used for the reversal printing method, also exists in the middle anxieties that produce obstruction such as slit mouth mould coating machine.

The addition of tinting materials such as pigment specifically, can be done suitable setting according to desired color depth of printing ink and printing adaptability etc. according to purposes of printing ink etc.

Solvent contains and has 50 ℃～the low-tension solvent of 150 ℃ boiling point and the surface tension of 12mN/m～21mN/m (25 ℃) and the fluorochemical surfactant that this low-tension solvent had the solubleness (23 ℃) below the 10g/100g.

As low-tension solvent with 50 ℃～150 ℃ boiling point and the surface tension of 12mN/m～21mN/m (25 ℃); For example can be to contain fluorous solvent, n-pentane (36 ℃ of boiling points; Surface tension 16.4mN/m), n-hexane (69 ℃ of boiling points, surface tension 18.4mN/m), n-heptane (98 ℃ of boiling points, surface tension 19.6mN/m), Virahol (82.4 ℃ of boiling points; Surface tension 20.8mN/m), low molecular weight silicone oil (98 ℃ of boiling points, surface tension 18～19mN/m) etc.These can use separately or share more than 2 kinds.In addition, in these solvents, preferably contain fluorous solvent.

As containing fluorous solvent, if contain fluorine atom, be flame retardant resistance and have 50 ℃～150 ℃ boiling point and the surface tension of 12mN/m～21mN/m (25 ℃) in the molecule, the various fluorous solvents that contain all can use.

Particularly, be preferably selected from not chloride hydrogen fluorine ethers and the hydro fluorocarbons at least a kind.

As hydrogen fluorine ethers, but the fluorinated compound of enumerative (1) expression:

X-O-Y (1)

(in the formula, X representes that the fluoroalkyl represented by CHF, Y represent the fluoroalkyl of being represented by CHF.In addition, a in two formulas, b, c, d, e, f are the integer that satisfies a >=1, b >=0, c >=1, d >=1, e >=1, f >=0.And a, b, c, d, e, f also satisfy b+c=2a+1, e+f=2d+1, a+d during b=0＞3, c+e+f＞8, b >=1 o'clock a+d >=3, and these 6 conditions of b+c+e+f >=8.〕

In addition; 9 >=a+d when a, b, c, d, e, f preferably satisfy b=0＞3,20 >=c+e+f＞8, b >=1 o'clock 8 >=a+d >=3, and these 4 conditions of 18 >=b+c+e+f >=8; 7 >=a+b when especially preferably satisfying b=0 >=5; 16 >=c+e+f＞12, b >=1 o'clock 8 >=a+d >=4, and these 4 conditions of 18 >=b+c+e+f >=10.

In the hydrogen fluorine ethers,, for example can be ethyl nine fluorine butyl ethers (76 ℃ of boiling points, surface tension 13.6mN/m), methyl nine fluorine butyl ethers (76 ℃ of boiling points, surface tension 13.6mN/m), 1,1 as material with 50 ℃～150 ℃ boiling point and the surface tension of 12mN/m～21mN/m (25 ℃); 1,2,3,4,4; 5,5,5-ten fluoro-2-trifluoromethyl-3-methyl amylethers (55 ℃ of boiling points, surface tension 14.1mN/m), 1,1; 2,3,3,3-hexafluoro propyl group (1-methyl-2,2; 3,4,4,4-hexafluoro butyl) ether (79 ℃ of boiling points, surface tension 13.3mN/m).These hydrogen fluorine ethers can use separately or share more than 2 kinds.

In addition, as the concrete commercially available article of hydrogen fluorine ethers, for example be NOVEC (registered trademark) HFE-7200 (76 ℃ of boiling points, surface tension 13.6mN/m) that Sumitomo 3M Co., Ltd. produces.This HFE-7200 is the mixture of ethyl nine fluorine isobutyl ethers (hydrogen fluorine ethers) and ethyl nine fluorine butyl ethers (hydrogen fluorine ethers).

As hydro fluorocarbons, for example can be 13 amyl fluorides (トリデカ Off Le オロペ Application タ Application) (58 ℃ of boiling points, surface tension 14.1mN/m), ten trifluoro hexanes (トリデカ Off Le オロヘキサ Application) (59 ℃ of boiling points, surface tension 12.5mN/m) etc.These hydro fluorocarbons can be used separately or share more than 2 kinds.

To boiling point that contain fluorous solvent and surface tension be adjusted in the above-mentioned scope, have only and select to have this boiling point and the capillary fluorous solvent that contains, or with containing the fluorous solvent fusion more than 2 kinds, be adjusted to boiling point and surface tension gets final product in specialized range.

The boiling point of low-tension solvent under normal pressure (1013.25hPa) is limited to 50 ℃～150 ℃ the reasons are as follows.

Boiling point is lower than 50 ℃ low-tension solvent and from printing ink, volatilizees easily.Along with volatilization, printing ink meeting drying and aggegation, its result has foreign matter to separate out in the printing ink, become the reason that occurs lengthwise streaking in the ink lay.In addition, the lengthwise streaking that causes even without separating out by foreign matter, but ink viscosity can rise, and causes that ink lay is irregular, and the ink logo shape can be because of lengthwise streaking and irregular and disorderly.

On the other hand, the boiling point at the low-tension solvent surpasses under 150 ℃ the situation the difficult drying of printing ink.Thus, after ink logo was transferred to substrate surface, because ink setting needs for a long time, the production efficiency of liquid crystal color filter etc. can reduce.In addition, boiling point surpasses 150 ℃ low-tension solvent, and inevitable surface tension is high on its chemical structure.Therefore, the effect that reduces ink surface tension becomes insufficient, its result, and ink lay can occur irregular, and the ink logo shape can be because of lengthwise streaking and irregular and disorderly.

In addition, even the boiling point of low-tension solvent is in above-mentioned scope, still preferably more than 60 ℃.If the boiling point of low-tension solvent is more than 60 ℃, just can be at silicon blanket surface no lengthwise streaking of formation and irregular etc. good ink lay.Thus, can form amorphism disorder etc., good ink logo at substrate surface.In addition, can make ink logo, the production efficiency of raising liquid crystal color filter etc. at short as far as possible time inner drying.

In addition, the surface tension (25 ℃) with the low-tension solvent is limited to the reasons are as follows of 12mN/m～21mN/m.

The surface tension of low-tension solvent is during less than 12mN/m, though it is proportional or with other solvent types of low-tension solvent combinations etc. and decide, printing ink is too high to the wettability of silicon blanket surface also need to look containing of low-tension solvent.Therefore, can not make ink logo be transferred to substrate surface well from the silicon blanket surface.Its result, the shape of the ink logo after the transfer printing can get muddled.

In addition, printing ink uprises the wettability of slit mouth mould coating machine etc.Thus, printing ink especially is prone to attached near the slit mouth.And the ink setting that existence is adhered to, binder resin etc. separate out, partly stop up the anxiety of slit mouth as foreign matter.Its result, lengthwise streaking can appear in ink lay, and the ink logo shape can be disorderly because of lengthwise streaking.

On the other hand, when the surface tension of low-tension solvent surpasses 21mN/m, can not obtain to improve the effect of printing ink to the wettability of silicon blanket surface.Therefore, when on printing ink being coated on roughly whole of silicon blanket surface, forming ink lay, occur easily repelling etc.Its result, owing to occur to repel etc., even pin hole etc. appears not in ink lay easily.

In addition, when the low-tension solvent when containing fluorous solvent, the surface tension of low-tension solvent is preferably 12mN/m～21mN/m, more preferably below 16mN/m.If the low-tension solvent is the fluorous solvent that contains in the above-mentioned scope, just can be at the silicon blanket surface formation good ink lay of even pin hole etc. invariably.And, can form the good ink logo of amorphism disorder etc. at substrate surface.

The surface tension of low-tension solvent can be that the dynamic surface tension meter SITA t60 that produces with Eko Instruments Trading under 25 ℃ the environment measures through maximum bubble pressure method in for example temperature.

In addition, with respect to the solvent total amount, the low-tension solvent contain proportional to be 5～50 quality %, to be preferably 5～40 quality %, more preferably 5～30 quality %.

Containing of low-tension solvent is proportional during less than 5 quality %, even contain the low-tension solvent in the solvent, also is difficult to make ink surface tension to reduce, thereby is difficult to improve the wettability of printing ink to the silicon blanket surface.Therefore, when on printing ink being coated on roughly whole of silicon blanket surface, forming ink lay, occur easily repelling etc.Its result, owing to occur to repel etc., even pin hole etc. appears not in ink lay easily.In addition, also be difficult to give printing ink with flame retardant resistance.

On the other hand, containing of low-tension solvent is proportional when surpassing 50 quality %, and insoluble binder resin etc. is separated out as foreign matter easily in the low-tension solvent.Its result, foreign matter can partly stop up the slit mouth, lengthwise streaking appears in ink lay, and the ink logo shape can be disorderly because of this lengthwise streaking.

In addition, if containing of low-tension solvent is proportional below 40 quality %, just can be at the no lengthwise streaking of silicon blanket surface formation, the good ink lay of even pin hole etc. not.And, can form the good ink logo of amorphism disorder etc. at substrate surface.

In addition, using separately under the situation of low-tension solvent, the ratio that contains of low-tension solvent is represented a kind of low-tension solvent shared ratio in the solvent total amount.On the other hand, and situation with low-tension solvent more than 2 kinds under, represent the ratio of the low-tension solvent shared total amount in the solvent total amount more than 2 kinds.

In addition, in the present invention, can and use low-tension solvent and other solvents as required.

As other solvents, can be to make the binder resin excellent dissolution, can prevent all kinds of SOLVENTS that binder resin is separated out.

Particularly; For example can be EGME (another name " methylcyclohexane ", " 2-methyl cellosolve "), ethylene glycol monoethyl ether (another name " cellosolve ", " cellosolvo "), propylene glycol monomethyl ether acetate (another name " 1-methoxyl group-2-propanol acetate ester ", below abbreviate " PGMEA " sometimes as), ethylene glycol monobutyl ether (another name " ethylene glycol butyl ether ", " butoxy ethanol ") etc.These solvents can use separately or share more than 2 kinds.In addition, especially preferred PGAME in these solvents.

In addition, other solvents except that the low-tension solvent contains proportional promptly, with respect to the solvent total amount, to be 50～95 quality % for containing the remainder of fluorous solvent in the solvent, to be preferably 60～95 quality %, more preferably 70～95 quality %.

Using separately under the situation of other solvents, the ratio that contains of other solvents is represented a kind of other solvent shared ratio in the solvent total amount.On the other hand, and situation with other solvents more than 2 kinds under, represent the ratio of other solvents shared total amount in the solvent total amount more than 2 kinds.

In addition; Low-tension solvent and as required and the whole solvent phase that other solvent combinations of blended form is proportional for containing of total ink; Can and/or contain proportional according to kind, the molecular weight of for example binder resin; For example the kind of tinting material and/or contain proportional etc. is set arbitrarily, makes printing ink reach the viscosity that is fit to the reversal printing method.

Fluorochemical surfactant is illustrated to reason such as front that the solubleness (23 ℃) of low-tension solvent is limited to below the 10g/100g.

Fluorochemical surfactant to the solubleness (23 ℃) of low-tension solvent preferably more than 0.5g/100g, more preferably more than the 1g/100g, below the 4g/100g.Solubleness becomes the core of pin hole less than the fluorochemical surfactant excessive aggegation in printing ink easily of 0.5g/100g, its result, and pin hole appears in ink lay easily, becomes easily to produce lengthwise streaking and inhomogenous reason.In addition,, just can more effectively suppress the generation of said variety of issue, at the no lengthwise streaking of silicon blanket surface formation, the ink lay with homogeneous thickness of even pin hole etc. not if solubleness is more than the 1g/100g, below the 4g/100g.

In addition; The solubleness of fluorochemical surfactant for example can be used in 23 ℃ the following low-tension solvent 100g limit of stirring of environment and slowly drip fluorochemical surfactant, and the quality (g) of the fluorochemical surfactant that in the low-tension solvent, does not dissolve, dripped when gonorrhoea occurring until this fluorochemical surfactant is represented.

In addition, containing of fluorochemical surfactant is proportional with respect to total ink, is 0.01～10 quality %, is preferably 0.3～8 quality %.

Containing of fluorochemical surfactant is proportional during less than 0.01 quality %, even add fluorochemical surfactant, can not have the ink logo of homogeneous thickness in substrate surface formation from levelling effect etc. through what ink surface tension is reduced produces.

In addition, if remedy fluorochemical surfactant deficiency and heavy addition surpass the low-tension solvent of 50 quality % of solvent total amount, then ink surface tension can be too low.Thus, printing ink can occur from the make progress phenomenon of irregular wetting diffusion of slit mouth mould coating machine top end part, this phenomenon is called as nozzle and pollutes.Have appropriate capillary printing ink and not only can also not have the anxiety of hanging down and dripping with certain width attached to slit mouth mould coating machine top end part, no longer further wetting diffusion.And the printing ink of irregular wetting diffusion, the surface tension of himself is low, and its part is hung down with the form of drop easily and dropped on the coated face.And the printing ink that drips down that hangs down is sneaked in the ink lay, makes ink lay disorderly easily.

On the other hand, under containing of the fluorochemical surfactant proportional situation that surpasses 10 quality %, there is the good wettability of solvent inherent to receive the anxiety of excessive fluorochemical surfactant infringement.Thus, printing ink integral body reduces the wettability of silicon blanket surface.Its result has the anxiety that can not form the ink lay with homogeneous thickness of no irregular, pin hole etc. in the silicon blanket surface.

In addition, also has anxiety in the excessive fluorochemical surfactant residual ink pattern.Thus, for example, when producing the LCD filter, the ITO film of lamination on filter, the binding property reduction of alignment film are peeled off easily.Its result has the anxiety that the problem that the LCD rate that manufactures a finished product reduces occurs making.

Using separately under the situation of fluorochemical surfactant, the ratio that contains of fluorochemical surfactant is represented a kind of fluorochemical surfactant shared ratio in total ink.On the other hand, share under the situation of fluorochemical surfactant more than 2 kinds the ratio of fluorochemical surfactant in total ink the shared total amount of expression more than 2 kinds.

In addition, the weight-average molecular weight Mw of fluorochemical surfactant is for example preferably more than 6000, especially more than 20000, and preferably below 80000, especially below 60000.

Weight-average molecular weight Mw is high to the solvability of low-tension solvent less than the lower molecular weight fluorochemical surfactant of said scope.Therefore, exist under 23 ℃ solubleness to low-tension solvent 100g exceed scope below the 10g, be dispersed in the printing ink equably, occur before the anxiety of variety of issue of explanation.

In addition, the HMW fluorochemical surfactant that weight-average molecular weight Mw exceeds above-mentioned scope is then opposite, and its solvability to the low-tension solvent is low.Therefore, exist in that the solubleness to low-tension solvent 100 under 23 ℃ is excessively low, excessive aggegation in printing ink, occur before the anxiety of variety of issue of explanation.

In addition, as fluorochemical surfactant, preferred nonionic class tensio-active agent.

Under with anionic species or the situation of cationic species as fluorochemical surfactant, for example, when making the LCD filter, if fluorochemical surfactant (anionic species or cationic) is sneaked in the liquid crystal then influential anxiety to LCD alignment.Therefore, the anxiety that bad grade occurs showing is arranged.And if nonionic class tensio-active agent, then there is not the anxiety of the associated problem of appearance.

In addition, printing ink of the present invention can contain various additives such as pigment dispersing agent, flow agent, thixotroping viscosity imparting agent, skimmer as required with arbitrary proportion.

And; Printing ink of the present invention can be through binder resin, tinting material, solvent (low-tension solvent and fluorochemical surfactant are necessary) are reached the various additives fusion of adding as required to scale, with mixing modulation such as three-roll grinder, ball mill, ball mill, masher, sand mills.

The surface tension of synthetic printing ink (25 ℃) is for example below 22mN/m, preferably below 20mN/m, and for example more than 15mN/m, preferably more than 16mN/m.

When the surface tension of printing ink surpasses 22mN/m, printing ink can appear to the insufficient situation of the wettability of silicon blanket surface.Therefore, when forming ink lay for roughly whole that printing ink is coated on the silicon blanket surface, the anxiety that grade occurs repelling is arranged.And, because the cause of repelling etc., have ink lay the anxiety of irregular, pin hole etc. to occur.

In addition, ink surface tension printing ink occurs to the too high situation of the wettability of silicon blanket surface during less than 15mN/m sometimes.Therefore, the anxiety that can not ink logo be transferred to well substrate surface from the silicon blanket surface is arranged.Its result, the anxiety that has the ink logo shape after the transfer printing to get muddled.

In addition, the viscosity of synthetic printing ink (25 ℃) is for example more than 0.5mPaS, preferably more than 1mPaS, and for example below 5mPaS, preferably below 3mPaS.If the viscosity of printing ink in above-mentioned scope, just can form good ink logo through the reversal printing method of using the silicon blanket.

As previously mentioned, printing ink of the present invention is suitable for using the reversal printing method of silicon blanket, under the situation that above-mentioned variety of issue do not occur, efficiently makes liquid crystal color filter that LCD for example uses etc.

At this moment, consider the raising printing precision, the swelling rate Δ V (%) of the silicon blanket that is produced by printing ink is preferably more than 5%, more preferably more than 10%.In addition, swelling rate Δ V (%) is preferably below 100%, more preferably below 50%, especially preferably below 30%.

Swelling rate Δ V (%) can be through will forming the silicon blanket the test portion of Zylox in being set at 23 ± 1 ℃ printing ink dipping 24 hours, make its swelling after, by the volume V before the dipping ₁With the volume V behind the dipping ₂(i) obtains according to formula.

ΔV(％)＝〔(V ₂-V ₁)/V ₁〕×100(i)

Swelling rate Δ V (%) was less than 5% o'clock, and printing ink is prone to be ostracised in the silicon blanket surface, and the anxiety of the ink film that can not form homogeneous is arranged.And surpass under 100% the situation at swelling rate Δ V (%), owing to the solvent in the printing ink can be absorbed rapidly by the silicon blanket, thereby the too fast anxiety of ink setting is arranged.

Swelling rate Δ V (%) can be through change solvent species, combination and amount than doing suitable adjusting.

< reversal printing method >

Fig. 1 (a)～(c) is for by the synoptic diagram as the reversal printing method of an embodiment of the present invention shown in the process sequence, and Fig. 1 (a) be the painting process of printing ink, and Fig. 1 (b) is the operation of removing of printing ink, and Fig. 1 (c) is a printing process.

Below, in conjunction with Fig. 1 (a)～Fig. 1 (c), the reversal printing method of aforementioned use printing ink is elaborated.

At first, shown in Fig. 1 (a), in painting process, printing ink 11 is coated on roughly whole of silicon blanket 10 surface, forms ink lay 12.

As silicon blanket 10, can be enumerated as the offset plate that its surface is made up of Zylox at least.

In addition, as silicon blanket 10, can be its whole offset plate for constituting by monolayer silicon rubber, or have at the offset plate of the stepped construction of the range upon range of silastic-layer of base material single face that constitutes by polyethylene terephthalate (PET) film, tinsel etc. etc.

Wherein, the whole silicon blanket 10 that is made up of monolayer silicon rubber for example can be peeled off Zylox and form from the square position through after being coated on aqueous Zylox on the square position, making it crosslinking reaction.

And the silicon blanket 10 with stepped construction for example can be through injecting Zylox, making it crosslinking reaction in metal die under the state that base material is installed in the metal die, perhaps makes it crosslinking reaction behind the substrate surface and form through aqueous Zylox is coated on.

Among Fig. 1 (a)～Fig. 1 (c), silicon blanket 10 is wound onto on the main body 13 of drum, the drum that the said main body 13 of Cheng Keyu is rotated together.

In order printing ink 11 to be coated on silicon blanket 10 surfaces, in this embodiment, use slit mouth mould coating machine 14.Slit mouth mould coating machine 14 has inking portion 15 that printing ink 11 supplied with and the gap nozzle 16 that is communicated with inking portion 15.

Gap nozzle 16 in painting process with the subtend configuration with interval of silicon blanket 10 surfaces.

Gap nozzle 16 becomes the elongated rectangular shape along the axis direction opening that is wound into silicon blanket 10 cylindraceous.Gap nozzle 16 is set to the width with the equidirectional same length of silicon blanket 10 along the A/F (horizontal A/F) of said axis direction.And the A/F of gap nozzle 16 edges and said axis direction orthogonal directions (circumferential direction of silicon blanket) (vertical A/F) is set to for example about 3 μ m～1000 μ m, about preferred 30 μ m～50 μ m.

In addition, silicon blanket 10 surfaces of subtend and the interval between narrow slit type nozzle 16 tops are set to for example about 10 μ m～150 μ m, about preferred 30 μ m～100 μ m.

Printing ink 11 of the present invention is supplied to inking portion 15, and shown in arrow among the figure, the limit makes silicon blanket 10 in one direction with the certain speed rotation, and printing ink 11 is supplied with continuously from gap nozzle 16 tops in the limit.Thus, on roughly whole of silicon blanket 10 surfaces, form ink lay 12.

The vertical A/F of the rotating speed that the thickness of ink lay 12 can be through changing silicon blanket 10, the viscosity of printing ink 11, gap nozzle 16 and the surface of silicon blanket 10 and gap nozzle 16 top interbody spacers etc. are suitably regulated.

Then, shown in Fig. 1 (b), in removing operation, silicon blanket 10 is rotated on version 17, make protuberance 18 selective exposures of ink lay 12 and version 17.Thus, the printing ink 11 of the part that contacts with protuberance 18 in the ink lay 12 is transferred on the protuberance 18, removes from silicon blanket 10 surfaces.Thus, form on silicon blanket 10 surface and the corresponding ink logo 20 of shape of the recess 19 of 18 of protuberances.

As version 17, can use the plate that constitutes by glass such as metal such as iron nickel alloy (42 alloys etc.), stainless steel or soda glass, non-alkali glasss.At the single face of this edition, like front explanation,, be formed with the corresponding recess 19 of shape with the ink logo 20 of printing through photolithography etc.

In addition, in order to improve version 17 weather resistance, on the surface of protuberance 18 etc., electrodepositable hard chromium etc.

Then, shown in Fig. 1 (c), in printing process, silicon blanket 10 is rotated on substrate 21.Thus, ink logo 20 is transferred on substrate 21 surfaces from silicon blanket 10 surfaces.Like this, at the shape corresponding ink logo 20 of substrate 21 surface formation with the recess 19 of version 17, a series of printing operations finish.

Afterwards, make printing ink 20 dryings, also can make the binder resin curing reaction as required, form the color filter layer of the LCD liquid crystal color filter that constitutes the front explanation, black matrix layer etc.

< liquid crystal color filter and method of manufacture thereof >

Fig. 2 is the expansion sectional drawing as the significant points of the liquid crystal color filter of an embodiment of the present invention.

Referring to Fig. 2, this routine liquid crystal color filter 22 possesses transparency carrier 23, the black matrix layer 24 of configured in parallel, color filter layer 25 that transparency carrier 23 and black matrix layer 24 are covered with interval each other on a side surface of transparency carrier 23.

Color filter layer 25 is arranged by this reiteration by the red color filter layer 23R that deceives the length direction configured in parallel of matrix layer 24 in transparency carrier 23 surperficial upper edges, green color filter layer 23G and blue color filter layer 23B and is constituted.

As transparency carrier 23, for example can be the substrate high to the light transmission rate of wavelength 400nm～700nm.As transparency carrier 23, for example can be sheet glass such as non-alkali glass, soda-lime glass, glass with lower alkali content, plastic plates such as polyethers, polysulfones, polyarylester, polyacrylic ester etc.

Black matrix layer 24 works to prevent the contrast gradient that colour mixture occurs between the different color filter layer 25R of all kinds of tone each other, 25G, 25B, improve liquid crystal color filter 22.

Black matrix layer 24 is not limited to ribbon, also can form reticulation.In addition, color filter layer 25 is not limited to ribbon, also can be the interior point-like of grid of the black matrix layer 23 of landfill.

When making liquid crystal color filter 22 through method of manufacture of the present invention, at first, the reversal printing method of explaining through the front at a side surface of transparency carrier 23 of the present invention forms black matrix layer 24.Then, as long as through reversal printing method of the present invention (though order is different) formation color filter layer 25R of all kinds, 25G, 25B successively, covering transparency carrier 23 and black matrix layer 24 get final product.

Embodiment of the present invention more than has been described, but the present invention can implement also through other modes.

For example, the drying of the printing ink after the printing and the sclerous reaction of carrying out through heating can be implemented separately when forming each layer.In addition, the sclerous reaction of carrying out through heating can only in the end be implemented once.

In addition, in method of manufacture of the present invention, can only form black matrix layer 24 or only form color filter layer 25 through reversal printing method of the present invention, other layers form with additive method.Said additive method can be photolithography or the intaglio offset print process of front explanation etc.

Embodiment

Below, through embodiment and comparative example the present invention is described, but the present invention does not receive the restriction of following examples.

The modulation of the printing ink in following illustrated example and the comparative example and test if no special instructions, are all carried out under the environment of 23 ± 2 ℃ of temperature, relative humidity 55 ± 1%.

< embodiment 1 >

Will be as polyester melamine resin (weight-average molecular weight Mw=10000) 100 mass parts, tinting material 20 mass parts of binder resin, contain fluorous solvent 100 mass parts, PGMEA 300 mass parts, fluorochemical surfactant 5 mass parts and pigment dispersing agent 5 mass parts as other solvents are mixed with planetary stirring machine; Then; Mixing with ball mill, be modulated into printing ink.

As tinting material, using primary particle size respectively is red pigment (anthraquinone class pigment), veridian (bromination phthalocyanine) and the blue pigments (copper phthalocyanine) of 1～100nm, modulates each red, green and blue color ink.

As containing fluorous solvent, use to be all the ethyl nine fluorine isobutyl ethers of hydrogen fluorine ethers and the mixture of ethyl nine fluorine butyl ethers (NOVEC (registered trademark) HFE-7200 of Sumitomo 3M Co., Ltd. production, 76 ℃ of boiling points, the surface tension 13.6mN/m under 25 ℃).

In addition, as fluorochemical surfactant, Surflon (registered trademark) S-611 that uses AGC Seimi Chemical Co., Ltd. to make.

And, as pigment dispersing agent, the mixture that the Solsperse 24000GR (SC) that the Solsperse (registered trademark) 5000 (pigment derivative class) of use Lubrizol manufactured and the said firm make forms by fusion in 1: 1.

In addition, in the printing ink fluorine-containing solvent phase proportional for containing of solvent total amount be 25 quality %.In addition, fluorochemical surfactant is proportional with respect to containing of total ink is 0.94 quality %.

< embodiment 2～5 and comparative example 1～2 >

Except contain the amount of fluorous solvent and other solvents through adjustment; Make contain containing of fluorous solvent proportional with respect to the solvent total amount be 4 quality % (comparative example 1), 5 quality % (embodiment 2), 10 quality % (embodiment 3), 30 quality % (embodiment 4), 50 quality % (embodiment 5) and 52 quality % (comparative example 2) in addition, by the method modulation printing ink identical with embodiment 1.In addition, the total amount that contains fluorous solvent and other solvents is the same with embodiment 1, is 400 mass parts.In addition, fluorochemical surfactant is proportional with respect to containing of total ink is 0.94 quality %.

< embodiment 6～8 and comparative example 3～4 >

Except conduct contains fluorous solvent; Use ethyl nine fluorine butyl ethers (76 ℃ of boiling points; Surface tension 13.6mN/m); Fluorine-containing solvent phase for containing of solvent total amount proportional be 0.5 quality % (comparative example 3), 5 quality % (comparative example 6), 30 quality % (embodiment 7), 50 quality % (embodiment 8) and 80 quality % (comparative example 4) in addition, by the method modulation printing ink identical with embodiment 1.In addition, the total amount that contains fluorous solvent and other solvents is the same with embodiment 1, is 400 mass parts.In addition, fluorochemical surfactant is proportional with respect to containing of total ink is 0.94 quality %.

< embodiment 9 >

Except as containing fluorous solvent, use methyl nine fluorine butyl ether (76 ℃ of boiling points, surface tension 13.6mN/m), fluorine-containing solvent phase is proportional for containing of solvent total amount to be beyond the 30 quality %, by modulating printing ink with embodiment 1 identical method.In addition, the total amount that contains fluorous solvent and other solvents is the same with embodiment 1, is 400 mass parts.In addition, fluorochemical surfactant is proportional with respect to containing of total ink is 0.94 quality %.

< embodiment 10 >

Except as containing fluorous solvent, use 1,1,1,2; 3,4,4,5,5; 5-ten fluoro-2-trifluoromethyl-3-methyl amylethers (55 ℃ of boiling points, surface tension 14.1mN/m), fluorine-containing solvent phase are proportional for containing of solvent total amount to be beyond the 30 quality %, by modulating printing ink with embodiment 1 identical method.In addition, the total amount that contains fluorous solvent and other solvents is the same with embodiment 1, is 400 mass parts.In addition, fluorochemical surfactant is proportional with respect to containing of total ink is 0.94 quality %.

< embodiment 11 and comparative example 5～6 >

Except conduct contains fluorous solvent; Replace HFE-7200; Surface tension when mixing boiling point that 100 mass parts obtain through the hydrogen fluorine ethers that mixes more than 2 kinds respectively and being 70 ℃, 25 ℃ be the solvent (comparative example 5) of 10mN/m, solvent (embodiment 11) that the surface tension when boiling point is 70 ℃, 25 ℃ is 18mN/m and the boiling point surface tension when being 70 ℃, 25 ℃ be 25mN/m solvent (comparative example 6) in addition, by the method modulation printing ink identical with embodiment 1.

In each printing ink fluorine-containing solvent phase proportional for containing of solvent total amount be 25 quality %.In addition, fluorochemical surfactant is proportional with respect to containing of total ink is 0.94 quality %.

< embodiment 12～13 and comparative example 7～8 >

Except conduct contains fluorous solvent; Replace HFE-7200; Surface tension when solvent (embodiment 13) that the surface tension when mixing boiling point that 100 mass parts obtain through the hydrogen fluorine ethers that mixes more than 2 kinds respectively and being 45 ℃, 25 ℃ is the solvent (comparative example 7) of 14mN/m, solvent (embodiment 12) that the surface tension when boiling point is 55 ℃, 25 ℃ is 14mN/m, the surface tension when boiling point is 90 ℃, 25 ℃ is 14mN/m and boiling point are 160 ℃, 25 ℃ be 14mN/m solvent (comparative example 8) in addition, by the method modulation printing ink identical with embodiment 1.

< embodiment 14 >

Except as containing fluorous solvent, replace HFE-7200, the surface tension when mixing boiling point that 100 mass parts obtain through the hydrogen fluorohydrocarbon class of mixing more than 2 kinds and being 70 ℃, 25 ℃ is beyond the solvent of 14mN/m, by the method modulation printing ink identical with embodiment 1.

< comparative example 9 >

Except as solvent, replace HFE-7200 and PGMEA, mix beyond the normal hexane of conduct low-tension solvent in the past of 400 mass parts, by the method modulation printing ink identical with embodiment 1.

< comparative example 10 >

Except as solvent, do not mix HFE-7200, and only mix beyond the PGMEA of 400 mass parts, by modulating printing ink with embodiment 1 identical method.

< evaluation >

(1) printing test

With each color ink that modulates in the foregoing description and the comparative example,, on glass substrate, print red, green and blue ribbon ink logo of all kinds (live width 100 μ m, spacing 300 μ m) successively through adopting the reversal printing method of silicon blanket.Make LCD thus and use filter.

As the silicon blanket, use to have silicon blanket in the stepped construction of the thick silastic-layer of the range upon range of 0.6mm of single face of the thick PET film of 0.35mm.

In addition, in order on roughly whole of silicon blanket surface, to form ink lay, used slit mouth mould coating machine.

Then, in the filter manufacturing process that explained the front of adopting the reversal printing method, estimate following order.

(2) ink lay state

Through ink lay visual and that observation by light microscope forms on the silicon blanket with slit mouth mould coating machine.Thus, free of pinholes is arranged, have or not lengthwise streaking and have or not irregular by following standard evaluation respectively.

(a) free of pinholes is arranged

Zero: do not see pin hole in the ink lay.

*: find pin hole in the ink lay.

(b) have or not lengthwise streaking

◎: do not see lengthwise streaking in the ink lay fully.

Zero: though lengthwise streaking slightly in the ink lay, for not influencing practical degree.

*: find many lengthwise streakings in the ink lay.

(c) have or not irregular

◎: ink lay does not have irregular, and is very even.

Zero: though slightly see the irregular of under opticmicroscope observable degree in the ink lay, for not influencing practical degree.

*: find in the ink lay that visual is the irregular of observable degree.

(3) printing shape

Be printed on the ink logo on the glass substrate through visual with observation by light microscope.Thus, press the disorder of following standard evaluation ink logo shape.

◎: do not see fully in the ink logo that shape is disorderly.

Zero: though slightly see the disorder of observable degree under opticmicroscope in the ink logo, for not influencing practical degree.

*: find in the ink logo that visual is the disorder of observable degree.

Above result is shown in table 1～table 5.In table 3～5,, listed the result of embodiment 1 respectively in the lump for relatively.Abbreviation in each table is following:

HFE: hydrogen fluorine ethers

HFC: hydrogen fluorohydrocarbon class

N-Hex: normal hexane

PGMEA: propylene glycol monomethyl ether acetate

(table 1)

Table 1

(table 2)

Table 2

(table 3)

Table 3

(table 4)

Table 4

(table 5)

Table 5

Embodiment 1～14 in table 1～table 5, the result of the comparative example 9～10 in the table 5 show; Through containing fluorous solvent and other solvents and being used as solvent, can obtain the silicon blanket surface is had concurrently wettability and the release of appropriateness and is not prone to safety issue and the printing ink of lengthwise streaking, problem such as irregular.

In addition, the embodiment 6～8 in embodiment in the table 1 1～5 and comparative example 1～2, the table 2 and the result of comparative example 3～4 show, obtain said effect, contain containing of fluorous solvent proportional must be more than the 5 quality %, below the 50 quality %.Especially, The above results shows that it is proportional preferably below 30 quality % to contain containing of fluorous solvent.

In addition, the embodiment 1,11 in the table 3 and the result of comparative example 5～6 show, obtain said effect, and as containing fluorous solvent, its surface tension in the time of 25 ℃ must be more than the 12mN/m, below the 18mN/m.Especially, The above results shows that the surface tension that contains fluorous solvent is preferably below 16mN/m.

In addition, the embodiment 1,12,13 in the table 4 and the result of comparative example 7～8 show, obtain said effect, and as containing fluorous solvent, its boiling point must be more than 50 ℃, below 150 ℃.Especially, The above results shows that the surface tension that contains fluorous solvent is preferably below 60 ℃.

In addition, the embodiment 7,9,10 in the table 2, the result of the embodiment 1,14 in the table 5 further shows, obtain said effect, contains fluorous solvent and is preferably hydrogen fluorine ethers or hydrogen fluorohydrocarbon class.

< embodiment 15 >

Will be as polyester-melamine resin (weight-average molecular weight Mw=10000) 100 mass parts of binder resin, tinting material 20 mass parts, as n-hexane 100 mass parts of low-tension solvent, as propylene glycol monomethyl ether acetate (PGMEA) 300 mass parts of other solvents, (AGC Seimi Chemical Co., Ltd. makes as Surflon (registered trademark) S-611 of fluorochemical surfactant; Weight-average molecular weight Mw=44000) 2.64 mass parts and pigment dispersing agent 5 mass parts are mixed with planetary stirring machine; Then; Mixing with ball mill, be modulated into printing ink.

Surflon S-611 is 2g to the solubleness (23 ℃) of n-hexane (low-tension solvent) 100g.In addition, Surflon S-611 is proportional with respect to containing of total ink is 0.5 quality %.

In addition, as tinting material, using primary particle size respectively is red pigment (anthraquinone class pigment), veridian (bromination phthalocyanine) and the blue pigments (copper phthalocyanine) of 1～100nm, modulates each red, green and blue color ink.

In addition, as pigment dispersing agent, the mixture that the Solsperse 24000GR (SC) that the Solsperse (registered trademark) 5000 (pigment derivative type) of use Lubrizol manufactured and the said firm make forms by fusion in 1: 1.

< embodiment 16～18 and comparative example 11～12 >

Addition except adjustment Surflon S-611; Make in the total ink contain proportional be 0.005 quality % (comparative example 11), 0.015 quality (embodiment 16), 5 quality % (embodiment 17), 9.5 quality % (embodiment 18) and 12 quality % (comparative example 12) in addition, by the methods modulation printing ink identical with embodiment 15.

< comparative example 13 >

Except replacing Surflon S-611, use fluorochemical surfactant Surflon S-651 (AGC Seimi Chemical Co., Ltd. makes, weight-average molecular weight Mw=5400) beyond 2.64 mass parts, by modulating printing ink with embodiment 15 identical methods.

Surflon S-651 is 15g to the solubleness (23 ℃) of n-hexane (low-tension solvent) 100g.In addition, Surflon S-651 is proportional with respect to containing of total ink is 0.5 quality %.

< comparative example 14 >

Except replacing Surflon S-611, use fluorochemical surfactant Megafac (registered trademark) F-444 (Dainippon Ink Chemicals makes, weight-average molecular weight Mw=4800) beyond 2.64 mass parts, by modulating printing ink with embodiment 15 identical methods.

Megafac F-444 is 20g to the solubleness (23 ℃) of n-hexane (low-tension solvent) 100g.In addition, Megafac F-444 is proportional with respect to containing of total ink is 0.5 quality %.

< embodiment 19 >

Except replacing Surflon S-611 as the low-tension solvent, by modulating printing ink with embodiment 15 identical methods with NOVEC (registered trademark) HFE-7200 (manufacturing of Sumitomo 3M Co., Ltd.) 100 mass parts.

Surflon S-611 is 3g to the solubleness (23 ℃) of HFE-7200 (low-tension solvent) 100g.

< comparative example 15 >

Except using NOVEC (registered trademark) HFE-7200 (manufacturing of Sumitomo 3M Co., Ltd.) 100 mass parts, by modulating printing ink with comparative example 13 identical methods as the low-tension solvent.

Surflon S-651 is 20g to the solubleness (23 ℃) of HFE-7200 (low-tension solvent) 100g.

< evaluation >

(1) measurement of surface tension

The surface tension of synthetic printing ink is through being that the dynamic surface tension meter SITAt60 that produces with Eko Instruments Trading under 25 ℃ the environment measures through maximum bubble pressure method in temperature in the foregoing description and the comparative example.

(2) viscosimetric analysis

The viscosity of synthetic printing ink is through being with cone-plate type viscometer (the Digital Viscometer LVDV-I of Brookfield manufactured) " with the viscosity measurement that circular cone-plate shaped rotational viscosimeter carries out " mensuration according to record among the JIS Z8803-1991 of JIS " viscosity-measuring method of liquid " in temperature under 25 ℃ the environment in the foregoing description and the comparative example.Condition determination is made as, cone diameter φ=48mm (radius R=24mm), angle=3 that form between circular cone and circular flat board °.

(3) printing test

Use synthetic each color ink in the foregoing description and the comparative example,, on glass substrate, print red, green and blue ribbon ink logo of all kinds (live width 100 μ m, spacing 300 μ m) successively through adopting the reversal printing method of silicon blanket.Make LCD thus and use filter.

As the silicon blanket, use blanket with the stepped construction that forms at the thick silastic-layer of the range upon range of 0.6mm of single face of the thick PET film of 0.35mm.

Then, adopt the reversal printing method, estimate following order in the filter manufacturing process that explained in front.

(4) state of ink lay

Through ink lay visual and that observation by light microscope forms on the silicon blanket with slit mouth mould coating machine.Thus, have or not lengthwise streaking and have or not irregular by following standard evaluation respectively.

(a) have or not lengthwise streaking

◎: do not see lengthwise streaking in the ink lay fully.

Zero: though slightly see lengthwise streaking in the ink lay, for not influencing practical degree.

*: find many lengthwise streakings in the ink lay.

(b) have or not irregular

◎: no irregular in the ink lay, homogeneous.

*: find the irregular of visual observable degree in the ink lay.

(5) printing shape

◎: do not see fully in the ink logo that shape is disorderly.

*: find the disorder of visual observable degree in the ink logo.

Above result is shown in table 6, table 7.In the table 7,, listed the result of embodiment 15 in the lump for relatively.Symbol in two tables is following.

N-Hex: normal hexane

HFE：HFE-7200

S-611：Surflon?S-611

F-444：Megafac?F-444

(table 6)

Table 6

(table 7)

Table 7

Embodiment 15～19 in table 6, the table 7, the result of comparative example 13～15 show; Through use solubleness to low-tension solvent 100g below 10g, be essentially the fluorochemical surfactant that is insoluble to solvent, can provide the silicon blanket surface is had concurrently the wettability of appropriateness and the printing ink of release.In addition, The above results shows, can form no lengthwise streaking, the ink lay with homogeneous thickness of even pin hole etc. not in the silicon blanket surface.Also have, The above results shows, can obtain forming on the surface that substrate etc. is printed body the reversal printing method that has the ink logo of homogeneous thickness and be not prone to safety issue and use printing ink.

In addition, the embodiment 15～18 in the table 6, the result of comparative example 11～12 show, obtain said effect, must the ratio more than the 0.01 quality % with total ink, below the 10 quality % contain fluorochemical surfactant.Especially, The above results shows, fluorochemical surfactant contain proportional be preferably 0.3 quality above, below the 7 quality %.

In addition, the integrant of in each embodiment of the present invention, explaining can make up within the scope of the invention.

The Japanese patent application of submitting to Japanese Patent office in Japanese patent application 2010-125913 number that submit to Japanese Patent office Japanese patent application on June 1st, 2009-255447 number 1 of submitting to Japanese Patent office in the application and on November 6th, 2009 and on June 2nd, 2010 2010-127006 number is corresponding, and whole disclosures of these applications are incorporated among the present invention by reference.

Nomenclature

10 ... The silicon blanket, 11 ... Printing ink, 12 ... Ink lay, 13 ... Main body, 14 ... Slit mouth mould coating machine; 15 ... Inking portion, 16 ... Gap nozzle, 17 ... Version, 18 ... Protuberance, 19 ... Recess; 20 ... Ink logo, 20 ... Tinting material, 21 ... Substrate, 22 ... Liquid crystal color filter, 23 ... Transparency carrier

Claims (according to the modification of the 19th of treaty)

1. the reversal printing method is used printing ink (to revise the back); Said reversal printing method comprises the ink lay that makes on roughly whole that is formed on the silicon blanket surface and surface and has the operation that contacts with the said surface of the version of the corresponding recess of ink logo of regulation; In the operation of the said surface formation of the said silicon blanket ink logo corresponding, said ink logo is printed onto the operation that be printed surface after forming said printing ink through removing on the said surface that the said ink lay beyond the said recess is transferred to said version, from the said surface selectivity ground of said silicon blanket with said recess;

Said reversal printing method contains binder resin, tinting material and solvent with printing ink; Said solvent contain with the ratio of 5～50 quality % that are equivalent to said solvent total amount have 50 ℃～150 ℃ boiling point and the surface tension of 12mN/m～18mN/m (25 ℃) contain fluorous solvent, and contain with the ratio of 0.01～10 quality % of total ink and contain the fluorochemical surfactant that fluorous solvent has the solubleness (23 ℃) below the 10g/100g said to be equivalent to said reversal printing method.

2. (deletion)

3. reversal printing method according to claim 1 is used printing ink (to revise the back), it is characterized in that the said fluorous solvent that contains is hydrogen fluorine ethers and/or hydrogen fluorohydrocarbon class.

4. (revise the back) and use printing ink, it is characterized in that said fluorochemical surfactant has 6000～80000 weight-average molecular weight Mw according to claim 1 or 3 described reversal printing methods.

5. (revise the back) and use printing ink, it is characterized in that said fluorochemical surfactant is a nonionic class tensio-active agent according to claim 1 or 3 described reversal printing methods.

6. (revise the back) and use printing ink according to claim 1 or 3 described reversal printing methods, it is characterized in that, said reversal printing method has surface tension (25 ℃) and the following viscosity (25 ℃) of 5mPaS below the 22m/Nm with printing ink.

7. (revise afterwards) reversal printing method; It comprises the ink lay that makes on roughly whole that is formed on the silicon blanket surface and surface and has the operation that contacts with the said surface of the version of the corresponding recess of ink logo of regulation; Form the operation of the ink logo corresponding through optionally removing on the said surface that the said ink lay beyond the said recess is transferred to said version, from the said surface of said silicon blanket on the said surface of said silicon blanket, after forming said printing ink and forming said ink logo is printed onto the operation that is printed the surface with said recess;

Form ink lay with claim 1 or 3 described reversal printing methods with printing ink.

8. liquid crystal color filter, it comprises transparency carrier, color filter layer and black matrix layer, and said color filter layer and said black matrix layer are formed on the said transparency carrier,

Said color filter layer and/or said black matrix layer form through the described reversal printing method of claim 6.

9. the method for manufacture of liquid crystal color filter, it is included in the operation that forms color filter layer and/or black matrix layer on the transparency carrier,

Said color filter layer and/or said black matrix layer form through the described reversal printing method of claim 7.

Explain or state (according to the modification of the 19th of treaty)

The 19th revised comment of PCT

The applicant according to the regulation of the 19th of PCT, has carried out following modification to the original rights claim in the application's the international application stage:

1. former claim 1 is revised as new claim 1.

2. leave out former claim 2.

3. former claim 3-7 is revised as new claim 3-7.

Claims

1. the reversal printing method is used printing ink, and said reversal printing method is that the ink logo of regulation that the ink lay on the silicon blanket is transferred on the intaglio plate, will be made up of the said ink lay that is transferred on this intaglio plate is printed onto the method that is printed on the body,

Said reversal printing method contains adhesive resin, tinting material and solvent with printing ink,

Said solvent contains with the ratio of 5～50 quality % that are equivalent to said solvent total amount and has 50 ℃～the low-tension solvent of 150 ℃ boiling point and the surface tension of 12mN/m～21mN/m (25 ℃), and contains the fluorochemical surfactant that said low-tension solvent is had the solubleness (23 ℃) below the 10g/100g to be equivalent to said reversal printing method with the ratio of 0.01～10 quality % of total ink.

2. reversal printing method according to claim 1 is used printing ink, it is characterized in that, said low-tension solvent contains the contain fluorous solvent of surface tension (25 ℃) for 12mN/m～18mN/m.

3. reversal printing method according to claim 2 is used printing ink, it is characterized in that, the said fluorous solvent that contains is hydrogen fluorine ethers and/or hydrogen fluorohydrocarbon class.

4. use printing ink according to each described reversal printing method in the claim 1～3, it is characterized in that said fluorochemical surfactant has 6000～80000 weight-average molecular weight Mw.

5. use printing ink according to each described reversal printing method in the claim 1～3, it is characterized in that, said fluorochemical surfactant is a nonionic class tensio-active agent.

6. use printing ink according to each described reversal printing method in the claim 1～3, it is characterized in that, said reversal printing method has surface tension (25 ℃) and the following viscosity (25 ℃) of 5mPaS below the 22m/Nm with printing ink.

7. reversal printing method, it comprises the ink lay on the silicon blanket is transferred to the operation on the intaglio plate and the ink logo of the regulation that will be made up of the said ink lay that is transferred on this intaglio plate is printed onto the operation that is printed on the body,

Form said ink lay with each described reversal printing method in the claim 1～3 with printing ink.