CN104981736A

CN104981736A - Photosensitive resin composition for inkjet application, heat-treated substance, manufacturing method therefor, resin-pattern manufacturing method, liquid-crystal display, organic electroluminescent display, touch panel, manufacturing method therefor, and touch-panel display

Info

Publication number: CN104981736A
Application number: CN201480008348.3A
Authority: CN
Inventors: 山下史绘; 藤本进二
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2013-02-14
Filing date: 2014-02-10
Publication date: 2015-10-14
Also published as: WO2014126034A1; TW201439229A; JPWO2014126034A1; KR20150091380A

Abstract

The purpose of the present invention is to provide a photosensitive resin composition that exhibits excellent inkjet discharge properties and storage stability, dries rapidly, and after heat treatment, is highly transparent. This photosensitive resin composition for inkjet application is characterized by containing the following: inorganic particles (component A); a solvent (component B); a polymer (component C) containing a constitutional unit that has a group in which an acid group is protected by an acid-degradable group; and a photoacid generator (component D). This photosensitive resin is further characterized in that component B contains a non-alcohol solvent that has a boiling point between 177 DEG C and 227 DEG C, inclusive, and an I/O value between 0.50 and 1.00, inclusive.

Description

Ink-jet application photosensitive polymer combination, thermal treatment thing and manufacture method thereof, resin pattern manufacture method, liquid crystal indicator, organic EL display, touch-screen and manufacture method thereof and touch panel display device

Technical field

The present invention relates to a kind of photosensitive polymer combination (following, sometimes referred to as " composition of the present invention ").In addition, the present invention relates to a kind of thermal treatment thing that above-mentioned photosensitive polymer combination is heat-treated and manufacture method thereof, the resin pattern manufacture method of the above-mentioned photosensitive polymer combination of use, the thermal treatment thing that above-mentioned photosensitive polymer combination is heat-treated and the various image display devices using above-mentioned thermal treatment thing.

More specifically; the present invention relates to one be suitable for the photosensitive polymer combination of the planarization film of the electronic component forming liquid crystal indicator, organic electroluminescent (Electroluminescence, EL) display device, touch-screen, touch panel display device, integrated circuit component, solid photographic element etc., diaphragm or interlayer dielectric and use its manufacture method of cured film.

Background technology

According to the development of solid photographic element or liquid crystal indicator, and start extensively to carry out utilizing organic material (resin) to make the optical components such as lenticule, optical waveguide, anti-reflective film.

In order to make the refractive index of these optical components uprise, and studying particles (with reference to following patent documentation 1) such as adding titanium dioxide.

In addition, as existing photosensitive polymer combination, there will be a known photosensitive polymer combination described in patent documentation 2 ~ patent documentation 4.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2006-98985 publication

[patent documentation 2] Japanese Patent Laid-Open 2008-158281 publication

[patent documentation 3] Japanese Patent Laid-Open 2011-248331 publication

[patent documentation 4] KR published patent 10-2012-0121850 publication

Summary of the invention

The problem that invention will solve

The object of the present invention is to provide the photosensitive polymer combination of the transparency excellence after a kind of ink-jet ejection, drying property, storage stability and thermal treatment.

The technological means of dealing with problems

Above-mentioned problem of the present invention is solved by means described in following <1>, <7> ~ <10> or <12> ~ <16>.Below <2> ~ the <6> as preferred example and <11> is recorded in the lump.

<1> ink-jet application photosensitive polymer combination; it is characterized in that: comprise (composition A) inorganic particulate, (composition B) solvent, (composition C) containing the polymkeric substance of Component units and (components D) light acid producing agent with the base that acidic group is protected by sour decomposability base; and composition B contains boiling point is more than 177 DEG C, less than 227 DEG C, and inorganic value/organic value (I/O value) is the non-alcohol series solvent of more than 0.50, less than 1.00.

The ink-jet application photosensitive polymer combination of <2> according to above-mentioned <1>, wherein above-mentioned non-alcohol series solvent is for being selected from least one solvent in the group that is made up of acidylate alkylene glycol monoalkyl ethers, acidylate two alkylene glycol monoalkyl ethers, two alkylene glycol dialkylether and three alkylene glycol dialkylether.

The ink-jet application photosensitive polymer combination of <3> according to above-mentioned <1> or <2>, wherein composition A is metal oxide particle.

The ink-jet application photosensitive polymer combination of <4> according to any one of above-mentioned <1> to <3>, wherein composition A is Titanium particles or Zirconia particles.

The ink-jet application photosensitive polymer combination of <5> according to any one of above-mentioned <1> to <4>, it also comprises (composition E) spreading agent.

The ink-jet application photosensitive polymer combination of <6> according to any one of above-mentioned <1> to <5>, it also comprises (composition F) thermal cross-linking agent.

The manufacture method of a <7> thermal treatment thing, is characterized in that: at least comprise step (a) ~ step (c),

A () utilizes ink-jet application mode the ink-jet application photosensitive polymer combination according to any one of above-mentioned <1> to <6> to be coated application step on substrate;

B () removes the solvent removal step of solvent in the resin combination be coated with; And

C heat treatment step that () is heat-treated the resin combination eliminating solvent.

<8> resin pattern manufacture method, is characterized in that: at least comprise step (1) ~ step (5),

(1) ink-jet application mode is utilized the ink-jet application photosensitive polymer combination according to any one of above-mentioned <1> to <6> to be coated application step on substrate;

(2) in the resin combination be coated with, remove the solvent removal step of solvent;

(3) utilize actinic ray that the resin combination eliminating solvent is exposed into the step of exposure of pattern-like;

(4) development step that aqueous developer solution is developed to the resin combination through exposure is utilized; And

(5) to the heat treatment step that the resin combination through development is heat-treated.

<9> thermal treatment thing, it is obtained by the manufacture method of the thermal treatment thing according to above-mentioned <7> or the resin pattern manufacture method according to above-mentioned <8>.

<10> thermal treatment thing, it is heat-treated the ink-jet application photosensitive polymer combination according to any one of above-mentioned <1> to <6> and is formed.

The thermal treatment thing of <11> according to above-mentioned <10>, it is interlayer dielectric.

<12> liquid crystal indicator, it comprises the thermal treatment thing according to above-mentioned <10> or <11>.

<13> organic electroluminescence display device and method of manufacturing same, it comprises the thermal treatment thing according to above-mentioned <10> or <11>.

The manufacture method of a <14> touch-screen, it has transparency carrier, tin indium oxide (Indium Tin Oxide, ITO) manufacture method of the touch-screen of electrode and insulation course, it comprises the steps: in the mode contacted with ITO electrode, utilizes ink-jet application mode to be coated with the step of the ink-jet application photosensitive polymer combination according to any one of above-mentioned <1> to <6>; Above-mentioned resin combination loads the mask with the patterns of openings of regulation shape and carries out active energy ray and irradiate the step of carrying out exposing; To the step that the resin combination after exposure develops; And the step manufacturing insulation course is heated to the resin combination after development.

<15> touch-screen, all or part of of its insulation course comprises the thermal treatment thing of the ink-jet application photosensitive polymer combination according to any one of above-mentioned <1> to <6>.

<16> touch panel display device, it comprises the thermal treatment thing according to above-mentioned <10> or <11> or the touch-screen according to above-mentioned <15>.

The effect of invention

According to the present invention, the photosensitive polymer combination of the transparency excellence after a kind of ink-jet ejection, drying property, storage stability and thermal treatment can be provided.

Accompanying drawing explanation

Fig. 1 represents the formation concept map of an example of liquid crystal indicator.Represent the constructed profile of the active-matrix substrate in liquid crystal indicator, and there is the cured film 17 as interlayer dielectric.

Fig. 2 represents the formation concept map of an example of organic EL display.Represent the constructed profile of the substrate in the organic EL display of bottom emission type, and there is planarization film 4.

Fig. 3 is the sectional view of the formation representing capacitive input device.

Fig. 4 is the key diagram of the example representing front panel.

Fig. 5 is the key diagram of the example representing the first transparent electrode pattern and the second transparent electrode pattern.

Embodiment

Below, content of the present invention is described in detail.The explanation of constitutive requirements described is below carried out based on representative example of the present invention sometimes, but the present invention is not limited thereto kind of an example.

Moreover, in present specification, represent that " ~ " of numerical range comprises numerical value described before and after it to use as the implication of lower limit and higher limit.

In addition; in the present invention; also by " (composition A) inorganic particulate " etc. referred to as " composition A " etc., also by " (a1) has the Component units of the base that acidic group is protected by sour decomposability base " described later etc. referred to as " Component units (a1) " etc.

And then, in the statement of base (atomic group) in this manual, do not record the statement being substituted and being unsubstituted and comprise not there is substituent base (atomic group), and comprise yet there is substituent base (atomic group).Such as, so-called " alkyl ", not only comprises and does not have substituent alkyl (alkyl be unsubstituted), also comprise and have substituent alkyl (alkyl be substituted).

(ink-jet application photosensitive polymer combination)

Ink-jet application photosensitive polymer combination of the present invention is (following; also referred to as " photosensitive polymer combination ") feature be: comprise (composition A) inorganic particulate, (composition B) solvent, (composition C) containing the polymkeric substance of Component units and (components D) light acid producing agent with the base that acidic group is protected by sour decomposability base; and composition B contains boiling point is more than 177 DEG C, less than 227 DEG C, and I/O value is the non-alcohol series solvent of more than 0.50, less than 1.00.

Photosensitive polymer combination of the present invention can be used as eurymeric anti-corrosion agent composition aptly.

The curable resin composition of the character that photosensitive polymer combination of the present invention preferably has Yin Re and hardens.

In addition, photosensitive polymer combination of the present invention is preferably positive type photosensitive organic compound, is more preferably the positive type photosensitive organic compound (chemically amplified positive photosensitive polymer combination) of chemical amplification type.

Photosensitive polymer combination of the present invention is preferably and does not contain 1,2-quinone di-azido compound as the photoactinic smooth acid producing agent of induction.1, although 2-quinone di-azido compound generates carboxyl by progressively type photochemical reaction, its quantum yield must be less than 1.

Relative to this; the acid that (components D) light acid producing agent used in the present invention generates because of induction actinic ray plays a role to the deprotection of the acidic group protected in composition C as catalyzer; therefore contribute to multiple deprotection reaction by the acid that the effect of 1 light quantum generates; quantum yield is more than 1; such as become value large as several powers of 10; as the result of so-called chemical amplification, high sensitivity can be obtained.

And then, photosensitive polymer combination of the present invention is preferably lenticule, optical waveguide, anti-reflective film, light emitting diode (LightEmitting Diode, LED) with the optical component resin combination of sealing material and LED chip coating material etc., or the observability reduction resin combination of the distribution electrode used in touch-screen.Moreover, the observability reduction composition of the distribution electrode used in so-called touch-screen, refer to the observability reducing the distribution electrode used in touch-screen, namely, make the component composition that distribution electrode is not easily in sight, include, for example ITO (tin indium oxide) interelectrode interlayer dielectric etc., photosensitive polymer combination of the present invention can be suitably used for described purposes.

Usually, if expose, then by the effect with light acid producing agent, the sour decomposability base that the polymkeric substance contained by positive type photosensitive organic compound has departs from, and is dissolved in developer solution, and unexposed portion is formed as pattern.

When the refractive index of obtained cured film will be made to uprise, need the high concentration of the content of inorganic particles in photosensitive polymer combination.If the content of inorganic particles in photosensitive polymer combination becomes many, then inorganic particulate condenses sometimes in photosensitive polymer combination, and the viscosity of photosensitive polymer combination increases, and its result, causes obstacle because the ejection in inkjet nozzle is bad to coating sometimes.In addition, the control of drying property becomes difficulty.

If even if spin coating mode, then, if for ink-jet application, then also there is the bad situation that maybe cannot spray of ejection in the resist that can be coated with equably without crawling.And, there is following problem: cause coated film to become uneven because of the uneven of ejection flow, and produce the membranaceous inequality of striated.

In addition, by making coated sheets number (application frequency) superpose, the front end of jetting nozzle is carried out moistening, dry repeatedly.If carry out drying in the front end of nozzle to the ink being dispersed with inorganic particulate, then there is solid component concentration increases sharp, and produces the situation of cohesion block.Produce the uneven of ejection flow because of these cohesion blocks, thus become by the bad caused crawling of ejection.And then described cohesion block is attached to the front end of nozzle, peels off from the front end of nozzle when again spraying ink and move on substrate.These cohesion blocks cannot easily be removed in step thereafter, and final residual is on substrate.This kind of cohesion block becomes defect, and becomes the bad reason of quality.If described bad phenomenon takes place frequently, then the yield of goods can decline, and is therefore regarded as one of phenomenon that must avoid.

In addition, in patent documentation 3, although there is the record utilizing spin application and squash type coating coating, do not disclose ink-jet application particularly, also do not carry out the coating utilizing ink-jet application in an embodiment.

The present inventor etc. carry out the result studied in great detail, find the photosensitive polymer combination by making containing composition A ~ components D, and can obtain the photosensitive polymer combination of the transparency excellence after ink-jet ejection, drying property, storage stability and thermal treatment.

Below, composition of the present invention is described in detail.

(composition A) inorganic particulate

Photosensitive polymer combination of the present invention contains (composition A) inorganic particulate to regulate for the purpose of refractive index or light transmission.

Composition A is preferably refractive index ratio and comprises the high composition of the refractive index of the resin combination of the material except above-mentioned particle, specifically, the refractive index be more preferably in the light of the wavelength with 400nm ~ 750nm is the particle of more than 1.50, and then be more preferably the particle that refractive index is more than 1.70, be particularly preferably the particle that refractive index is more than 1.90.In addition, being preferably refractive index is the particle of less than 5.00.

Herein, so-called refractive index in the light of wavelength with 400nm ~ 750nm is more than 1.50, referring to that the mean refractive index in the light of the wavelength with above-mentioned scope is more than 1.50, is more than 1.50 without the need to the refractive index in all light of wavelength with above-mentioned scope.In addition, mean refractive index is by for having the summation of measured value of refractive index of each light of wavelength of above-mentioned scope divided by the value of the quantity gained of measuring point.

There is as this kind the inorganic particulate of high index of refraction, be preferably metal oxide particle.Metal oxide particle is high and have light transmission because of the transparency, therefore easily can obtain the high and transparent excellent photosensitive polymer combination of refractive index.

Moreover the metal of the metal oxide particle in the present invention also comprises the semimetals such as B, Si, Ge, As, Sb, Te.

As the light transmission metal oxide particle that refractive index is high, preferably comprise the equiatomic oxide particle of Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, be more preferably titanium dioxide, titanium composite oxide, zinc paste, zirconia, indium/tin-oxide, antimony/tin-oxide, and then be more preferably titanium dioxide, titanium composite oxide, zirconia, be particularly preferably titanium dioxide, zirconia, most preferably be titanium dioxide.As titanium dioxide, be especially preferably the high rutile-type of refractive index.In order to give dispersion stabilization, the surface of organic material to these metal oxide particles also can be utilized to process.

With regard to the viewpoint of the transparency of resin combination, the average primary particle diameter of composition A is preferably 1nm ~ 200nm, is particularly preferably 3nm ~ 80nm., utilize the particle diameter of arbitrary 200 particles of determination of electron microscopy herein, and using the average primary particle diameter of its arithmetic mean as particle.In addition, when the shape of particle and aspherical time, using longest edge as diameter.

In addition, composition A can be used alone a kind, also can and use two or more.

As long as the content of the composition A in photosensitive polymer combination of the present invention is considered the refractive index required by the optical component obtained by photosensitive polymer combination or light transmission etc., and be suitable for determining, but relative to the total solid composition of photosensitive polymer combination, preferably be set to 5 quality % ~ 80 quality %, be more preferably and be set to 10 quality % ~ 70 quality %.Moreover the solid constituent amount of so-called photosensitive polymer combination, represents the amount desolventized etc. beyond volatile ingredient.

In the present invention, inorganic particulate also can be used as following dispersion liquid come in, above-mentioned dispersion liquid is by (composition E) spreading agent described later and solvent, uses the mixing arrangement such as bowl mill, rod mill to carry out mixing the dispersion liquid prepared by dispersion.

The solvent used in preparation as above-mentioned dispersion liquid, such as except (composition B) described later solvent, the alcohols etc. such as 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl-2-propanol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 3-methyl-1-butanol, 2-methyl-2-butanols, neopentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol can be enumerated.

These solvents can be used alone a kind or two or more is used in combination.

(composition B) solvent

Photosensitive polymer combination of the present invention contains (composition B) solvent.

In addition, it is more than 177 DEG C, less than 227 DEG C that composition B contains boiling point, and I/O value is the non-alcohol series solvent (hereinafter also referred to as " specific solvent ") of more than 0.50, less than 1.00.Photosensitive polymer combination of the present invention by containing above-mentioned specific solvent, drying property and ink-jet ejection excellent especially.

Photosensitive polymer combination of the present invention is preferably as making of the present invention must composition and arbitrary component dissolves described later or the solution be scattered in (composition B) solvent preparation.

Above-mentioned boiling point in the present invention is normal boiling point, the boiling point namely under 1 atmospheric pressure (101,325Pa).

The boiling point of above-mentioned specific solvent is more than 177 DEG C, less than 227 DEG C, is preferably more than 178 DEG C, less than 225 DEG C, is more preferably more than 178 DEG C, less than 220 DEG C.If above-mentioned scope, then the transparency after ink-jet ejection, drying property, developability and thermal treatment is excellent.

In addition, if the boiling point of above-mentioned specific solvent is less than 177 DEG C, then ink-jet ejection worsens.On the other hand, if boiling point is more than 227 DEG C, then drying property and developability not good enough.

So-called I/O value, refer to the organic value conceptually processing the polarity of various organic compound being also referred to as inorganic value/organic value, and be the one of the functional group's contribution approach (group-contribution method) to each functional group's setup parameter.

I/O value in the present invention be according to " new edition organic conceptional diagram basis with application " (first Tian Shansheng, help rattan four youth, kind husband's work between this, three are total to publication (2008)) the value that calculates of record.

Such as, obtain aptly by organic conceptional diagram reckoner (http://www.ecosci.jp/chem9/interaction.html).

In addition, about I/O value, at " organic conceptional diagram " (first Tian Shansheng work, three publish (1984) altogether); " Kumamoto pharmacy publication (KUMAMOTO PHARMACEUTICAL BULLETIN) ", No. 1, the 1st ~ the 16th (1954); " field of chemistry ", the 11st volume, No. 10, the 719th ~ the 725th (nineteen fifty-seven); " fragrance magazine (FRAGRANCE JOURNAL) ", No. 34, the 97th ~ the 111st (1979); " fragrance magazine ", also has detailed description in the 79th ~ document such as the 82nd (1981) by No. 50.

The concept of I/O value the character of compound is divided into representing the Organic base of covalency key and the inorganic nature base representing ion key, and all organic compounds are positioned called after and have arbor, represent without on every 1 on the craspedodrome coordinate of arbor.

Above-mentioned inorganic value refers to hydroxyl to be benchmark, and the various substituting group had by organic compound or key etc. are quantized for the size of the influence power of boiling point.Specifically, if at carbon number be the distance measuring the boiling curve of straight chain alcohol and the boiling curve of linear paraffin near 5, then become about 100 DEG C, therefore in numerical value, the influence power of 1 hydroxyl is decided to be 100, according to described numerical value, various substituting group or various keys etc. is become for the value that the influence power of boiling point is quantized the substituent inorganic value that organic compound has.Such as, the inorganic value of-COOH base is 150, and the inorganic value of carbon-to-carbon double bond is 2.Therefore, the inorganic value of certain organic compound refers to the summation of the inorganic value of the various substituting group that compound has or key etc.

In addition, above-mentioned organic value refers to using intramolecular methylene as unit, the value determined for benchmark for the influence power of boiling point with the carbon atom representing described methylene.Namely, by the carbon number at straight chain saturation alkane compound for 5 ~ 10 near add that the mean value that boiling point caused by 1 carbon rises is 20 DEG C, therefore for benchmark, the organic value of 1 carbon atom is decided to be 20 with it, based on this value that various substituting group or key etc. are quantized for the influence power of boiling point is become organic value.Such as, nitro (-NO ₂) organic value be 70.

I/O value, more close to 0, more represents the organic compound of nonpolar (hydrophobicity, Organic are large), is worth larger, more represent the organic compound of polarity (water wettability, inorganic nature are large).

The I/O value of above-mentioned specific solvent is more than 0.50, less than 1.00, is preferably more than 0.53, less than 0.90, is more preferably more than 0.53, less than 0.85, and then is more preferably more than 0.55, less than 0.82.If above-mentioned scope, then the transparency after developability, storage stability and thermal treatment is excellent.

If the I/O value of above-mentioned specific solvent is less than 0.50, then developability and storage stability not good enough.On the other hand, if I/O value is more than 1.00, then the transparency deterioration after thermal treatment.

In addition, the surface tension of above-mentioned specific solvent at 25 DEG C (also referred to as " surface tension ") is preferably 20dyn/cm ²~ 35dyn/cm ², be more preferably 22dyn/cm ²~ 35dyn/cm ², and then be more preferably 22dyn/cm ²~ 33dyn/cm ², be particularly preferably 23dyn/cm ²~ 31dyn/cm ².If above-mentioned scope, if above-mentioned scope, then the transparency after ink-jet ejection and thermal treatment is more excellent.

As the capillary assay method of above-mentioned specific solvent at 25 DEG C, known method can be used, but preferably utilize suspension ring method or hang sheet method (Wilhelmy method) and measure.Such as can preferably enumerate: the automatic surface tensiometer CBVP-Z using consonance interface science (share) to manufacture carries out method for measuring or uses the SIGMA702 of KSV instrument (KSV INSTRUMENTS) company limited manufacture to carry out method for measuring.

Above-mentioned specific solvent is non-alcohol series solvent, does not namely have the solvent of hydroxyl.If above-mentioned specific solvent is alcohol series solvent, then drying property, developability and storage stability are not good enough.

As above-mentioned specific solvent; preferably be selected from least one solvent in the group be made up of acidylate alkylene glycol monoalkyl ethers, acidylate two alkylene glycol monoalkyl ethers, two alkylene glycol dialkylether and three alkylene glycol dialkylether; be more preferably at least one solvent in the group being selected from and being made up of two alkylene glycol dialkylether and three alkylene glycol dialkylether, and then be more preferably two alkylene glycol dialkylether.If above-mentioned form, then the transparency after ink-jet ejection, drying property and thermal treatment is more excellent.

Above-mentioned specific solvent can be used alone a kind, also can and use two or more.

As the concrete example of above-mentioned specific solvent, can preferably enumerate following.

(BMGAC, boiling point is 188 DEG C to ethylene glycol monomethyl ether acetate, and surface tension is 27.4dyn/cm ², I/O value is 0.632)

(EDGAC, boiling point is 217 DEG C to diethylene glycol monoethyl ether acetic acid esters, and surface tension is 30.9dyn/cm ², I/O value is 0.818)

(DPMA, boiling point is 213 DEG C to dipropylene glycol monomethyl ether acetic acid esters, and surface tension is 27.3dyn/cm ², I/O value is 0.556)

(PGMEP, boiling point is 178 DEG C to propylene glycol monomethyl ether propionate, and surface tension is 27.2dyn/cm ², I/O value is 0.571)

(EDE (DEDG), boiling point is 189 DEG C to diethylene glycol diethyl ether, and surface tension is 25.1dyn/cm ², I/O value is 0.636)

(MTM, boiling point is 216 DEG C to TRIGLYME, and surface tension is 30.0dyn/cm ², I/O value is 0.800)

(MEDG (EDM), boiling point is 176 DEG C to diethylene glycol ethyl methyl ether, and surface tension is 26.8dyn/cm ², I/O value is 0.700)

(IPDM, boiling point is 179 DEG C to diethylene glycol isopropyl methyl ether, and surface tension is 23.9dyn/cm ², I/O value is 0.636)

(BDM, boiling point is 212 DEG C to 1-[2-(2-methoxy ethoxy) ethoxy] butane, and surface tension is 24.1dyn/cm ², I/O value is 0.583)

Wherein, as above-mentioned specific solvent, be preferably at least one solvent containing being selected from the group that is made up of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether and TRIGLYME, being more preferably at least one solvent containing being selected from the group that is made up of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol isopropyl methyl ether, being particularly preferably diethylene glycol diethyl ether.If above-mentioned form, then the transparency after ink-jet ejection, drying property and thermal treatment is more excellent.

In addition, as above-mentioned specific solvent, be particularly preferably propylene glycol monomethyl ether propionate, diethylene glycol diethyl ether and TRIGLYME.

As the solvent beyond the above-mentioned specific solvent used in photosensitive polymer combination of the present invention, known solvent can be used, can illustrate: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, ester class, ketone, amide-type, lactone etc.In addition, as the concrete example of the solvent used in photosensitive polymer combination of the present invention, also can enumerate solvent described in the paragraph 0167 ~ paragraph 0168 of solvent described in the paragraph 0174 ~ paragraph 0178 of Japanese Patent Laid-Open 2011-221494 publication, Japanese Patent Laid-Open 2012-194290 publication, these content can be incorporated into in present specification.

In addition, optionally also in these solvents, benzyl ether, two hexyl ethers, ethyleneglycol monophenylether acetic acid esters, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, methyl phenyl ethers anisole, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, ethylene carbonate, propylene carbonate equal solvent can be added further.

These solvents can be used alone a kind or two or more is used in combination.Solvent used in the present invention be preferably used alone a kind or and with 2 kinds.

Among these, as the solvent beyond above-mentioned specific solvent, be preferably non-alcohol series solvent, be more preferably propylene-glycol monoalky lether acetate esters, be particularly preferably propylene glycol methyl ether acetate.If above-mentioned form, then ink-jet ejection is more excellent.

In addition, for the concrete example of the solvent beyond the above-mentioned specific solvent that can be used as other solvents, represent boiling point, surface tension and/or I/O value.

(PGDA, boiling point is 190 DEG C to propylene-glycol diacetate, and surface tension is 31.2dyn/cm ², I/O value is 1.200)

(1,3-BGDA, boiling point is 232 DEG C to 1,3-BDO diacetate esters, and surface tension is 31.4dyn/cm ², I/O value is 0.750)

(Isosorbide-5-Nitrae-BDDA, boiling point is 232 DEG C to BDO diacetate esters, and surface tension is 34.2dyn/cm ², I/O value is 0.750)

(1,6-HDDA, boiling point is 260 DEG C to 1,6-hexanediol diacetate esters, and surface tension is 34.1dyn/cm ², I/O value is 0.600)

(CHXA, boiling point is 173 DEG C to adnoral acetate, and surface tension is 30.5dyn/cm ², I/O value is 0.438)

(PGMEA, boiling point is 146 DEG C to propylene glycol methyl ether acetate, and surface tension is 26.7dyn/cm ², I/O value is 0.667)

1-ethoxy-2-propyl-acetic acid ester (boiling point is 160 DEG C, and I/O value is 0.571)

(BDGAC, boiling point is 247 DEG C to butyl carbitol acetate, and surface tension is 29.7dyn/cm ², I/O value is 0.692)

Dipropylene glycol list positive propyl ether acetic acid esters (DPNPA, boiling point is 232 DEG C, and I/O value is 0.455)

Dipropylene glycol mono-n-butyl ether acetic acid esters (DPNBA, boiling point is 251 DEG C, and I/O value is 0.417)

(MBA, boiling point is 171 DEG C to butylene glycol methyl methyl ether acetate, and surface tension is 27.9dyn/cm ², I/O value is 0.571)

3-ethoxyl ethyl propionate (EEP, boiling point is 170 DEG C, and I/O value is 0.571)

(MDM, boiling point is 162 DEG C to diethylene glycol dimethyl ether, and surface tension is 28.1dyn/cm ², I/O value is 0.778)

(BDB, boiling point is 256 DEG C to dibutyl ethylene glycol ether, and surface tension is 24.9dyn/cm ², I/O value is 0.467)

(MTEM, boiling point is 275 DEG C to tetraethyleneglycol dimethyl ether, and surface tension is 31.8dyn/cm ², I/O value is 0.813)

(MDPOM, boiling point is 171 DEG C to tripropylene glycol dimethyl ether, and surface tension is 24.7dyn/cm ², I/O value is 0.375)

(DPMNP, boiling point is 203 DEG C to dipropylene glycol methyl-positive propyl ether, and surface tension is 25.2dyn/cm ², I/O value is 0.300)

(MTPOM, boiling point is 215 DEG C to two (2-methoxymethylethoxy) propane of 1,2-, and surface tension is 26.4dyn/cm ², I/O value is 0.364)

(BTM, boiling point is 261 DEG C to triethylene glycol butyl methyl ether, and surface tension is 27.5dyn/cm ², I/O value is 0.645)

(MPM, boiling point is 264 DEG C ~ 294 DEG C to Polyethylene glycol dimethyl ether, and surface tension is 33.4dyn/cm ²)

(MMM, boiling point is 85 DEG C to glycol dimethyl ether, and surface tension is 22.6dyn/cm ²)

(DRA-150, boiling point is 260 DEG C to glyceryl triacetate, and surface tension is 35.2dyn/cm ², I/O value is 1.000)

Cyclohexanone (boiling point is 156 DEG C, and I/O value is 0.625)

Methyl amyl ketone (boiling point is 151 DEG C for 2-HEPTANONE, MAK, and I/O value is 0.464)

Tetrahydrofurfuryl alcohol (THFA, boiling point is 176 DEG C, and I/O value is 1.300)

(DPM, boiling point is 188 DEG C to dipropylene glycol monomethyl ether, and surface tension is 27.9dyn/cm ², I/O value is 1.000)

(DM, boiling point is 194 DEG C to diethylene glycol monomethyl ether, and surface tension is 34.3dyn/cm ², I/O value is 1.375)

(DB, boiling point is 230 DEG C to diethylene glycol monobutyl ether, and surface tension is 29.1dyn/cm ², I/O value is 1.000)

(boiling point is 245 DEG C to ethyleneglycol monophenylether for 2-phenoxetol, EPH, and surface tension is 41.9dyn/cm ², I/O value is 0.844)

(TM, boiling point is 249 DEG C to triethylene glycol monomethyl ether, and surface tension is 36.4dyn/cm ², I/O value is 1.217)

(PM, boiling point is 290 DEG C ~ 310 DEG C to poly glycol monomethyl ether, and surface tension is 37.3dyn/cm ²)

(MB, boiling point is 161 DEG C to 3-methoxybutanol, and surface tension is 28.9dyn/cm ², I/O value is 1.200)

(1,3-BG, boiling point is 208 DEG C to 1,3-BDO, and surface tension is 36.1dyn/cm ², I/O value is 2.500)

(PNP, boiling point is 150 DEG C to propylene glycol list positive propyl ether, and surface tension is 25.9dyn/cm ², I/O value is 1.000)

(PNB, boiling point is 170 DEG C to propylene glycol mono-n-butyl ether, and surface tension is 26.3dyn/cm ², I/O value is 0.875)

(EDG, boiling point is 202 DEG C to diethylene glycol monoethyl ether, and surface tension is 31.3dyn/cm ², I/O value is 1.200)

(DPNP, boiling point is 212 DEG C to dipropylene glycol list positive propyl ether, and surface tension is 27.6dyn/cm ², I/O value is 0.778)

(DPNB, boiling point is 229 DEG C to dipropylene glycol mono-n-butyl ether, and surface tension is 28.8dyn/cm ², I/O value is 0.700)

(TPM, boiling point is 242 DEG C to Tripropylene glycol monomethyl Ether, and surface tension is 30.0dyn/cm ², I/O value is 0.800)

(TPNB, boiling point is 274 DEG C to tripropylene glycol mono-n-butyl ether, and surface tension is 29.7dyn/cm ², I/O value is 0.615)

(MMPG (PGME), boiling point is 121 DEG C to propylene glycol monomethyl ether, and surface tension is 27.7dyn/cm ²)

There is no particular restriction for the content of above-mentioned specific solvent, but relative to the gross mass of the solvent in photosensitive polymer combination, be preferably 1 quality % ~ 100 quality %, be more preferably 5 quality % ~ 95 quality %, and then be more preferably 5 quality % ~ 90 quality %.If above-mentioned scope, then ink-jet ejection and drying property more excellent.

Relative to the gross mass of photosensitive polymer combination, the content of (composition B) solvent in photosensitive polymer combination of the present invention is preferably 10 quality % ~ 95 quality %, be more preferably 50 quality % ~ 95 quality %, and then be more preferably 60 mass parts ~ 90 mass parts.

(composition C) is containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base

Photosensitive polymer combination of the present invention comprises (composition C) containing the polymkeric substance of Component units with the base that acidic group is protected by sour decomposability base.

Moreover, in the present invention, also " having the Component units of the base that acidic group is protected by sour decomposability base " is called " Component units that (a1) has the base that acidic group is protected by sour decomposability base ".

Photosensitive polymer combination of the present invention and then can comprise the polymkeric substance beyond the polymkeric substance containing the Component units with the base that acidic group is protected by sour decomposability base.

Photosensitive polymer combination of the present invention is preferably containing the component of polymer comprising the polymkeric substance of at least one meeting following (1) and following (2).

(1) containing (a1), there is the polymkeric substance that the Component units of the base that acidic group is protected by sour decomposability base and (a2) have the Component units of bridging property base

(2) containing (a1), there is the polymkeric substance of the Component units of the base that acidic group is protected by sour decomposability base and there is containing (a2) polymkeric substance of the Component units of bridging property base

The polymkeric substance that photosensitive polymer combination of the present invention can and then contain beyond these.As long as no special instructions, then the composition C in the present invention refers to except above-mentioned (1) and/or (2), contains optionally and the composition of other polymkeric substance of interpolation.Moreover, except composition E described later and composition F.

With regard to sclerosis after the transparency (mist degree) and unexposed portion residual film ratio viewpoint with regard to, photosensitive polymer combination of the present invention be preferably containing meeting the composition of above-mentioned (1) as composition C.

On the other hand, with regard to the viewpoint of the degree of freedom of MOLECULE DESIGN, photosensitive polymer combination of the present invention is preferably containing meeting the composition of above-mentioned (2) as composition C.

Moreover; when containing when meeting the composition of above-mentioned (1), also and then can comprise and containing (a1), there is the polymkeric substance of the Component units of the base that acidic group protect by sour decomposability base and/or contain the polymkeric substance that (a2) has the Component units of bridging property base.

In addition; when containing when meeting the composition of above-mentioned (2); when at least comprise be equivalent to containing (a1) have the Component units of the base that acidic group is protected by sour decomposability base and (a2) there is the composition of the polymkeric substance of the Component units of bridging property base time, also as situation about being equivalent to containing the composition meeting above-mentioned (1).

Composition C is preferably the resin of addition polymerization type, is more preferably the polymkeric substance containing the Component units being derived from (methyl) acrylic acid and/or its ester.Moreover, also can have the Component units beyond the Component units being derived from (methyl) acrylic acid and/or its ester, such as, be derived from cinnamic Component units or be derived from the Component units etc. of vinyl compound.

Moreover, also " being derived from the Component units of (methyl) acrylic acid and/or its ester " is called " acrylic acid series Component units ".In addition, " (methyl) acrylic acid " refers to " methacrylic acid and/or acrylic acid ".

< Component units (a1) >

Composition C comprises the polymkeric substance at least containing (a1) with the Component units of the base that acidic group is protected by sour decomposability base.Comprise the polymkeric substance containing Component units (a1) by composition C, and can be made into the high photosensitive polymer combination of sensitivity.

" base that acidic group is protected by sour decomposability base " in the present invention can be used as acidic group and the known base of sour decomposability base, is not particularly limited.As concrete acidic group, can preferably enumerate carboxyl and phenolic hydroxyl group.In addition, as sour decomposability base, can use than base acetal system functional groups such as () such as ester structure described later, oxinane ester group or tetrahydrofuran ester groups being easier to decompose because of acid or compare base carbonic acid three grades of alkyl ester groups such as () such as three grades of alkyl ester groups such as tert-butyl ester base, t-butyl carbonate bases being difficult to decompose because of sour.

(a1) Component units with the base that acidic group is protected by sour decomposability base preferably has the Component units of the protection carboxyl that carboxyl is protected by sour decomposability base (also referred to as " having the Component units of the protection carboxyl protected by sour decomposability base ") or has the Component units (also referred to as " having the Component units of the protection phenolic hydroxyl group protected by sour decomposability base ") of the protection phenolic hydroxyl group that phenolic hydroxyl group is protected by sour decomposability base.

Below, successively the Component units (a1-1) with the protection carboxyl protected by sour decomposability base and the Component units (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base are described respectively.

<< (a1-1) has the Component units >> of the protection carboxyl protected by sour decomposability base

The above-mentioned Component units (a1-1) with the protection carboxyl protected by sour decomposability base is the Component units of carboxyl by the following protection carboxyl protected by the sour decomposability base described in detail of the Component units had containing carboxyl.

As can be used for the above-mentioned above-mentioned Component units with carboxyl with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base, known Component units can be used with no particular limitation.Include, for example: be derived from the Component units (a1-1-1) in unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids equimolecular with the unsaturated carboxylic acid of at least one carboxyl etc., or there is ethene unsaturated group and the Component units (a1-1-2) of structure being derived from acid anhydrides simultaneously.

Below, be derived from molecule the Component units of the unsaturated carboxylic acid with at least one carboxyl etc. and (a1-1-2) to can be used as above-mentioned (a1-1-1) with the Component units of carboxyl there is ethene unsaturated group be simultaneously described respectively with the Component units of the structure being derived from acid anhydrides successively.

<<< (a1-1-1) is derived from molecule the Component units >>> of the unsaturated carboxylic acid with at least one carboxyl etc.

As the above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least one carboxyl etc., the unsaturated carboxylic acid lifted as listed below can be used as the unsaturated carboxylic acid used in the present invention.Namely, as unsaturated monocarboxylic, include, for example: acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(methyl) acryloyloxyethylsuccinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid etc.In addition, as unsaturated dicarboxylic, include, for example: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.In addition, the unsaturated polybasic carboxylic acid for obtaining the Component units with carboxyl also can be its acid anhydrides.Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride etc. can be enumerated.In addition, unsaturated polybasic carboxylic acid also can be list (2-(methyl) acryloxyalkyl) ester of polybasic carboxylic acid, include, for example: succinic acid list (2-acryloyl-oxyethyl) ester, succinic acid list (2-methacryloxyethyl) ester, phthalic acid list (2-acryloyl-oxyethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.And then unsaturated polybasic carboxylic acid also can be list (methyl) acrylate of its two ends dicarboxyl polymkeric substance, include, for example ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates etc.In addition, as unsaturated carboxylic acid, acrylic acid-2-carboxyethyl, methacrylic acid-2-carboxyethyl, maleic acid mono alkyl ester, fumaric acid mono alkyl ester, 4-carboxyl styrene etc. also can be used.

Wherein, with regard to the viewpoint of developability, in order to form the above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least one carboxyl etc., preferably use the acid anhydride etc. of acrylic acid, methacrylic acid, 2-(methyl) acryloyloxyethylsuccinic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid or unsaturated polybasic carboxylic acid, be more preferably and use acrylic acid, methacrylic acid, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid.

The above-mentioned Component units (a1-1-1) being derived from molecule the unsaturated carboxylic acid with at least one carboxyl etc. can comprise separately a kind, also can comprise two or more.

<<< (a1-1-2) has ethene unsaturated group and the Component units >>> of structure being derived from acid anhydrides simultaneously

There is the unit that ethene unsaturated group and the Component units (a1-1-2) of structure being derived from acid anhydrides are preferably derived from the monomer that hydroxyl existing in the Component units making to have ethene unsaturated group and acid anhydrides carry out reacting and obtain simultaneously.

As above-mentioned acid anhydrides, known acid anhydrides can be used, specifically, can enumerate: the dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; The acid anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxyacid acid acid anhydride.Among these acid anhydrides, with regard to the viewpoint of developability, be preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.

With regard to the viewpoint of developability, above-mentioned acid anhydrides is preferably 10 % by mole ~ 100 % by mole for the reaction rate of hydroxyl, is more preferably 30 % by mole ~ 100 % by mole.

-can be used for the sour decomposability base of Component units (a1-1)-

As can be used for the above-mentioned above-mentioned sour decomposability base with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base, above-mentioned sour decomposability base can be used.

Among these sour decomposability bases; with regard to the basic physical properties of photosensitive polymer combination; the particularly viewpoint of sensitivity or pattern form, the formative of contact hole, the storage stability of photosensitive polymer combination, being preferably carboxyl is the protection carboxyl protected by the form of acetal.And then, among sour decomposability base, with regard to the viewpoint of sensitivity, be more preferably carboxyl for by the protection carboxyl protected with the form of the acetal represented by following general formula (a1-10).Moreover at carboxyl for by the protection carboxyl protected with the form of the acetal represented by following formula (a1-10), the entirety of protection carboxyl becomes-(C=O)-O-CR ¹⁰¹r ¹⁰²(OR ¹⁰³) structure.

[changing 1]

(in formula (a1-10), R ¹⁰¹and R ¹⁰²separately represent hydrogen atom, alkyl or aryl, wherein, get rid of R ¹⁰¹with R ¹⁰²be the situation of hydrogen atom.R ¹⁰³represent alkyl or aryl.R ¹⁰¹or R ¹⁰²with R ¹⁰³can link and form cyclic ether)

In above-mentioned formula (a1-10), R ¹⁰¹~ R ¹⁰³in alkyl can be straight-chain, branched, ring-type any one.Herein, there is not R ¹⁰¹and R ¹⁰²all represent the situation of hydrogen atom, R ¹⁰¹and R ¹⁰²at least one represent alkyl.

In above-mentioned formula (a1-10), work as R ¹⁰¹, R ¹⁰²and R ¹⁰³when representing alkyl, abovementioned alkyl can be any one of straight-chain, branched or ring-type.

As the alkyl of above-mentioned straight-chain or branched, being preferably carbon number is 1 ~ 12, and being more preferably carbon number is 1 ~ 6, and then to be more preferably carbon number be 1 ~ 4.Specifically, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.

As above-mentioned cyclic alkyl, being preferably carbon number is 3 ~ 12, and being more preferably carbon number is 4 ~ 8, and then to be more preferably carbon number be 4 ~ 6.As above-mentioned cyclic alkyl, include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norcamphanyl, different camphyl etc.

Abovementioned alkyl also can have substituting group, alternatively base, can illustrate halogen atom, aryl, alkoxy.When have halogen atom alternatively base time, R ¹⁰¹, R ¹⁰², R ¹⁰³become haloalkyl, when have aryl alternatively base time, R ¹⁰¹, R ¹⁰², R ¹⁰³become aralkyl.

As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be illustrated, among these halogen atoms, be preferably fluorine atom or chlorine atom.

In addition, as above-mentioned aryl, being preferably carbon number is the aryl of 6 ~ 20, is more preferably the aryl that carbon number is 6 ~ 12.Specifically, can illustrate phenyl, Alpha-Methyl phenyl, naphthyl etc., overall as the alkyl replaced by aryl, i.e. aralkyl, can illustrate benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc.

As above-mentioned alkoxy, being preferably carbon number is the alkoxy of 1 ~ 6, is more preferably the alkoxy that carbon number is 1 ~ 4, and then is more preferably methoxy or ethoxy.

In addition, when abovementioned alkyl is naphthenic base, it is the straight-chain of 1 ~ 10 or the alkyl alternatively base of branched that above-mentioned naphthenic base can have carbon number, when alkyl is the alkyl of straight-chain or branched, can have the naphthenic base alternatively base that carbon number is 3 ~ 12.

These substituting groups also can be replaced by above-mentioned substituting group further.

In above-mentioned formula (a1-10), work as R ¹⁰¹, R ¹⁰²and R ¹⁰³when representing aryl, it is 6 ~ 12 that above-mentioned aryl is preferably carbon number, and being more preferably carbon number is 6 ~ 10.Above-mentioned aryl can have substituting group, as above-mentioned substituting group, preferably can illustrate the alkyl that carbon number is 1 ~ 6.As aryl, such as, can illustrate phenyl, tolyl, xylyl, cumenyl, 1-naphthyl etc.

In addition, R ¹⁰¹, R ¹⁰²and R ¹⁰³can bond mutually, and together form ring with the carbon atom of these bonds.As R ¹⁰¹with R ¹⁰², R ¹⁰¹with R ¹⁰³or R ¹⁰²with R ¹⁰³ring structure during bond, include, for example: cyclobutyl, cyclopentyl, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc.

Moreover, in above-mentioned formula (a1-10), be preferably R ¹⁰¹and R ¹⁰²any one be hydrogen atom or methyl.

Free radical polymerization monomer for the formation of the Component units containing the protection carboxyl represented by above-mentioned formula (a1-10) can use commercially available free radical polymerization monomer, also can use the free radical polymerization monomer synthesized by known method.Such as, synthetic method etc. described in the paragraph 0037 ~ paragraph 0040 of Japanese Patent Laid-Open 2011-221494 publication can be utilized to synthesize.

Above-mentioned the first preferred form with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base is the Component units represented by following formula.

[changing 2]

(in formula, R ¹and R ²separately represent hydrogen atom, alkyl or aryl, at least R ¹and R ²any one be alkyl or aryl, R ³represent alkyl or aryl, R ¹or R ²with R ³can link and form cyclic ether, R ⁴represent hydrogen atom or methyl, X represents singly-bound or arlydene)

Work as R ¹and R ²during for alkyl, being preferably carbon number is the alkyl of 1 ~ 10.Work as R ¹and R ²during for aryl, be preferably phenyl.R ¹and R ²be preferably separately for hydrogen atom or carbon number are the alkyl of 1 ~ 4.

R ³represent alkyl or aryl, being preferably carbon number is the alkyl of 1 ~ 10, is more preferably the alkyl of 1 ~ 6.

X represents singly-bound or arlydene, is preferably singly-bound.

The above-mentioned preferred form of the second with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base is the Component units of following formula.

[changing 3]

(in formula, R ¹²¹represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, L ¹represent carbonyl or phenylenecarbonyl, R ¹²²~ R ¹²⁸separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4)

R ¹²¹be preferably hydrogen atom or methyl.

L ¹be preferably carbonyl.

R ¹²²~ R ¹²⁸be preferably hydrogen atom.

As the above-mentioned preferred concrete example with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base, following Component units can be illustrated.Moreover R represents hydrogen atom or methyl.

[changing 4]

<< (a1-2) has the Component units >> of the protection phenolic hydroxyl group protected by sour decomposability base

The above-mentioned Component units (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base is that the Component units with phenolic hydroxyl group has following by the Component units of the protection phenolic hydroxyl group protected by sour decomposability base of detailed description.

<<< (a1-2-1) has the Component units >>> of phenolic hydroxyl group

As the above-mentioned Component units with phenolic hydroxyl group, the Component units in the resin of hydroxy styrenes system Component units or novolaks system can be enumerated, among these Component units, with regard to the viewpoint of sensitivity, be preferably derived from the Component units of hydroxy styrenes or Alpha-Methyl hydroxy styrenes.In addition, as the Component units with phenolic hydroxyl group, with regard to the viewpoint of sensitivity, the Component units represented by following formula (a1-20) is also preferred.

[changing 5]

(in formula (a1-20), R ²²⁰represent hydrogen atom or methyl, R ²²¹represent the concatenating group of singly-bound or divalence, R ²²²represent that halogen atom or carbon number are the alkyl of the straight or branched of 1 ~ 5, a represents the integer of 1 ~ 5, and b represents the integer of 0 ~ 4, and a+b is less than 5.Moreover, as the R of existence more than 2 ²²²time, these R ²²²can be mutually different, also can be identical)

In above-mentioned formula (a1-20), R ²²⁰represent hydrogen atom or methyl, be preferably methyl.

In addition, R ²²¹represent the concatenating group of singly-bound or divalence.Work as R ²²¹during for singly-bound, can sensitivity be promoted, and then the transparency of cured film can be promoted, therefore preferably.As R ²²¹the concatenating group of divalence, can illustrate alkylidene, being preferably carbon number is the alkylidene of 1 ~ 12, is more preferably the alkylidene that carbon number is 1 ~ 8, and then is more preferably the alkylidene that carbon number is 1 ~ 3.As R ²²¹for concrete example during alkylidene, can enumerate: methylene, ethylidene, propylidene, isopropylidene, sub-normal-butyl, isobutylidene, the sub-tert-butyl group, pentylidene, isoamylidene, sub-neopentyl, hexylidene etc.Wherein, R ²²¹be preferably singly-bound, methylene, ethylidene, 1,2-propylidene, 1,3-propylidene or 2-hydroxyl-1,3-propylidene.In addition, the concatenating group of above-mentioned divalence can have substituting group, and alternatively base can enumerate halogen atom, hydroxyl, alkoxy etc.In addition, a represents the integer of 1 ~ 5, but with regard to effect of the present invention viewpoint or easily manufacture with regard to this point, being preferably a is 1 or 2, and being more preferably a is 1.

In addition, when will with R ²²¹when the carbon atom carrying out bond is as benchmark (1), the binding site of the hydroxyl in phenyl ring is preferably binding on 4.

R ²²²separately represent that halogen atom or carbon number are the alkyl of the straight or branched of 1 ~ 5.Specifically, can enumerate: fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl etc.Wherein, just easily manufacture with regard to this point, be preferably chlorine atom, bromine atoms, methyl or ethyl.

In addition, b represents the integer of 0 or 1 ~ 4.

-can be used for the sour decomposability base of Component units (a1-2)-

As can be used for the above-mentioned above-mentioned sour decomposability base with the Component units (a1-2) of the protection phenolic hydroxyl group protected by sour decomposability base; with can be used in the same manner as the above-mentioned above-mentioned sour decomposability base with the Component units (a1-1) of the protection carboxyl protected by sour decomposability base; known sour decomposability base can be used, be not particularly limited.Among acid decomposability base; with regard to the basic physical properties of photosensitive polymer combination; particularly the viewpoint of sensitivity or pattern form, the storage stability of photosensitive polymer combination, the formative of contact hole, preferably has the Component units of the protection phenolic hydroxyl group protected by acetal.And then, among sour decomposability base, with regard to the viewpoint of sensitivity, be more preferably phenolic hydroxyl group for by the protection phenolic hydroxyl group protected with the form of the acetal represented by above-mentioned formula (a1-10).Moreover in phenolic hydroxyl group for by the protection phenolic hydroxyl group protected with the form of the acetal represented by above-mentioned formula (a1-10), the entirety of protection phenolic hydroxyl group becomes-Ar-O-CR ¹⁰¹r ¹⁰²(OR ¹⁰³) structure.Moreover Ar represents arlydene.

The preference of the acetal ester structure of phenolic hydroxyl group can illustrate R ¹⁰¹=hydrogen atom, R ¹⁰²=R ¹⁰³the combination of=methyl or R ¹⁰¹=hydrogen atom, R ¹⁰²=methyl and R ¹⁰³the combination of=benzyl, R ¹⁰¹=hydrogen atom, R ¹⁰²=methyl and R ¹⁰³the combination of=ethyl.

In addition; as for the formation of the free radical polymerization monomer of Component units with the protection phenolic hydroxyl group that the form of phenolic hydroxyl group by acetal is protected, include, for example free radical polymerization monomer etc. described in the paragraph 0042 of Japanese Patent Laid-Open 2011-215590 publication.

Among these free radical polymerization monomers, with regard to the viewpoint of the transparency, be preferably the 1-alkoxyalkyl protective of methacrylic acid 4-hydroxylphenyl ester, the THP trtrahydropyranyl protective of methacrylic acid 4-hydroxylphenyl ester.

As the concrete example of the acetal protecting group of phenolic hydroxyl group; 1-alkoxyalkyl can be enumerated; include, for example 1-ethoxyethyl group, 1-methoxy ethyl, 1-n-butoxyethyl, 1-isobutoxyethy, 1-(2-chloroethoxy) ethyl, 1-(2-ethyl hexyl oxy) ethyl, 1-positive propoxy ethyl, 1-cyclohexyloxy ethyl, 1-(2-cyclohexylethoxy radical) ethyl, 1-Benzyloxyethyl etc., these bases can be used alone a kind or two or more combinationally used.

Commercially available free radical polymerization monomer can be used for the formation of the above-mentioned free radical polymerization monomer with the Component units (a1-2) of the protection phenolic hydroxyl group protected by sour decomposability base, also can use the free radical polymerization monomer synthesized by known method.Such as, compound and vinyl ether by making to have phenolic hydroxyl group in the presence of acid catalyst carry out reacting synthesizing.Above-mentioned synthesis also can make to have the monomer of phenolic hydroxyl group in advance and other monomers carry out copolymerization, then reacts with vinyl ether in the presence of acid catalyst.

As the above-mentioned preferred concrete example with the Component units (a1-2) of the protection phenolic hydroxyl group protected by sour decomposability base, following Component units can be illustrated, but the present invention is not limited to these Component units.In following concrete example, R represents hydrogen atom or methyl.

[changing 6]

-the preferred form of Component units (a1)-

When the polymkeric substance containing above-mentioned Component units (a1) is not in fact containing Component units (a2), in the polymkeric substance containing described Component units (a1), Component units (a1) is preferably 20 % by mole ~ 100 % by mole, is more preferably 30 % by mole ~ 90 % by mole.

When the polymkeric substance containing above-mentioned Component units (a1) contains following Component units (a2), with regard to the viewpoint of sensitivity, in the polymkeric substance containing described Component units (a1) and Component units (a2), single Component units (a1) is preferably 3 % by mole ~ 70 % by mole, is more preferably 10 % by mole ~ 60 % by mole.In addition, especially when the Component units that above-mentioned Component units (a1) is the protection carboxyl that has carboxyl and protected by the form of acetal, 20 % by mole ~ 50 % by mole are preferably.

And then in the present invention, when specifying the content of " Component units " with mol ratio, the implication of described " Component units " is identical with " monomeric unit ".In addition, in the present invention, described " monomeric unit " is modified after polymerisation by high molecular weight reactive etc.Below like this too.

Compared with the above-mentioned Component units (a1-2) with the protection phenolic hydroxyl group protected by sour decomposability base, the above-mentioned Component units (a1-1) with the protection carboxyl protected by sour decomposability base has development this feature fast.Therefore, when for rapid development, preferably there is the Component units (a1-1) of the protection carboxyl protected by sour decomposability base.On the contrary, when making development slack-off, be preferably the Component units (a1-2) using and there is the protection phenolic hydroxyl group protected by sour decomposability base.

< (a2) has the Component units > of bridging property base

Composition C contains polymkeric substance, and this polymkeric substance contains the Component units (a2) with bridging property base.As long as above-mentioned bridging property base produces the base of sclerous reaction by heating, be then not particularly limited.As the form of Component units preferably with bridging property base, can enumerate containing be selected from by epoxy radicals, oxetanylmethoxy, by-NH-CH ₂the Component units of at least one in the group that base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20) and ethene unsaturated group form, is preferably selected from by epoxy radicals, oxetanylmethoxy and by-NH-CH ₂at least one in the group that base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20) forms.Wherein, photosensitive polymer combination of the present invention is more preferably mentioned component C and comprises Component units containing at least one in epoxy radicals and oxetanylmethoxy.More specifically, following Component units can be enumerated.

<< (a2-1) has the Component units >> of epoxy radicals and/or oxetanylmethoxy

Composition C is preferably containing polymkeric substance, and this polymkeric substance contains the Component units (Component units (a2-1)) with epoxy radicals and/or oxetanylmethoxy.The cyclic ether group of 3 rings is also referred to as epoxy radicals, and the cyclic ether group of 4 rings is also referred to as oxetanylmethoxy.

Above-mentioned have the Component units (a2-1) of epoxy radicals and/or oxetanylmethoxy as long as have at least one epoxy radicals or oxetanylmethoxy in 1 Component units, epoxy radicals and more than 1 oxetanylmethoxy, the epoxy radicals of more than 2 or the oxetanylmethoxy of more than 2 of more than 1 can be had, be not particularly limited, but preferably there is the epoxy radicals and/or oxetanylmethoxy that add up to 1 ~ 3, be more preferably the epoxy radicals and/or oxetanylmethoxy that have and add up to 1 or 2, and then be more preferably there is 1 epoxy radicals or oxetanylmethoxy.

As for the formation of the concrete example of free radical polymerization monomer of Component units with epoxy radicals, include, for example glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid-3, 4-epoxy radicals butyl ester, methacrylic acid-3, 4-epoxy radicals butyl ester, acrylic acid-3, 4-epoxycyclohexanecarboxylate, methacrylic acid-3, 4-epoxycyclohexanecarboxylate, α-ethylacrylate-3, 4-epoxycyclohexanecarboxylate, adjacent vinylbenzyl glycidyl ether, between vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, the compound etc. containing ester ring type epoxy radicals skeleton described in the paragraph 0031 ~ paragraph 0035 of Jap.P. No. 4168443 publication, these content can be incorporated into in present specification.

As for the formation of the concrete example of free radical polymerization monomer of Component units with oxetanylmethoxy, include, for example (methyl) acrylate etc. with oxetanylmethoxy described in the paragraph 0011 ~ paragraph 0016 of Japanese Patent Laid-Open 2001-330953 publication, these content can be incorporated into in present specification.

As for the formation of the above-mentioned concrete example with the free radical polymerization monomer of the Component units (a2-1) of epoxy radicals and/or oxetanylmethoxy, be preferably containing the monomer of metacrylic acid ester structure, the monomer containing acrylate structural.

Among these, be preferably glycidyl methacrylate, acrylic acid 3,4-epoxycyclohexanecarboxylate, methacrylic acid 3,4-epoxycyclohexanecarboxylate, acrylic acid (3-Ethyloxetane-3-base) methyl esters and methacrylic acid (3-Ethyloxetane-3-base) methyl esters.These Component units can be used alone a kind or two or more combinationally used.

As the preferred concrete example of Component units (a2-1) with epoxy radicals and/or oxetanylmethoxy, following Component units can be illustrated.Moreover R represents hydrogen atom or methyl.

[changing 7]

<< (a2-2) has the Component units >> of ethene unsaturated group

As above-mentioned a kind with the Component units (a2) of bridging property base, the Component units (a2-2) (hereinafter also referred to as " Component units (a2-2) ") with ethene unsaturated group can be enumerated.As the above-mentioned Component units (a2-2) with ethene unsaturated group, be preferably Component units side chain with ethene unsaturated group, be more preferably end and there is ethene unsaturated group and there is the Component units that carbon number is the side chain of 3 ~ 16.

In addition, there is about (a2-2) Component units of ethene unsaturated group, can with reference to the record of the paragraph 0013 ~ paragraph 0031 of the record of the paragraph 0072 ~ paragraph 0090 of Japanese Patent Laid-Open 2011-215580 publication and Japanese Patent Laid-Open 2008-256974 publication, these content can be incorporated into in present specification.

<< (a2-3) has by-NH-CH ₂the Component units >> of the base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20)

The multipolymer used in the present invention also preferably has by-NH-CH ₂the Component units (a2-3) of the base represented by-O-R (R represents the alkyl that hydrogen atom or carbon number are 1 ~ 20).By containing Component units (a2-3), the heating of mitigation can be utilized to produce sclerous reaction, and the cured film of various excellent can be obtained.Herein, R is preferably the alkyl that carbon number is 1 ~ 20, is more preferably the alkyl that carbon number is 1 ~ 9, and then is more preferably the alkyl that carbon number is 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, but is preferably the alkyl of straight chain or branch.Component units (a2) is more preferably the Component units of the base had represented by following formula (a2-30).

[changing 8]

(in formula (a2-30), R ³¹represent hydrogen atom or methyl, R ³²represent that carbon number is the alkyl of 1 ~ 20)

R ³²being preferably carbon number is the alkyl of 1 ~ 9, is more preferably the alkyl that carbon number is 1 ~ 4.In addition, alkyl can be any one of alkyl of straight chain, branch or ring-type, but is preferably the alkyl of straight chain or branch.

As R ³²concrete example, can enumerate: methyl, ethyl, normal-butyl, isobutyl, cyclohexyl and n-hexyl.Wherein, isobutyl, normal-butyl, methyl is preferably.

-the preferred form of Component units (a2)-

When the polymkeric substance containing above-mentioned Component units (a2) is not in fact containing Component units (a1), in the polymkeric substance containing described Component units (a2), Component units (a2) is preferably 5 % by mole ~ 90 % by mole, is more preferably 20 % by mole ~ 80 % by mole.

When the polymkeric substance containing above-mentioned Component units (a2) contains above-mentioned Component units (a1), with regard to the viewpoint of chemical-resistant, in the polymkeric substance containing described Component units (a1) and Component units (a2), the content of Component units (a2) is preferably 3 % by mole ~ 70 % by mole, is more preferably 10 % by mole ~ 60 % by mole.

And then, in the present invention, no matter which kind of form, in all Component units of composition C, be preferably the Component units (a2) containing 3 % by mole ~ 70 % by mole, be more preferably the Component units (a2) containing 10 % by mole ~ 60 % by mole.

If in the scope of above-mentioned numerical value, then the transparency of the cured film obtained by photosensitive polymer combination and chemical-resistant become good.

< (a3) other Component units >

In the present invention, composition C, also can containing other Component units (a3) beyond these except above-mentioned Component units (a1) and/or Component units (a2).These Component units can contain above-mentioned component of polymer (1) and/or component of polymer (2).In addition, except above-mentioned component of polymer (1) or component of polymer (2), also can comprise the component of polymer in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3).When except above-mentioned component of polymer (1) or component of polymer (2), when comprising the component of polymer in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3), in all component of polymer, the allotment amount of described component of polymer is preferably below 60 quality %, be more preferably below 40 quality %, and then be more preferably below 20 quality %.In addition, the lower limit of above-mentioned allotment amount is 0 quality %.

As the monomer becoming other Component units (a3), there is no particular restriction, include, for example: phenylethylene, (methyl) alkyl acrylate, (methyl) acrylic acid cyclic alkyl ester, (methyl) benzyl acrylate, unsaturated dicarboxylic diester, dicyclo unsaturated compound class, maleimide compounds class, unsaturated aromatics, conjugated diolefine based compound, unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic acid anhydride, other unsaturated compounds.In addition, as aftermentioned, also can containing the Component units with acidic group.The monomer becoming other Component units (a3) can be used alone a kind or two or more combinationally used.

Specifically, other Component units (a3) can enumerate the Component units formed by following compound etc.: styrene, methyl styrene, hydroxy styrenes, α-methyl styrene, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, vinylbenzoate, vinyl benzoic acid ethyl ester, 4-HBA (3-methacryloxypropyl) ester, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) benzyl acrylate, the different camphane ester of (methyl) acrylic acid, vinyl cyanide, ethylene glycol single acetyl acetic acid list (methyl) acrylate.In addition, compound described in the paragraph 0021 ~ paragraph 0024 of Japanese Patent Laid-Open 2004-264623 publication can be enumerated.

In addition, as other Component units (a3), with regard to the viewpoint of electrical characteristics, be preferably derived from phenylethylene or there is the Component units of monomer of aliphatics ring type skeleton.Specifically, can enumerate: styrene, methyl styrene, hydroxy styrenes, α-methyl styrene, (methyl) acrylic acid two ring pentyl ester, (methyl) cyclohexyl acrylate, the different camphane ester of (methyl) acrylic acid, (methyl) benzyl acrylate etc.

And then, as other Component units (a3), with regard to the viewpoint of adherence, be preferably derived from the Component units of (methyl) alkyl acrylate.Specifically, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate etc. can be enumerated, be more preferably (methyl) methyl acrylate.Form in the Component units of polymkeric substance, the containing ratio of above-mentioned Component units (a3) is preferably less than 60 % by mole, is more preferably less than 50 % by mole, and then is more preferably less than 40 % by mole.As lower limit, can be 0 % by mole, but be such as preferably set to more than 1 % by mole, be more preferably and be set to more than 5 % by mole.If in the scope of above-mentioned numerical value, then the various characteristics of the cured film obtained by photosensitive polymer combination become good.

Polymkeric substance contained in composition C is preferably containing having the Component units of acidic group as other Component units (a3).Polymkeric substance by having acidic group, and is easily dissolved in the developer solution of alkalescence, and effect of the present invention is more effectively played.Acidic group in the present invention refers to the proton dissociation base that pKa is less than 10.5.Usually, use the monomer that can form acidic group as the Component units with acidic group, and acidic group is directed in polymkeric substance.There is by comprising this kind in the polymer the Component units of acidic group, and there is the tendency in the developer solution being easily dissolved in alkalescence.

As acidic group; can illustrate carboxylic acid group, sulfoamido, phosphonate group, sulfonic group, phenolic hydroxyl group, sulfoamido, sulfonyl imide and these acidic groups anhydride group and these acidic groups are neutralized and are formed the base etc. of salt structure, be preferably carboxylic acid group and/or phenolic hydroxyl group.As above-mentioned salt, there is no particular restriction, can preferably illustrate alkali metal salt, alkali salt and organic ammonium salt.

The Component units with acidic group used in the present invention is more preferably the Component units being derived from the distyryl compound with acidic group or the Component units being derived from the vinyl compound with acidic group, be derived from (methyl) acrylic acid Component units and/or be derived from the Component units of (methyl) acrylate with acidic group.Such as can use the compound recorded in the paragraph 0021 ~ paragraph 0023 of Japanese Patent Laid-Open 2012-88459 publication and paragraph 0029 ~ paragraph 0044, described content can be incorporated into in present specification.Wherein, the Component units of 4-Vinyl phenol, (methyl) acrylic acid, maleic acid, maleic anhydride is preferably derived from.

In the present invention, except above-mentioned component of polymer (1) or component of polymer (2), also can comprise the polymkeric substance in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3).

As this kind of polymkeric substance, be preferably resin side chain with carboxyl.Include, for example as No. 59-44615, Japanese Patent Laid-Open No. Sho, No. 54-34327, Jap.P. examined patent publication, No. 58-12577, Jap.P. examined patent publication, No. 54-25957, Jap.P. examined patent publication, No. 59-53836, Japanese Patent Laid-Open No. Sho, methacrylic acid copolymer as described in each publication of No. 59-71048, Japanese Patent Laid-Open No. Sho, acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, acid/maleic acid copolymers, partial esterification acid/maleic acid copolymers etc., and side chain has the acid cellulose derivant of carboxyl, in the polymkeric substance with hydroxyl addition acid anhydrides etc., and then also can enumerate on side chain there is (methyl) acryloyl group high molecular polymer as preferred polymkeric substance.

Include, for example: (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid 2-hydroxy propyl ester/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer described in Japanese Patent Laid-Open 7-140654 publication, acrylic acid 2-hydroxyl-3-phenoxy-propyl/polymethylmethacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc.

In addition, also can use known macromolecular compound described in Japanese Patent Laid-Open 7-207211 publication, Japanese Patent Laid-Open 8-259876 publication, Japanese Patent Laid-Open 10-300922 publication, Japanese Patent Laid-Open 11-140144 publication, Japanese Patent Laid-Open 11-174224 publication, Japanese Patent Laid-Open 2000-56118 publication, Japanese Patent Laid-Open 2003-233179 publication, Japanese Patent Laid-Open 2009-52020 publication etc., these content can be incorporated into in present specification.

These polymkeric substance only containing a kind, also can contain two or more.

As these polymkeric substance, also commercially available SMA 1000P can be used, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA2625P, SMA 3840F (more than, Sartomer (Sartomer) company manufactures), A Lufeng (ARUFON) UC-3000, A Lufeng (ARUFON) UC-3510, A Lufeng (ARUFON) UC-3900, A Lufeng (ARUFON) UC-3910, A Lufeng (ARUFON) UC-3920, A Lufeng (ARUFON) UC-3080 (more than, East Asia synthesis (share) manufactures), Zhuan Chen (JONCRYL) 690, Zhuan Chen (JONCRYL) 678, Zhuan Chen (JONCRYL) 67, Zhuan Chen (JONCRYL) 586 (more than, BASF (BASF) company manufactures) etc.

In the present invention, with regard to the viewpoint of sensitivity, be particularly preferably containing there is the Component units of carboxyl or there is the Component units of phenolic hydroxyl group.Such as can use the compound recorded in the paragraph 0021 ~ paragraph 0023 of Japanese Patent Laid-Open 2012-88459 publication and paragraph 0029 ~ paragraph 0044, described content can be incorporated into in present specification.

The Component units with acidic group is preferably 1 % by mole ~ 80 % by mole of the Component units of all component of polymer, be more preferably 1 % by mole ~ 50 % by mole, and then be more preferably 5 % by mole ~ 40 % by mole, be particularly preferably 5 % by mole ~ 30 % by mole, most preferably be 5 % by mole ~ 20 % by mole.

Below, enumerate the preferred example of the component of polymer in the present invention, but the present invention is not limited to these examples.

-1 example-

Component of polymer (1) and then the form containing one kind or two or more other Component units (a3).

-2 example-

Contain (a1) of component of polymer (2) has the polymkeric substance of the Component units of the base that acidic group is protected by sour decomposability base and then the form containing one kind or two or more other Component units (a3).

-3 example-

Contain (a2) of component of polymer (2) has the polymkeric substance of the Component units of bridging property base and then the form containing one kind or two or more other Component units (a3).

-4 example-

In arbitrary example of above-mentioned 1st example ~ the 3rd example, there is in any one polymkeric substance the form of the Component units at least containing acidic group as other Component units (a3).

-5 example-

Except above-mentioned component of polymer (1) or component of polymer (2), and then there is the form of the polymkeric substance in fact not containing Component units (a1) and Component units (a2) containing other Component units (a3).

-6 example-

Comprise the form of the combination of more than two kinds of above-mentioned 1st example ~ the 5th example.

-molecular weight of the polymkeric substance in composition C-

The molecular weight of the polymkeric substance in composition C, with polystyrene conversion weight average molecular weight, is preferably 1,000 ~ 200,000, is more preferably 2,000 ~ 50, the scope of 000.If in the scope of above-mentioned numerical value, then various characteristic is good.The ratio (dispersion degree, Mw/Mn) of number average molecular weight Mn and weight average molecular weight Mw is preferably 1.0 ~ 5.0, is more preferably 1.5 ~ 3.5.

Moreover the weight average molecular weight in the present invention or the mensuration of number average molecular weight preferably utilize gel filtration chromatography (gel filtration chromatography) to measure.The mensuration of gel filtration chromatography that utilizes in the present invention preferably uses HLC-8020GPC (eastern Cao (Tosoh) (share) manufactures), and use tsk gel (TSKgel) Super HZ M-H, tsk gel (TSK gel) Super HZ4000, tsk gel (TSKgel) SuperHZ200 (eastern Cao (share) manufacture, 4.6mmID × 15cm) as tubing string, use tetrahydrofuran (Tetrahydrofuran, THF) as eluent.

-manufacture method of the polymkeric substance in composition C-

About the synthetic method of the polymkeric substance in composition C, also there will be a known various method, if enumerate an example, then by utilizing radical polymerization initiator, make at least to carry out being polymerized in organic solvent synthesizing containing the free radical polymerization monomer potpourri for the formation of the free radical polymerization monomer of above-mentioned Component units (a1).In addition, also synthesize by so-called high molecular weight reactive.

Relative to the total solid composition of photosensitive polymer combination, the content of the composition C in photosensitive polymer combination of the present invention is preferably 20 quality % ~ 99.9 quality %, be more preferably 50 quality % ~ 98 quality %, and then be more preferably 70 quality % ~ 95 quality %.If content is described scope, then the patternability carried out when developing becomes good, in addition, can obtain the hardening thing that refractive index is higher.Moreover the solid constituent amount of so-called photosensitive polymer combination, represents the amount desolventized etc. beyond volatile ingredient.

(components D) light acid producing agent

Photosensitive polymer combination of the present invention contains (components D) light acid producing agent.The light acid producing agent used in the present invention be induction be preferably wavelength be more than 300nm, be more preferably actinic ray and acidic compound that wavelength is 300nm ~ 450nm, but do not limit by its chemical constitution.In addition, be the photoactinic smooth acid producing agent of more than 300nm about directly not responding to wavelength, if by being used for responding to sensitizer the actinic ray and acidic compound that wavelength is more than 300nm, then preferably use after also can combining with sensitizer.As the light acid producing agent used in the present invention, be preferably and produce the light acid producing agent that pKa is the acid of less than 4, be more preferably and produce the light acid producing agent that pKa is the acid of less than 3, most preferably be and produce the light acid producing agent that pKa is the acid of less than 2.In addition, the light acid producing agent that generation pKa is more than-15 acid is preferably.

As the example of light acid producing agent, can enumerate: trichloromethyl-symmetrical triazines, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds etc.Among these light acid producing agents, with regard to the viewpoint of insulativity, sensitivity, preferably use oxime sulfonate compounds.These light acid producing agents can be used alone a kind or two or more combinationally used.As the concrete example of trichloromethyl-symmetrical triazines, two fragrant base Iodonium salts, triaryl matte salt, quarternary ammonium salt class and diazomethane derivative, compound described in the paragraph 0083 ~ paragraph 0088 of Japanese Patent Laid-Open 2011-221494 publication can be illustrated.

As oxime sulfonate compounds, namely have the compound of oxime sulfonates structure, preferably can illustrate the compound containing the oxime sulfonates structure represented by following formula (D1), these content can be incorporated into in present specification.

[changing 9]

(in formula (D1), R ²¹represent alkyl or aryl, wave-like line part represents the bond position with other bases)

Any base all can be substituted, R ²¹in alkyl can be straight-chain, also can be branch-like, also can be ring-type.The substituting group of allowing below is described.

As R ²¹alkyl, be preferably carbon number be 1 ~ 10 straight-chain alkyl or branch-like alkyl.R ²¹alkyl can be 6 ~ 11 by carbon number aryl, carbon number be 1 ~ 10 alkoxy or naphthenic base (comprise the bridge-type alicyclic groups such as 7,7-dimethyl-2-side oxygen norcamphanyl, be preferably bicyclic alkyl etc.) replace.

As R ²¹aryl, be preferably carbon number be the aryl of 6 ~ 11, be more preferably phenyl or naphthyl.R ²¹aryl can be 1 ~ 10 by carbon number alkyl, carbon number be 1 ~ 10 alkoxy or halogen atom replace.

Above-claimed cpd containing oxime sulfonates structure represented by above-mentioned formula (D1) for the oxime sulfonate compounds represented by following formula (D2) also preferred.

[changing 10]

(in formula (D2), R42 represents alkyl or aryl, and X represents alkyl, alkoxy or halogen atom, and m4 represents the integer of 0 ~ 3, and when m4 is 2 or 3, multiple X can be identical, also can be different)

Alkyl as X is preferably straight-chain alkyl or the branch-like alkyl that carbon number is 1 ~ 4.

Alkoxy as X is preferably straight-chain alkoxy or the branch-like alkoxy that carbon number is 1 ~ 4.

Halogen atom as X is preferably chlorine atom or fluorine atom.

M4 is preferably 0 or 1.In above-mentioned formula (D2), to be particularly preferably m4 be 1, X is methyl, and the position of substitution of X is ortho position, R42 to be carbon number be 1 ~ 10 straight-chain alkyl, 7,7-dimethyl-2-side oxygen norcamphanyl methyl or the compounds to toluyl groups.

Compound containing oxime sulfonates structure represented by above-mentioned formula (D1) for the oxime sulfonate compounds represented by following formula (D3) also preferred.

[changing 11]

(in formula (D3), R ⁴³implication and formula (D2) in R ⁴²identical, X ¹alkoxy, cyano group or nitro that the alkyl that expression halogen atom, hydroxyl, carbon number are 1 ~ 4, carbon number are 1 ~ 4, n4 represents the integer of 0 ~ 5)

As the R in above-mentioned formula (D3) ⁴³, be preferably methyl, ethyl, n-pro-pyl, normal-butyl, n-octyl, trifluoromethyl, pentafluoroethyl group, perfluor-n-pro-pyl, perfluor-normal-butyl, p-methylphenyl, 4-chlorphenyl or pentafluorophenyl group, be particularly preferably n-octyl.

X ¹being preferably carbon number is the alkoxy of 1 ~ 5, is more preferably methoxyl.

N4 is preferably the integer of 0 ~ 2, is particularly preferably 0 or 1.

As the concrete example of the compound represented by above-mentioned formula (D3) and the concrete example of preferred oxime sulfonate compounds, can with reference to the record of the paragraph 0080 ~ paragraph 0082 of Japanese Patent Laid-Open 2012-163937 publication, described content can be incorporated into in present specification.

Compound containing oxime sulfonates structure represented by above-mentioned formula (D1) for the compound represented by following formula (OS-1) also preferred.

[changing 12]

In above-mentioned formula (OS-1), R ¹⁰¹represent hydrogen atom, alkyl, thiazolinyl, alkoxy, alkoxy carbonyl, acyl group, carbamyl, sulfamoyl, sulfo group, cyano group, aryl or heteroaryl.R ¹⁰²represent alkyl or aryl.

X ¹⁰¹represent-O-,-S-,-NH-,-NR ¹⁰⁵-,-CH ₂-,-CR ¹⁰⁶h-or-CR ¹⁰⁵r ¹⁰⁷-, R ¹⁰⁵~ R ¹⁰⁷represent alkyl or aryl.

R ¹²¹~ R ¹²⁴separately represent hydrogen atom, halogen atom, alkyl, thiazolinyl, alkoxy, amino, alkoxy carbonyl, alkyl-carbonyl, aryl carbonyl, amide group, sulfo group, cyano group or aryl.R ¹²¹~ R ¹²⁴in 2 can mutual bond and form ring respectively.

As R ¹²¹~ R ¹²⁴, be preferably separately hydrogen atom, halogen atom or alkyl, in addition, also preferably can enumerate R ¹²¹~ R ¹²⁴in at least two mutual bonds and form the form of aryl.Wherein, with regard to the viewpoint of sensitivity, be preferably R ¹²¹~ R ¹²⁴be the form of hydrogen atom.

Already described functional group all can have substituting group further.

Compound represented by above-mentioned formula (OS-1) is preferably the compound represented by general formula (OS-2) described in the paragraph 0087 ~ paragraph 0089 of such as Japanese Patent Laid-Open 2012-163937 publication, and described content can be incorporated into in present specification.

As the concrete example that can be suitably used for the compound represented by above-mentioned formula (OS-1) of the present invention, can enumerate compound (exemplary compounds b-1 ~ exemplary compounds b-34) described in the paragraph 0128 ~ paragraph 0132 of Japanese Patent Laid-Open 2011-221494 publication, but the present invention is not limited thereto.

In the present invention, as the compound containing the oxime sulfonates structure represented by above-mentioned formula (D1), be preferably the oxime sulfonate compounds represented by following formula (OS-3), following formula (OS-4) or following formula (OS-5).

[changing 13]

(in formula (OS-3) ~ formula (OS-5), R ²², R ²⁵and R ²⁸separately represent alkyl, aryl or heteroaryl, R ²³, R ²⁶and R ²⁹separately represent hydrogen atom, alkyl, aryl or halogen atom, R ²⁴, R ²⁷and R ³⁰separately represent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or alkyloxysulfonyl, X ¹~ X ³separately represent oxygen atom or sulphur atom, n ¹~ n ³separately represent 1 or 2, m ¹~ m ³separately represent the integer of 0 ~ 6)

In addition, compound containing oxime sulfonates structure represented by above-mentioned formula (D1) is particularly preferably the compound in the paragraph 0117 of such as Japanese Patent Laid-Open 2012-163937 publication represented by any one by general formula (OS-6) ~ general formula (OS-11) described, and described content can be incorporated into in present specification.

Preferred scope in above-mentioned general formula (OS-6) ~ general formula (OS-11) is identical with the preferred scope in general formula (OS-6) ~ general formula (OS-11) described in the paragraph 0110 ~ paragraph 0112 of Japanese Patent Laid-Open 2011-221494 publication.

As the concrete example of the oxime sulfonate compounds represented by above-mentioned formula (OS-3) ~ above-mentioned formula (OS-5), can enumerate compound described in the paragraph 0114 ~ paragraph 0120 of Japanese Patent Laid-Open 2011-221494 publication, but the present invention is not limited to these compounds.

Compound containing oxime sulfonates structure represented by above-mentioned formula (D1) for the oxime sulfonate compounds represented by following formula (D1-4) also preferred.

[changing 14]

(in formula (D1-4), R ^d1represent alkyl or aryl, R ^d2represent alkyl, aryl or heteroaryl, R ^d3~ R ^d6separately represent hydrogen atom, alkyl, aryl or halogen atom, R ^d3with R ^d4, R ^d4with R ^d5, or R ^d5with R ^d6can bond and form alicyclic ring or aromatic rings, X ^drepresent-O-or-S-)

R ^d1represent alkyl or aryl.Alkyl preferably has the alkyl of branched structure or the alkyl of ring texture.

The carbon number of alkyl is preferably 3 ~ 10.Especially when alkyl has branched structure, being preferably carbon number is the alkyl of 3 ~ 6, and when having ring texture, being preferably carbon number is the alkyl of 5 ~ 7.

As alkyl, include, for example propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl, 1,1-dimethyl propyl, hexyl, 2-ethylhexyl, cyclohexyl, octyl group etc., be preferably isopropyl, the tert-butyl group, neopentyl, cyclohexyl.

The carbon number of aryl is preferably 6 ~ 12, is more preferably 6 ~ 8, and then is more preferably 6 or 7.As above-mentioned aryl, can phenyl, naphthyl etc. be enumerated, be preferably phenyl.

R ^d1represented alkyl and aryl can have substituting group.Alternatively base, include, for example: halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine), the alkyl (such as methyl, ethyl, propyl group etc.) of straight chain, branch or ring-type, thiazolinyl; alkynyl, aryl, acyl group, alkoxy carbonyl; aryloxycarbonyl, carbamyl, cyano group, carboxyl; hydroxyl, alkoxy, aryloxy group, alkylthio group; arylthio, heterocyclic oxy group, acyloxy, amino; nitro, diazanyl, heterocyclic radical etc.In addition, also can be replaced further by these bases.Be preferably halogen atom, methyl.

In photosensitive polymer combination of the present invention, with regard to the viewpoint of the transparency, R ^d1be preferably alkyl, just make storage stability and sensitivity and with regard to the viewpoint of depositing, R ^d1be preferably carbon number be 3 ~ 6 the alkyl with branched structure, carbon number be alkyl or the phenyl of the ring texture of 5 ~ 7, be more preferably carbon number be 3 ~ 6 the alkyl with branched structure or carbon number be the alkyl of the ring texture of 5 ~ 7.By adopting this kind of bulky base (particularly bulky alkyl) as R ^d1, and the transparency can be promoted further.

Among bulky substituting group, be preferably isopropyl, the tert-butyl group, neopentyl, cyclohexyl, be more preferably the tert-butyl group, cyclohexyl.

R ^d2represent alkyl, aryl or heteroaryl.As R ^d2represented alkyl, being preferably carbon number is the straight chain of 1 ~ 10, the alkyl of branch or ring-type.As abovementioned alkyl, include, for example methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, amyl group, neopentyl, hexyl, cyclohexyl etc., be preferably methyl.

As aryl, being preferably carbon number is the aryl of 6 ~ 10.As above-mentioned aryl, phenyl, naphthyl can be enumerated, to toluyl groups (p-methylphenyl) etc., be preferably phenyl, to toluyl groups.

As heteroaryl, include, for example: pyrrole radicals, indyl, carbazyl, furyl, thienyl etc.

R ^d2represented alkyl, aryl and heteroaryl can have substituting group.Substituent implication and R ^d1the substituting group that represented alkyl and aryl can have is identical.

R ^d2be preferably alkyl or aryl, be more preferably aryl, and then be more preferably phenyl.As the substituting group of phenyl, be preferably methyl.

R ^d3~ R ^d6represent hydrogen atom, alkyl, aryl or halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine) respectively.R ^d3~ R ^d6the implication of represented alkyl and R ^d2represented alkyl is identical, and preferred scope is also identical.In addition, R ^d3~ R ^d6the implication of represented aryl and R ^d1represented aryl is identical, and preferred scope is also identical.

R ^d3~ R ^d6among, R ^d3with R ^d4, R ^d4with R ^d5, or R ^d5with R ^d6can bond and form ring, as ring, be preferably and form alicyclic ring or aromatic rings, be more preferably phenyl ring.

R ^d3~ R ^d6be preferably hydrogen atom, alkyl, halogen atom (fluorine atom, chlorine atom, bromine atoms), or R ^d3with R ^d4, R ^d4with R ^d5, or R ^d5with R ^d6bond and form phenyl ring, is more preferably hydrogen atom, methyl, fluorine atom, chlorine atom, bromine atoms, or R ^d3with R ^d4, R ^d4with R ^d5, or R ^d5with R ^d6bond and form phenyl ring.

R ^d3~ R ^d6preferred form as follows.

(form 1) at least two is hydrogen atom.

The quantity of (form 2) alkyl, aryl or halogen atom is less than 1.

(form 3) R ^d3with R ^d4, R ^d4with R ^d5, or R ^d5with R ^d6bond and form phenyl ring.

(form 4) meets the form of above-mentioned form 1 and form 2 and/or meets the form of above-mentioned form 1 and form 3.

X ^drepresent-O-or-S-.

As the concrete example of above-mentioned formula (D1-4), the compound that can be listed below, but the present invention is not particularly limited to this.Moreover in exemplary compounds, Ts represents tosyl (p-toluenesulfonyl), and Me represents methyl, and Bu represents normal-butyl, and Ph represents phenyl.

[changing 15]

In photosensitive polymer combination of the present invention, relative to the composition C100 mass parts in photosensitive polymer combination, the content of (components D) light acid producing agent is preferably 0.1 mass parts ~ 10 mass parts, is more preferably 0.5 mass parts ~ 10 mass parts.

In addition, components D can be used alone a kind, also can and use two or more.

(composition E) spreading agent

Photosensitive polymer combination of the present invention is preferably containing (composition E) spreading agent.By containing spreading agent, and the dispersiveness of composition A in resin combination can be promoted further.

As spreading agent, known spreading agent can be used, such as, can be suitable for selecting known pigment dispersing agent to use.

In addition, as spreading agent, preferably macromolecule dispersing agent can be used.Moreover so-called macromolecule dispersing agent, refers to that molecular weight (weight average molecular weight) is the spreading agent of 1, more than 000.

As spreading agent, multiple compounds can be used, specifically, include, for example: organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), (methyl) acrylic acid series (being total to) polymkeric substance Po Lifuluo (Polyflow) No.75, No.90, No.95 (common prosperity society chemistry (share) manufacture), the kation system surfactants such as W001 (abundant business (share) manufacture), the nonionic system surfactants such as polyoxyethylene laurel ether, polyoxyethylene stearyl ether, polyoxyl 10 oleyl ether, polyoxethylene octylphenyl phenylate, ethylene nonyl phenylate, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty acid esters, the negative ion system surfactants such as W004, W005, W017 (abundant business (share) manufacture), EFKA (EFKA)-46, EFKA (EFKA)-47, EFKA (EFKA)-47EA, EFKA polymkeric substance (EFKA Polymer) 100, EFKA polymkeric substance (EFKA Polymer) 400, EFKA polymkeric substance (EFKA Polymer) 401, EFKA polymkeric substance (EFKAPolymer) 450 (being Ciba (Ciba Specialty Chemicals) company to manufacture), this Paasche of enlightening Ai De (DisperseAid) 6, this Paasche of enlightening Ai De (Disperse Aid) 8, this Paasche of enlightening Ai De (Disperse Aid) 15, the macromolecule dispersing agents such as this Paasche of enlightening Ai De (Disperse Aid) 9100 (being Sheng Nuopuke (San Nopco) (share) to manufacture), various Suo Sipa (Solsperse) spreading agents such as Suo Sipa (Solsperse) 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000 (AstraZeneca (AstraZeneca) (share) manufactures), Ai Dike pluronic (AdekaPluronic) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Ai Dike (ADEKA) (share) manufactures) and her Nat difficult to understand (IONET) S-20 (Sanyo changes into industry (share) manufacture), Di Sipabike (DISPERBYK) 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactures of Bi Ke chemistry (BYK-Chemie) company).In addition, oligomer or the polymkeric substance that acrylic acid series copolymer etc. has polar group in molecular end or side chain can be enumerated.

Spreading agent can be used alone a kind, also can and use two or more.

Relative to the total solid composition of photosensitive polymer combination, the content of the spreading agent in photosensitive polymer combination of the present invention is preferably the scope of 5 quality % ~ 70 quality %, is more preferably the scope of 10 quality % ~ 50 quality %.

(composition F) thermal cross-linking agent

Photosensitive polymer combination of the present invention is preferably optionally and contains thermal cross-linking agent.By adding thermal cross-linking agent, and the cured film obtained by photosensitive polymer combination of the present invention can be made to become more firmly film.

As thermal cross-linking agent, as long as produce cross-linking reaction by heat, then and unrestricted (but, except composition C).Such as, there is in the molecule that can add the following stated the compound of the epoxy radicals of more than 2 or oxetanylmethoxy, the crosslinking chemical containing alkoxy methyl, the compound with at least one ethene unsaturated double-bond or blocked isocyanate compound etc.

Relative to total solid composition 100 mass parts of photosensitive polymer combination, the addition of the thermal cross-linking agent in photosensitive polymer combination of the present invention is preferably 0.01 mass parts ~ 50 mass parts, be more preferably 0.1 mass parts ~ 30 mass parts, and then be more preferably 0.5 mass parts ~ 20 mass parts.By adding in described scope, and the cured film of physical strength and excellent solvent resistance can be obtained.Thermal cross-linking agent also can and with multiple, in the case, calculate the total content of all thermal cross-linking agents.

There is in < molecule the epoxy radicals of more than 2 or the compound > of oxetanylmethoxy

As the concrete example of compound of epoxy radicals in molecule with more than 2, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin etc.

These compounds can be used as commercially available product and obtain.Include, for example JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (Mitsubishi Chemical's holding (Mitsubishi Chemical Holdings) (share) manufactures) etc., commercially available product etc. described in the paragraph 0189 of Japanese Patent Laid-Open 2011-221494 publication, in addition, Ai Dike resin (ADEKA RESIN) EP-4000S can also be enumerated, Ai Dike resin (ADEKA RESIN) EP-4003S, Ai Dike resin (ADEKARESIN) EP-4010S, Ai Dike resin (ADEKARESIN) EP-4011S (more than, Ai Dike (share) manufactures), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (more than, Ai Dike (share) manufactures), Dai Nake (Denacol) EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (more than, long rapids change into (Nagase chemteX) (share) manufactures), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (more than, Nippon Steel's chemistry (share) manufactures) etc.

These can be used alone a kind or two or more combinationally used.

Among these, can more preferably enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin and aliphatic epoxy resin, particularly preferably can enumerate bisphenol A type epoxy resin.

As the concrete example of compound of oxetanylmethoxy in molecule with more than 2, can use sub-imperial oxetanes (ARONE OXETANE) OXT-121, OXT-221, OX-SQ, PNOX (more than, East Asia synthesis (share) manufacture).

In addition, the compound containing oxetanylmethoxy is preferably used alone or used in combination with the compound containing epoxy radicals.

In addition, as other thermal cross-linking agents, described containing the crosslinking chemical of alkoxy methyl and there is the compound etc. of at least one ethene unsaturated double-bond in the paragraph 0107 ~ paragraph 0108 of Japanese Patent Laid-Open 2012-8223 publication also preferably can be used.As the crosslinking chemical containing alkoxy methyl, be preferably aikoxymethytated glycolurils.

< blocked isocyanate compound >

In photosensitive polymer combination of the present invention, also can preferably use blocked isocyanate compound as thermal cross-linking agent.As long as blocked isocyanate compound has the compound of blocked isocyanate base, then there is no particular restriction, but with regard to photosensitive viewpoint, be preferably the compound in 1 molecule with the blocked isocyanate base of more than 2.

Such as, moreover the blocked isocyanate base in the present invention refers to the base generating isocyanate group by heat, preferably can illustrate the base making sealer and isocyanate group carry out reacting to protect isocyanate group.In addition, above-mentioned blocked isocyanate base is preferably the heat by 90 DEG C ~ 250 DEG C and generates the base of isocyanate group.

In addition, as blocked isocyanate compound, its skeleton is not particularly limited, as long as have the compound of 2 isocyanate group in 1 molecule, then can be any compound, can be aliphatics, alicyclic or aromatic polyisocyanate, such as, can use aptly: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1,9-nine methylene diisocyanate, 1,10-decamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-diethyl ether diisocyanate, diphenyl methane-4,4 '-diisocyanate, o-xylene diisocyanate, m xylene diisocyanate, P-xylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, 3,3 '-xylene-4,4 '-diisocyanate, 4,4 '-diphenyl ether diisocyanate, tetrachloro phenylene vulcabond, norcamphane diisocyanate, hydrogenation 1,3-eylylene diisocyanate, the isocyanate compounds such as hydrogenation Isosorbide-5-Nitrae-eylylene diisocyanate and the compound of the skeleton of prepolymer type gone out from these compound derivings.Among these, be particularly preferably toluene diisocyanate (Tolylene Diisocyanate, or methyl diphenylene diisocyanate (Diphenyl MethaneDiisocyanate TDI), MDI), hexamethylene diisocyanate (Hexamethylene Diisocyanate, HDI), isophorone diisocyanate (Isophorone Diisocyanate, IPDI).

As the parent structure of the blocked isocyanate compound in photosensitive polymer combination of the present invention, can enumerate: biuret form, isocyanuric acid ester (Isocyanurate) type, adduct type, two functional prepolymer types etc.

As the sealer of the enclosed construction of the above-mentioned blocked isocyanate compound of formation, can enumerate: oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, imidazole compound, imide series compound etc.Among these, be particularly preferably the sealer be selected from oxime compound, lactam compound, phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound.

As above-mentioned oxime compound, aldoxime and ketoxime can be enumerated, specifically, can illustrate: acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone-oxime, diphenyl-ketoxime etc.

As above-mentioned lactam compound, can illustrate: epsilon-caprolactams, butyrolactam etc.

As above-mentioned phenolic compounds, can illustrate: phenol, naphthols, cresols, xylenol, halogen substiuted phenol etc.

As above-mentioned alcoholic compound, can illustrate: methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, ethylene glycol monoalkyl ether, propylene-glycol monoalky lether, lactic acid alkyl ester etc.

As above-mentioned amines, primary amine and secondary amine can be enumerated, can be aromatic amine, fatty amine, cycloaliphatic amines any one, can illustrate: aniline, diphenylamine, aziridine, polyethyleneimine etc.

As above-mentioned activity methene compound, can illustrate: diethyl malonate, dimethyl malenate, ethyl acetoacetate, methyl acetoacetate etc.

As above-mentioned pyrazole compound, can illustrate: pyrazoles, methylpyrazole, dimethyl pyrazole etc.

As above-mentioned mercaptan compound, can illustrate: alkyl sulfhydryl, aryl mercaptan etc.

The blocked isocyanate compound of photosensitive polymer combination used in the present invention can be used as commercially available product and obtains, such as, can preferably use: the Crow AP of resistance to moral Si Tebu (Coronate AP Stable) M, the resistance to moral in Crow (Coronate) 2503, 2515, 2507, 2513, 2555, rice Leo resistance to moral (Millionate) MS-50 (more than, Japanese polyurethane industry (NipponPolyurethane Industry) (share) manufactures), the resistance to moral of Plutarch (Takenate) B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (more than, Mitsui Chemicals (share) manufactures), how resistance to moral (Duranate) 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (more than, Asahi Chemical Industry's chemistry (Asahi Kasei Chemicals) (share) manufactures), De Shimo is (Desmodur) BL1100, BL1265MPA/X, BL3575/1, BL3272MPA, BL3370MPA, BL3475BA/SN, BL5375MPA, VPLS2078/2, BL4265SN, PL340, PL350, Soviet Union rice all (Sumidur) BL3175 (more than, live change Baeyer polyurethane (Sumika Bayer Urethane) (share) manufacture) etc.

Other compositions of < >

In photosensitive polymer combination of the present invention, except mentioned component, optionally preferably can add (composition G) sensitizer, (composition H) alkoxysilane compound containing trialkylsilyl group in molecular structure, (composition I) alkali compounds, (composition J) surfactant, (composition K) antioxidant.And then, in photosensitive polymer combination of the present invention, ultraviolet light absorber, metal passivator or acid proliferation generator can be added, development accelerant, plasticiser, hot radical produce agent, thermal acid generator, thickening agent and organic or inorganic the known adjuvant such as antisettling agent.In addition, as these compounds, also can see, for example the record of the paragraph 0201 ~ paragraph 0224 of Japanese Patent Laid-Open 2012-88459 publication, these content can be incorporated into in present specification.

(composition G) sensitizer

Photosensitive polymer combination of the present invention be preferably with the combination of (components D) light acid producing agent in containing sensitizer, to promote the decomposition of light acid producing agent.Sensitizer absorbs actinic ray or radioactive ray and becomes electron excitation state.The sensitizer becoming electron excitation state contacts with light acid producing agent, and produces the effects such as electronics moves, energy moves, heating.Thus, light acid producing agent produces chemical change and decomposes, and generates acid.As the example of preferred sensitizer, can enumerate belong to following compounds and the wavelength region may of 350nm ~ 450nm any one in there is the compound of absorbing wavelength.

The polynuclear aromatic same clan (such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxy anthracene, 9,10-diethoxy anthracene, 3,7-dimethoxy anthracene, 9,10-dipropoxy anthracene), xanthene (xanthene) class (such as fluorescein (fluorescein), eosin, erythrosine (erythrosine), rhodamine B (Rhodamine B), rose bengal (Rose Bengal)), xanthone (such as xanthone, thioxanthone, dimethyl thioxanthone, diethyl thioxanthone), cyanine class (such as thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (such as merocyanine, carbonyl merocyanine), if red cyanines (rodacyanine) class, oxonols class, thiazide (such as thionine, methylenum careuleum, toluidine blue), acridine (such as acridine orange, chloroflavin, acriflavine), acridine ketone (such as acridone, 10-butyl-2-chloro-acridine ketone), Anthraquinones (such as anthraquinone), side's acid compound class (such as square acid compound), styrene base class, basicity styrene base class (such as 2-{2-[4-(dimethylamino) phenyl] vinyl } benzoxazole), Coumarins (such as 7-lignocaine-4-methylcoumarin, Hymecromone, 2,3,6,7-tetrahydrochysene-9-methyl isophthalic acid H, 5H, 11H [1] chromene is [6,7,8-ij] quinolizine-11-ketone also).

Among these sensitizers, be preferably the polynuclear aromatic same clan, acridine ketone, styrene base class, basicity styrene base class, Coumarins, be more preferably the polynuclear aromatic same clan.Among the polynuclear aromatic same clan, most preferably be anthracene derivant.

Relative to light acid producing agent 100 mass parts of photosensitive polymer combination, the addition of the sensitizer in photosensitive polymer combination of the present invention is preferably 0 mass parts ~ 1,000 mass parts, is more preferably 10 mass parts ~ 500 mass parts, and then is more preferably 50 mass parts ~ 200 mass parts.

In addition, sensitizer can be used alone a kind, also can and use two or more.

(composition H) alkoxysilane compound containing trialkylsilyl group in molecular structure

Photosensitive polymer combination of the present invention can contain (composition H) alkoxysilane compound containing trialkylsilyl group in molecular structure.If use alkoxysilane compound containing trialkylsilyl group in molecular structure, then can promote the character of the film that the adherence of film and the substrate formed by photosensitive polymer combination of the present invention or adjustable are formed by photosensitive polymer combination of the present invention.(composition H) alkoxysilane compound containing trialkylsilyl group in molecular structure of photosensitive polymer combination used in the present invention is preferably the compound of the adherence promoting inorganics silicon compounds such as (, the metals such as gold, copper, molybdenum, titanium, aluminium) such as silicon, monox, silicon nitrides and the dielectric film becoming base material.Specifically, known silane coupling agent etc. are also effective.

As silane coupling agent, include, for example: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyl trialkyl oxysilane.Among these, be more preferably γ-glycidyloxypropyl silane or γ-methacryloxypropyl trialkoxy silane, and then be more preferably γ-glycidyloxypropyl silane, be particularly preferably 3-glycidoxypropyltrimewasxysilane.These silane coupling agents can be used alone a kind or two or more combinationally used.

In addition, the compound represented by following formula can also preferably be adopted.

(R ¹) _4-n-Si-(OR ²) _n(H)

In above-mentioned formula (H), R ¹represent that the carbon number without reactive base is the alkyl of 1 ~ 20, R ²represent that carbon number is the alkyl or phenyl of 1 ~ 3, n represents the integer of 1 ~ 3.

As concrete example, following compound can be enumerated.Moreover Ph represents phenyl.

[changing 16]

[changing 17]

(composition H) alkoxysilane compound containing trialkylsilyl group in molecular structure in photosensitive polymer combination of the present invention is not particularly limited to these alkoxysilane compound containing trialkylsilyl group in molecular structure, can use known alkoxysilane compound containing trialkylsilyl group in molecular structure.

Relative to total solid composition 100 mass parts in photosensitive polymer combination, the content of the alkoxysilane compound containing trialkylsilyl group in molecular structure in photosensitive polymer combination of the present invention is preferably 0.1 mass parts ~ 30 mass parts, is more preferably 0.5 mass parts ~ 20 mass parts.

(composition I) alkali compounds

Photosensitive polymer combination of the present invention can contain (composition I) alkali compounds.

As (composition I) alkali compounds, at random select in the alkali compounds that can use in Chemical amplification resist to use.Include, for example: the quarternary ammonium salt etc. of fatty amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium, carboxylic acid.As these concrete example, compound described in the paragraph 0204 ~ paragraph 0207 of Japanese Patent Laid-Open 2011-221494 publication can be enumerated.

Specifically, as fatty amine, include, for example: trimethylamine, diethylamine, triethylamine, two-n-propylamine, three-n-propylamine, two-n-amylamine, three-n-amylamine, diethanolamine, triethanolamine, dicyclohexyl amine, dicyclohexylmethylamine etc.

As aromatic amine, include, for example: aniline, benzyl amine, DMA, diphenylamine etc.

As hetero ring type amine, include, for example: pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, DMAP, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2, 4, 5-triphenylimidazolyl, nicotine, nicotinic acid, niacinamide, quinoline, oxine (8-oxyquinoline), pyrazine, pyrazoles, pyridazine, purine, pyrrolidine, piperidines, piperazine, morpholine, 4-methyl morpholine, N-cyclohexyl-N '-[2-(4-morpholinyl) ethyl] thiocarbamide, 1, 5-diazabicyclo [4.3.0]-5-nonene, 1, 8-diazabicyclo [5.3.0]-7-hendecene etc.

As hydroxide level Four ammonium, include, for example: tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide four-normal-butyl ammonium, hydroxide four-n-hexyl ammonium etc.

As the quarternary ammonium salt of carboxylic acid, include, for example: acetic acid tetramethyl-ammonium, benzoic acid tetramethyl-ammonium, acetic acid four-normal-butyl ammonium, benzoic acid four-normal-butyl ammonium etc.

Wherein, be preferably hetero ring type amine, be particularly preferably N-cyclohexyl-N '-[2-(4-morpholinyl) ethyl] thiocarbamide.

Alkali compounds used in the present invention can be used alone a kind, also can and use two or more.

Relative to total solid composition 100 mass parts in photosensitive polymer combination, the content of the alkali compounds in photosensitive polymer combination of the present invention is preferably 0.001 mass parts ~ 3 mass parts, is more preferably 0.005 mass parts ~ 1 mass parts.

(composition J) surfactant

Photosensitive polymer combination of the present invention can contain (composition J) surfactant.

As (composition J) surfactant, can use negative ion system, kation system, nonionic system or both sexes any one, but preferred surfactant is nonionic system surfactant.As the surfactant used in composition of the present invention, such as can use surfactant described in the paragraph 0185 ~ paragraph 0188 of surfactant described in the paragraph 0201 ~ paragraph 0205 of Japanese Patent Laid-Open 2012-88459 publication or Japanese Patent Laid-Open 2011-215580 publication, these records can be incorporated into in present specification.

As the example of nonionic system surfactant, can enumerate: the higher aliphatic acid diesters class of polyoxyethylene higher alkyl ether, polyoxyethylene higher alkyl benzene ethers, polyoxyethylene glycol, silicone-based, fluorine system surfactant.In addition, following trade name can be enumerated: KP-341, X-22-822 (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), Po Lifuluo (Polyflow) No.99C (common prosperity society chemistry (share) manufacture), Ai Futuo (Eftop) (Mitsubishi Materials electronics changes into (share) and manufactures), Mei Jiafa (Megafac) (Di Aisheng (DIC) (share) manufactures), Fu Ladenuo Bake (Fluorad Novec) FC-4430 (Sumitomo 3M (share) manufacture), Sha Fulong (Surflon) S-242 (AGC beautifies clearly (AGC SEIMI CHEMICAL) company and manufactures), Pohle Floex (PolyFox) PF-6320 (manufacture of Ou Nuofa (OMNOVA) company), SH-8400 (eastern beautiful DOW CORNING silicone (Dow Corning Toray Silicone) (share) manufacture), each series such as Fu Jite (Ftergent) FTX-218G (manufacture of Ni Ousi (Neos) company).

In addition, as surfactant, the multipolymer that can be listed below is as preference, described multipolymer contains Component units A represented by following formula (J-1) and Component units B, and be 1 using tetrahydrofuran (THF) as the weight average molecular weight (Mw) of the polystyrene conversion measured by gel permeation chromatography during solvent, more than 000,10, less than 000.

[changing 18]

(in formula (J-1), R ⁴⁰¹and R ⁴⁰³separately represent hydrogen atom or methyl, R ⁴⁰²represent that carbon number is the straight-chain alkyl-sub-of more than 1, less than 4, R ⁴⁰⁴represent that hydrogen atom or carbon number are the alkyl of more than 1, less than 4, L represents that carbon number is the alkylidene of more than 3, less than 6, p and q is the quality percentage representing polymerization ratio, p represents the numerical value of more than 10 quality %, below 80 quality %, q represents the numerical value of more than 20 quality %, below 90 quality %, r represents the integer of more than 1, less than 18, and s represents the integer of more than 1, less than 10)

Above-mentioned L is preferably the branched alkylene groups represented by following formula (J-2).R in formula (J-2) ⁴⁰⁵represent that carbon number is the alkyl of more than 1, less than 4, with regard to compatibility and the viewpoint for the wetting state of applied, be preferably the alkyl that carbon number is more than 1, less than 3, be more preferably the alkyl that carbon number is 2 or 3.P and q is preferably p+q=100 with (p+q), is 100 quality %.

[changing 19]

The weight average molecular weight (Mw) of above-mentioned multipolymer is more preferably 1, more than 500,5, less than 000.

Photosensitive polymer combination of the present invention is preferably and contains phenylate surfactant as surfactant, is more preferably containing polyoxy alkylidene substituted benzene ether surface active agent as surfactant.If above-mentioned form, then the generation of the residue after development is inhibited.Especially, the generation of the residue after developing significantly is on an ito substrate inhibited.

As phenylate surfactant, be preferably the compound represented by following formula (J-3).

[changing 20]

(in formula (J-3), R ^jrepresent alkylidene, nj represents the integer of 1 ~ 50, R ^jthe substituting group of ' expression monovalence, mj represents the integer of 1 ~ 5, when mj is more than 2, there is multiple R ^j' each other can be identical, also can be different, when nj is more than 2, there is multiple R ^jeach other can be identical, also can be different)

In formula (J-3), R ^jrepresent alkylidene.That is, (R ^jo) alkylene oxide group is represented.As R ^j, being preferably carbon number is the alkylidene of 2 ~ 8, is more preferably the alkylidene that carbon number is 2 ~ 6, and then is more preferably the alkylidene that carbon number is 2 ~ 4, be particularly preferably ethylidene or propylidene.

In formula (J-3), R ^jthe substituting group of ' expression monovalence.As R ^j', can illustrate halogen atom, alkyl, aryl, thiazolinyl, hydroxyl, alkoxy, aryloxy group, above-mentioned substituting group can be further substituted.R ^j' total carbon number be preferably 1 ~ 50, be more preferably 1 ~ 20.

Compound represented by formula (J-3) as polyoxyalkylene alkyl phenylate, can replace and have aliphatic alkyl as R ^j', but be preferably R ^j' for containing the base of the monovalence of aromatic hydrocarbyl.

As polyoxy alkylidene substituted benzene ether surface active agent, be preferably the compound represented by following formula (J-4).

[changing 21]

(in formula (J-4), R ^jrepresent alkylidene, X ^jrepresent the concatenating group of singly-bound or divalence, Q ^jrepresent alkyl, xj represents the integer of 0 ~ 5, and mj represents the integer of 0 ~ 5, and nj represents the integer of 1 ~ 50, and when xj is more than 2, there is multiple Q each other can be identical, also can be different, when mj is more than 2, there is multiple X ^j, phenyl ring and containing Q ^jbase each other can be identical, also can be different, when nj is more than 2, there is multiple R ^jeach other can be identical, also can be different)

In formula (J-4), R ^jrepresent alkylidene.That is, (R ^jo) alkylene oxide group is represented.As R ^j, being preferably carbon number is the alkylidene of 2 ~ 8, is more preferably the alkylidene that carbon number is 2 ~ 6, and then is more preferably the alkylidene that carbon number is 2 ~ 4, be particularly preferably ethylidene or propylidene.That is, be particularly preferably and have containing inferior ethoxyl or the sub-propoxyl group poly-alkylene oxide group as repetitive.Moreover, when having alkylene oxide group of more than two kinds, such as when having multiple inferior ethoxyl and multiple sub-propoxyl group, poly-inferior ethoxyl can become segmented copolymer with poly-sub-propoxyl group, also can be random copolymers, in addition, also can there is the part of segmented copolymer and both parts of random copolymers, be not particularly limited.

In formula (J-4), X ^jrepresent the concatenating group of singly-bound or divalence, as the concatenating group of divalence, be preferably the alkyl of divalence, be preferably carbon number be 1 ~ 8 alkylidene (alkane two base (alkanediyl group)), carbon number be 2 ~ 8 alkene two base (alkenediylgroup), be more preferably carbon number be 1 ~ 4 alkylidene, carbon number be 2 ~ 4 alkene two base.X ^jbe particularly preferably carbon number be 1 ~ 4 alkylidene or carbon number be 2 ~ 4 alkene two base.Above-mentioned alkylidene and alkene two base can be straight-chain, also can be branch-like.

In formula (J-4), Q ^jfor the substituting group for phenyl ring, being preferably carbon number is the alkyl of 1 ~ 6, and being more preferably carbon number is 1 ~ 4, and then is more preferably methyl, ethyl, propyl group or butyl.

In formula (J-4), the base (-X-Ph-(Q alternatively on the phenyl ring of alkylene oxide group institute bond ^j) _xj), can illustrate: phenyl (-Ph), benzyl (-CH ₂-Ph), 2-phenyl-propane-2-base (-C (CH ₃) ₂-Ph), styryl (-CH=CH-Ph), 1-phenylethyl (-CH (CH ₃)-Ph).Moreover so-called Ph, represents phenyl ring, represents phenyl, represent phenylene when divalence when monovalence.

In formula (J-4), x ^jrepresent the integer of 0 ~ 5, be preferably the integer of 0 ~ 3, be more preferably the integer of 0 ~ 2, and then be more preferably 0 or 1, be particularly preferably 0.

In formula (J-4), mj represents the integer of 0 ~ 5, is preferably the integer of 1 ~ 5, is more preferably 1 ~ 4, and then is more preferably 1 ~ 3.

In formula (J-4), nj represents the integer of 1 ~ 50, is more preferably the integer of 3 ~ 40, and then is more preferably the integer of 5 ~ 35, is particularly preferably the integer of 8 ~ 30.

Compound represented by formula (J-4) is more preferably the compound represented by following formula (J-5).

[changing 22]

(in formula (J-5), R ^j1~ R ^j4separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, n1 ' and n2 ' separately represents the integer of 0 ~ 50, and n1 '+n2 ' represents the integer of 1 ~ 50, the integer of mj ' expression 1 ~ 5.But, get rid of R ^j1with R ^j2identical situation)

In formula (J-5), R ^j1and R ^j2separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, but get rid of R ^j1with R ^j2identical situation.Work as R ^j1with R ^j2time identical, single alkylene oxide group repeats, and therefore as n2 '=0, represents the sum of repetitive with n1 '.R ^j1and R ^j2separately for hydrogen atom or carbon number are the alkyl of 1 ~ 4, be preferably hydrogen atom, methyl or ethyl, be more preferably hydrogen atom or methyl.That is, the compound represented by formula (J-5) is particularly preferably has inferior ethoxyl, sub-propoxyl group or inferior ethoxyl and sub-propoxyl group.

Moreover when having multiple inferior ethoxyl and sub-propoxyl group, poly-inferior ethoxyl can become segmented copolymer with poly-sub-propoxyl group, also can be random copolymers, in addition, also can there is the part of segmented copolymer and both parts of random copolymers, be not particularly limited.

In formula (J-5), R ^j3and R ^j4separately represent that hydrogen atom or carbon number are the alkyl of 1 ~ 4, are preferably hydrogen atom, methyl or ethyl, are more preferably hydrogen atom or methyl.Be more preferably R ^j3and R ^j4be methyl or one is hydrogen atom and another one is methyl, being particularly preferably one is hydrogen atom, and another one is methyl.

In formula (J-5), n1 ' and n2 ' separately represents the integer of 0 ~ 50, and n1 '+n2 ' represents the integer of 1 ~ 50.N1 '+n2 ' is preferably the integer of 3 ~ 40, is more preferably the integer of 5 ~ 35, and then is more preferably the integer of 8 ~ 30.

In formula (J-5), the integer of mj ' expression 1 ~ 5, is more preferably the integer of 1 ~ 4, and then is more preferably the integer of 1 ~ 3.

In the present invention, the total number of the quantity of the phenyl ring in 1 molecule of polyoxy alkylidene substituted benzene ether surface active agent is preferably the scope of 1 ~ 4, is more preferably the scope of 2 ~ 4.If the total number of the quantity of phenyl ring is above-mentioned scope, then the generation of the residue after development is inhibited.

In the present invention, hydrophilic-lipophilic balance (Hydrophile-LipophileBalance, the HLB) value of polyoxy alkylidene substituted benzene ether surface active agent is preferably 5 ~ 50, is more preferably 8 ~ 30, and then be more preferably 10 ~ 20, be particularly preferably 12 ~ 16.If above-mentioned scope, then the generation of residue is inhibited further.

Herein, HLB value is the abbreviation of hydrophilic-lipophilic balance (hydrophile-lipophile balance), and is one of index of manifesting the effect that surfactant is reached, and HLB value is larger, and water wettability becomes higher.The molecular structure of HLB value can calculate according to many experiments, is not particularly limited.

In the present invention, HLB value preferably utilizes Griffin method (Griffin method) to measure.

In Griffin method, HLB value is defined by following formula.

Summation/the molecular weight of the formula weight of HLB value=20 × hydrophilic portion

Therefore, in composition F, HLB value become as shown in the formula as.

HLB value=20 × (summation of the formula weight of polyoxyalkylene moieties)/molecular weight

As polyoxy alkylidene substituted benzene ether surface active agent, can composite be used, in addition, also can use commercially available product, be not particularly limited.

As the goods gone on the market, can enumerate: Pi Aoning (Pionin) D-6112, proud peaceful (Pionin) D-6115 of skin, proud peaceful (Pionin) D-6112-W of skin, proud peaceful (Pionin) D-6108-W of skin, proud peaceful (Pionin) D-6115X of skin, proud peaceful (Pionin) D-6120X of skin, D-6414, proud peaceful (Pionin) D-6512 of skin, proud peaceful (Pionin) D-6310 of skin, proud peaceful (Pionin) D-6315 of skin, proud peaceful (Pionin) D-6320 of skin (more than, this grease of bamboo (share) manufactures), knob Cole (Newcol) CMP6, knob Cole (Newcol) CMP-11, knob Cole (Newcol) 610, knob Cole (Newcol) 710, knob Cole (Newcol) 710-F, knob Cole (Newcol) 2609, knob Cole (Newcol) 2600-FB (more than, Japan's emulsifying agent (share) manufactures).Among these, be preferably Pi Aoning (Pionin) D-6112-W, Pi Aoning (Pionin) D-6512.

These surfactants can be used alone a kind or two or more is used in combination.

Relative to total solid composition 100 mass parts in photosensitive polymer combination, the addition of the surfactant in photosensitive polymer combination of the present invention is preferably below 10 mass parts, be more preferably 0.001 mass parts ~ 10 mass parts, and then be more preferably 0.01 mass parts ~ 3 mass parts.

(composition K) antioxidant

Photosensitive polymer combination of the present invention is preferably containing antioxidant.Can containing known antioxidant as antioxidant.By adding antioxidant, there is following advantage: can prevent cured film painted, maybe the thickness that can reduce caused by decomposing reduce, in addition, heat resistant transparent is excellent.

As this kind of antioxidant, include, for example: phosphorous antioxidant, amide-type, hydrazides class, hindered amine system antioxidant, sulphur system antioxidant, phenol system antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxylamine derivative etc.Among these antioxidants, with regard to the viewpoint that painted, the thickness of cured film reduces, be particularly preferably phenol system antioxidant, acid amides system antioxidant, hydrazides system antioxidant, sulphur system antioxidant, most preferably be phenol system antioxidant.These antioxidants can be used alone a kind, also can mix two or more.

As concrete example, can enumerate compound described in the paragraph 0026 ~ paragraph 0031 of Japanese Patent Laid-Open 2005-29515 publication, these content can be incorporated into in present specification.

As the commercially available product of phenol system antioxidant, include, for example: Ai Di Coase tower ripple (Adekastab) AO-15, Ai Di Coase tower ripple (Adekastab) AO-18, Ai Di Coase tower ripple (Adekastab) AO-20, Ai Di Coase tower ripple (Adekastab) AO-23, Ai Di Coase tower ripple (Adekastab) AO-30, Ai Di Coase tower ripple (Adekastab) AO-37, Ai Di Coase tower ripple (Adekastab) AO-40, Ai Di Coase tower ripple (Adekastab) AO-50, Ai Di Coase tower ripple (Adekastab) AO-51, Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-70, Ai Di Coase tower ripple (Adekastab) AO-80, Ai Di Coase tower ripple (Adekastab) AO-330, Ai Di Coase tower ripple (Adekastab) AO-412S, Ai Di Coase tower ripple (Adekastab) AO-503, Ai Di Coase tower ripple (Adekastab) A-611, Ai Di Coase tower ripple (Adekastab) A-612, Ai Di Coase tower ripple (Adekastab) A-613, Ai Di Coase tower ripple (Adekastab) PEP-4C, Ai Di Coase tower ripple (Adekastab) PEP-8, Ai Di Coase tower ripple (Adekastab) PEP-8W, Ai Di Coase tower ripple (Adekastab) PEP-24G, Ai Di Coase tower ripple (Adekastab) PEP-36, Ai Di Coase tower ripple (Adekastab) PEP-36Z, Ai Di Coase tower ripple (Adekastab) HP-10, Ai Di Coase tower ripple (Adekastab) 2112, Ai Di Coase tower ripple (Adekastab) 260, Ai Di Coase tower ripple (Adekastab) 522A, Ai Di Coase tower ripple (Adekastab) 1178, Ai Di Coase tower ripple (Adekastab) 1500, Ai Di Coase tower ripple (Adekastab) C, Ai Di Coase tower ripple (Adekastab) 135A, Ai Di Coase tower ripple (Adekastab) 3010, Ai Di Coase tower ripple (Adekastab) TPP, Ai Di Coase tower ripple (Adekastab) CDA-1, Ai Di Coase tower ripple (Adekastab) CDA-6, Ai Di Coase tower ripple (Adekastab) ZS-27, Ai Di Coase tower ripple (Adekastab) ZS-90, Ai Di Coase tower ripple (Adekastab) ZS-91 (more than, Ai Dike (share) manufactures), Yi Jialesi (Irganox) 245FF, Yi Jialesi (Irganox) 1010FF, Yi Jialesi (Irganox) 1010, Yi Jialesi (Irganox) MD1024, Yi Jialesi (Irganox) 1035FF, Yi Jialesi (Irganox) 1035, Yi Jialesi (Irganox) 1098, Yi Jialesi (Irganox) 1330, Yi Jialesi (Irganox) 1520L, Yi Jialesi (Irganox) 3114, Yi Jialesi (Irganox) 1726, easily add Floex (Irgafos) 168, Yi Jiamode (Irgamod) 295 (BASF AG's manufacture) etc., ground slave refined (Tinuvin) 405 (BASF AG's manufacture).Wherein, can use aptly Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-80, Yi Jialesi (Irganox) 1726, Yi Jialesi (Irganox) 1035, Yi Jialesi (Irganox) 1098, refined (Tinuvin) 405 of slave.

Relative to the total solid composition of photosensitive polymer combination, the content of antioxidant is preferably 0.1 quality % ~ 10 quality %, is more preferably 0.2 quality % ~ 5 quality %, is particularly preferably 0.5 quality % ~ 4 quality %.By being set in described scope, the film formed can obtain the sufficient transparency and pattern formed time sensitivity also become good.

In addition, also using various ultraviolet light absorber described in " new development (Nikkan Kogyo Shimbun (share)) of polymeric additive " or metal passivator etc. as the adjuvant beyond antioxidant, can be added in photosensitive polymer combination of the present invention.

(composition L) has the heterogeneous ring compound of the nitrogen-atoms of more than 2

Smooth photosensitive composite of the present invention is preferably the heterogeneous ring compound containing (composition L) with the nitrogen-atoms of more than 2.Infer because composition L is adsorbed in the surface of inorganic particulate, therefore produce inorganic particulate Coulomb repulsion each other or steric repulsion, the cohesion of inorganic particulate when especially preventing coating composition and carry out dry, therefore mist degree diminishes.

As composition L, except the nitrogen-atoms with more than 2, there is no particular restriction, but the nitrogen-atoms preferably with more than 2 is as the heterogeneous ring compound of the ring element of heterocycle, be more preferably the compound of the heterocycle structure had on 1,3 at least containing nitrogen-atoms, and then be more preferably and have on 1,3 at least containing 5 yuan of heterocycle structures of nitrogen-atoms or the compound of 6 yuan of heterocycle structures.If above-mentioned form, then can obtain the hardening thing that dispersiveness is more excellent, mist degree is less of inorganic particulate.

Moreover so-called " heterocycle structure at least containing nitrogen-atoms on 1,3 ", as long as nitrogen-atoms is binding on the structure of the both sides of carbon atom in heterocycle, is not 1 and 3 on the heterocycle in formal nomenclature yet.

The ring element of the heterocycle in composition L preferably at least comprises carbon atom and nitrogen-atoms, can so that containing oxygen atom or sulphur atom as ring element, but be particularly preferably and comprise carbon atom and nitrogen-atoms.

The quantity of the nitrogen-atoms that composition L has is more than 2, is preferably 2 ~ 6, is more preferably 2 ~ 4.In addition, composition L preferably has the ring element of 2 ~ 4 nitrogen-atoms as heterocycle, is more preferably and has 2 or 3 nitrogen-atoms ring element as heterocycle, and then is more preferably and has the ring element of 2 nitrogen-atoms as heterocycle.

Heterocycle in composition L can be saturated heterocyclic, also can be unsaturated heterocycle, also can be heteroaromatic.

In addition, the heterocycle in composition L and then can carry out condensation with other rings.In addition, as other rings above-mentioned, be not only heterocycle, can be aliphatics ring, also can be aromatic rings.

As the concrete example of the heterocycle structure that composition L has, can preferably enumerate is selected from by glyoxaline structure, benzimidazole structure, 1, 2, 4-triazole structure, 4, 5-dihydro-1, 2, 4-triazole structure, tetrazolium structure, 2-imidazoline structure, 4-imidazoline structure (2, 3-glyoxalidine structure), imidazolidine structure, pyrimidine structure, quinoxaline structure, purine formation, pteridine structure, and the ring structure in the group that forms of pyridine structure pah, can more preferably enumerate is selected from by glyoxaline structure, benzimidazole structure, 1, 2, 4-triazole structure, 4, 5-dihydro-1, 2, 4-triazole structure, tetrazolium structure, 2-imidazoline structure, 4-imidazoline structure, imidazolidine structure, and the ring structure in the group that forms of pyrimidine structure, particularly preferably can enumerate benzimidazole structure or imidazolidine structure.If above-mentioned form, then can obtain the hardening thing that dispersiveness is more excellent, mist degree is less of metal oxide particle.

Composition L preferably has sulfydryl (-SH) or thioketones base (=S).If above-mentioned form, then can obtain the hardening thing that dispersiveness is more excellent, mist degree is less of metal oxide particle.

In addition, as composition L, be preferably the compound represented by following formula (L-a).

[changing 23]

(in formula (L-a), R ^a1and R ^a2separately represent the organic group of hydrogen atom, halogen atom or monovalence, R ^a1with R ^a2can bond and be the organic group of divalence, R ^a3and R ^a4separately represent the organic group of hydrogen atom or monovalence, L ^a1represent the concatenating group of the divalence of formation 5 ring or 6 rings, R ^a3or R ^a4with L ^a1can bond and form ring, in addition, when there is the nitrogenous double bond described in dotted line, the bond of dotted line represents to there is not R ^a2and R ^a4, when there is not the nitrogenous double bond described in dotted line, the bond of dotted line represents to there is R ^a2and R ^a4)

As R ^a1~ R ^a4in the organic group of monovalence, alkyl can be enumerated and (comprise naphthenic base, bicyclic alkyl, tricyclic alkyl), thiazolinyl (comprises cycloalkenyl group, bicyclic alkenyl), alkynyl, aryl, heterocycle (heterocyclic ring) base (also referred to as heterocycle (heterocycle) base), cyano group, hydroxyl, nitro, carboxyl, alkoxy, aryloxy group, silicon alkoxy, heterocyclic oxy group, acyloxy, carbamoyloxy group, alkoxy carbonyl oxygen base, aryloxy group carbonyl oxygen base, amino (comprises alkyl amino, arylamino, heterocyclic amino group), ammonium, acyl amino, amino carbonyl amino, alkoxycarbonyl amino, aryloxycarbonylamino, sulphamoylamino, alkyl sulfonyl-amino and arlysulfonylamino, sulfydryl, alkylthio group, arylthio, heterocyclethio, alkyl-dithio, aryl disulfide group, heterocycle disulfide group, sulfamoyl, sulfo group, alkyl sulphinyl and aryl sulfonyl kia, alkyl sulphonyl and aryl sulfonyl, acyl group, aryloxycarbonyl, alkoxy carbonyl, carbamyl, arylazo base and heterocycle azo base, imide, phosphino-, phosphinyl, phosphinyl oxygen base, phosphinyl is amino, phosphono, silylation, diazanyl, urea groups, ghiourea group, boronate (-B (OH) ₂), phosphoric acid foundation (-OPO (OH) ₂), sulphate groups (-OSO ₃h), other known substituting groups as an example.In addition, above-mentioned base can be replaced by substituting group further.

As R ^a1and R ^a2in the organic group of monovalence, among these bases, be particularly preferably sulfydryl.

In addition, R ^a1and R ^a2in the carbon number of organic group of monovalence be preferably 0 ~ 20, be more preferably 0 ~ 8, be particularly preferably 0.

In addition, as R ^a1with R ^a2the organic group of the divalence that bond is formed, can enumerate side oxygen base, thioketones base, alkylidene etc. as an example.Among these bases, be particularly preferably thioketones base.

R ^a1and R ^a2being particularly preferably is separately hydrogen atom or sulfydryl, in addition, works as R ^a1with R ^a2bond and when forming the organic group of divalence, be particularly preferably thioketones base.

As R ^a3and R ^a4in the organic group of monovalence, be preferably alkyl or aryl, be more preferably morpholinyl methyl or phenyl.In addition, abovementioned alkyl or aryl can be replaced by substituting group.

R ^a3and R ^a4in the carbon number of organic group of monovalence be preferably 0 ~ 20, be more preferably 1 ~ 10, and then be more preferably 4 ~ 8.

R ^a3and R ^a4being preferably is separately hydrogen atom, alkyl or aryl, is more preferably hydrogen atom, morpholinyl methyl or phenyl, and then is more preferably hydrogen atom or phenyl.

L ^a1represent the concatenating group of the divalence of formation 5 ring or 6 rings, the carbon atom in itself and formula (L-a) and 2 nitrogen-atoms together form heterocycle.

As the concatenating group of divalence, as long as together form the base of 5 yuan of heterocycles or 6 yuan of heterocycles with the carbon atom in formula (L-a) and 2 nitrogen-atoms, then there is no particular restriction, but the base that its ring element is preferably formed by carbon atom and/or nitrogen-atoms, is more preferably the base of the concrete example forming above-mentioned heterocycle structure.Wherein, and then be more preferably and form the base of benzimidazole structure, namely 1,2-phenylene, forms the base of imidazolidine structure, and namely 1,2-ethylidene, 1,1-dimethyl-1,2-ethylidene or ethene-1,2-bis-base, be particularly preferably 1,2-ethylidene, 1,1-dimethyl-1,2-ethylidene or ethene-1,2-bis-base.

And then, as composition L, be more preferably the compound represented by following formula (L-a-1) or formula (L-a-2).

[changing 24]

(in formula (L-a-1) and formula (L-a-2), R ^a6~ R ^a8separately represent the organic group of hydrogen atom or monovalence, L ^a2and L ^a3separately represent the concatenating group of the divalence of formation 5 ring or 6 rings, R ^a6with L ^a2can bond and form ring, R ^a7or R ^a8with L ^a3can bond and form ring)

R in formula (L-a-1) or formula (L-a-2) ^a6~ R ^a8implication and above-mentioned formula (L-a) in R ^a3and R ^a4identical, preferred form is also identical.

In addition, the L in formula (L-a-1) or formula (L-a-2) ^a2and L ^a3implication and above-mentioned formula (L-a) in L ^a1identical, preferred form is also identical.

Below represent the preferred concrete example (AF-1 ~ AF-14) of composition L.But, in the present invention, do not limit by these concrete examples.

[changing 25]

Among these, be preferably AF-3 ~ AF-14, be more preferably AF-3, AF-5, AF-6, AF-9, AF-12, AF-13 or AF-14, and then be more preferably AF-5, AF-9, AF-12, AF-13 or AF-14, be particularly preferably AF-9, AF-12, AF-13 or AF-14.

In addition, composition L can be used alone a kind, also can and use two or more.

Relative to the total solid composition of photosensitive polymer combination of the present invention, the content of the composition L in photosensitive polymer combination of the present invention is preferably 0.1 quality % ~ 20 quality %, be more preferably 0.5 quality % ~ 15 quality %, and then be more preferably 0.5 quality % ~ 10 quality %.If above-mentioned scope, then can obtain the hardening thing that dispersiveness is more excellent, mist degree is less of inorganic particulate.

< acid proliferation generator >

In order to promote sensitivity, photosensitive polymer combination of the present invention can use acid proliferation generator.

Acid proliferation generator used in the present invention produces acid further by acid catalyst reaction and make the compound that the acid concentration in reactive system rises, and the compound for stably existing under the state that there is not acid.

As the concrete example of this kind of acid proliferation generator, can enumerate acid proliferation generator described in the paragraph 0226 ~ paragraph 0228 of Japanese Patent Laid-Open 2011-221494 publication, described content can be incorporated into in present specification.

This kind of compound increases the acid of more than a kind by 1 secondary response, therefore with the progress of reaction, reaction is carried out post, but the acid produced itself can bring out selfdecomposition, therefore the intensity of the acid of this place generation is in acid ionization constant, pKa, is preferably less than 3, is particularly preferably less than 2.In addition, pKa is preferably more than-15.

As the concrete example of acid proliferation generator, can enumerate: compound described in page the 2nd row of the paragraph 0203 ~ paragraph 0223 of Japanese Patent Laid-Open 10-1508 publication, the paragraph 0016 ~ paragraph 0055 of Japanese Patent Laid-Open 10-282642 publication and Jap.P. JP-A 9-512498 publication the 39th page of the 12nd row ~ 47.

As acid proliferation generator used in the present invention, the acid because producing from acid producing agent can be enumerated and decompose, and producing the compound that the pKa such as dichloroacetic acid, trichloroacetic acid, methane-sulforic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl-phosphonic acid are the acid of less than 3.

Specifically, following compound etc. can be enumerated.

[changing 26]

With regard to the viewpoint of the dissolving contrast in exposure portion and unexposed portion, relative to light acid producing agent 100 mass parts, the content of acid proliferation generator in photosensitive polymer combination is preferably set to 10 mass parts ~ 1,000 mass parts, is more preferably and is set to 20 mass parts ~ 500 mass parts.

< development accelerant >

Photosensitive polymer combination of the present invention can contain development accelerant.

As development accelerant, the arbitrary compound with development accelaration effect can be used, but preferably there is the compound of at least one structure in the group selecting free carboxyl group, phenolic hydroxyl group and alkylene oxide group to form, be more preferably the compound with carboxyl or phenolic hydroxyl group, most preferably be the compound with phenolic hydroxyl group.

As development accelerant, can with reference to the record of the paragraph 0171 ~ paragraph 0172 of Japanese Patent Laid-Open 2012-042837 publication, described content can be incorporated into in present specification.

Development accelerant can be used alone a kind, also can and use two or more.

With regard to the viewpoint of sensitivity and residual film ratio, relative to total solid composition 100 mass parts of photosensitive composite, the addition of the development accelerant in photosensitive polymer combination of the present invention is preferably 0 mass parts ~ 30 mass parts, be more preferably 0.1 mass parts ~ 20 mass parts, most preferably be 0.5 mass parts ~ 10 mass parts.

In addition, the molecular weight of development accelerant is preferably 100 ~ 2, and 000, be more preferably 150 ~ 1,500, and then be more preferably 150 ~ 1,000.

< plasticiser >

Resin combination of the present invention can contain plasticiser.

As plasticiser, include, for example: dibutyl phthalate, dioctyl phthalate, phthalic acid two-ten diester, polyglycol, glycerine, dimethyl glyceryl phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerine etc.

Relative to content 100 mass parts of composition C, the content of the plasticiser in resin combination of the present invention is preferably 0.1 mass parts ~ 30 mass parts, is more preferably 1 mass parts ~ 10 mass parts.

In addition, in hot radical generation agent described in also can using in the paragraph 0120 ~ paragraph 0121 of Japanese Patent Laid-Open 2012-8223 publication, No. 2011/136074th, International Publication, described nitrogen-containing compound and thermal acid generator are as other adjuvants, and these content can be incorporated into in present specification.

The preferred physical property > of < photosensitive polymer combination

Photosensitive polymer combination of the present invention is with regard to the adaptive viewpoint of lifting ink-jet application, and the solid constituent of photosensitive polymer combination is preferably the scope of below 40 quality %, is more preferably the scope of below 35 quality %.In addition, spray with regard to this viewpoint with regard to ink-jet can be carried out well, solid constituent and then be more preferably below 30 quality %.If above-mentioned scope, then spray stability and operability excellence.

In addition, the solid constituent in photosensitive polymer combination of the present invention range preferably from 10 quality % ~ 30 quality %, be more preferably 12 quality % ~ 30 quality %.If above-mentioned scope, then can realize higher ejection stability.

With regard to the adaptive viewpoint of lifting coating, the viscosity of photosensitive polymer combination of the present invention at 25 DEG C is preferably the scope of below 50mPas, is more preferably the scope of below 30mPas.Herein, the viscosity of 25 DEG C adopts the value using E type viscosity meter to measure.

In addition, just can carry out spraying with regard to this viewpoint well, viscosity during ink-jet application when using photosensitive polymer combination of the present invention is preferably below 20mPas.If above-mentioned scope, then spray stability and operability excellence.

In addition, range of viscosities during ink-jet application when using photosensitive polymer combination of the present invention is more preferably 1mPas ~ 20mPas, and then is more preferably 1mPas ~ 15mPas.If above-mentioned scope, then can realize high ejection stability.

The surface tension of photosensitive polymer combination of the present invention at 25 DEG C is preferably more than 18mN/m, below 35mN/m, is more preferably more than 22mN/m, below 35mN/m, and then is more preferably more than 26mN/m, below 32mN/m.If above-mentioned scope, then spray stability and operability excellence.

Moreover, as the capillary assay method of photosensitive polymer combination at 25 DEG C, known method can be used, but preferably utilize suspension ring method or hang sheet method to measure.Such as can preferably enumerate: the automatic surface tensiometer CBVP-Z using consonance interface science (share) to manufacture carries out method for measuring or uses the SIGMA702 of KSV Instrument Ltd. manufacture to carry out method for measuring.

The preparation method > of < photosensitive polymer combination

As the preparation method of photosensitive polymer combination of the present invention, there is no particular restriction, can use known method.Such as, can with regulation ratio and with arbitrary method by each composition mix and blend, then carry out dissolving or disperse to prepare photosensitive polymer combination.In addition, such as, after each composition also can being made in advance to be dissolved or dispersed in respectively make solution in solvent, with the ratio specified, resin combination is prepared in the mixing of these solution.The photosensitive polymer combination prepared in the above described manner also can such as use aperture to be after the filtrator etc. of 0.2 μm filters, in.

(manufacture method of resin pattern)

Secondly, the manufacture method of resin pattern of the present invention is described.

The manufacture method of resin pattern of the present invention preferably comprises the step of following (1) ~ (5).

(1) ink-jet application mode is utilized ink-jet application photosensitive polymer combination of the present invention to be coated application step on substrate;

Next coming in order are described each step.

In the application step of (1), preferably utilize ink-jet application mode to be coated by photosensitive polymer combination of the present invention substrate makes the moistening film containing solvent.Be preferably and coat the cleaning that substrate goes forward to carry out the substrates such as alkali cleaning or plasma clean photonasty being set resin combination, be more preferably after base-plate cleaning and then utilize hexamethyldisilazane to process substrate surface.By carrying out described process, photosensitive polymer combination promotes for the adherence of substrate.As the method utilizing hexamethyldisilazane to process substrate surface, be not particularly limited, include, for example and make the method etc. of exposure of substrates in hexamethyldisilazane steam in advance.

As aforesaid substrate, can enumerate: inorganic substrate, resin, resin composite materials, ITO, indium zinc oxide (Indium ZincOxide, IZO), Cu substrate, the plastic base of polyethylene terephthalate, cellulose triacetate (Cellulose Triacetate, TAC) etc.

As inorganic substrate, include, for example: glass, quartz, silicon, silicon nitride, and on the substrate such as these composite base plate of evaporation molybdenum, titanium, aluminium, copper etc.

As resin, the substrate comprising following resin can be enumerated: polybutylene terephthalate, polyethylene terephthalate, Polyethylene Naphthalate, poly-naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyethersulfone, polyarylate, allyl diglycol carbonates, polyamide, polyimide, polyamidoimide, polyetherimide, polybenzoxazole, polyphenylene sulfide, polycyclic alkene, norcamphene resin, the fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acryl resin, epoxy resin, silicone resin, ionomeric resins, cyanate ester resin, crosslinked fumaric acid diester resin, cyclic polyolefin, aromatic ether resin, maleimide-olefin resin, cellulose, the synthetic resin such as episulfide resin (episulfide resin).

The situation that these substrates directly use with above-mentioned form is few, is generally the form according to end article, such as, be formed with the situation of the multilayer laminated structure as thin film transistor (TFT) (Thin Film Transistor, TFT) element.

Just cut down coating fluid use amount significantly, and reduce the impact of mist (mist) accompanying when utilizing spin-coating method etc., suppress the viewpoint that foreign matter generation etc. is comprehensive, compared with the existing coating process such as spin-coating method, slot coated method, be preferably the coating of ink-jetting style.

Such as, as long as utilize, the application conditions of ink-jetting style is suitable according to the kind of the composition of photosensitive polymer combination or manufactured film etc. to be selected.In order to regulate the thickness of coated film, as long as adjust the spray volume of aqueous photosensitive polymer combination or the ejection number of times towards a same part.In addition, about shape or the position of photosensitive resin coating composition, as long as be also suitable for selecting as required.As the device used in the coating of ink-jetting style, there is no particular restriction, as long as apply known ink-jet coating apparatus.

Specifically, can enumerate: drop on demand ink jet apparatus for coating IJ-DESK-S, IJ-DESK-H (PMT (share) manufacture), Di Matisi file printing machine (Dimatix Materials Printer) DMP2831, DMP-3000 (manufacture of Fujiphoto Di Matisi (FUJIFILM Dimatix) company) etc.

As the ink-jet recording apparatus that can be used for above-mentioned ink-jet application mode, there is no particular restriction, can at random select the known ink-jet recording apparatus can reached as the resolution of target to use.That is, as long as comprise the known ink-jet recording apparatus of commercially available product, the ink-jet application mode that utilizes just can implemented in above-mentioned application step is coated with photosensitive polymer combination of the present invention on substrate.

As ink-jet recording apparatus used in the present invention, include, for example the device comprising composition feed system, temperature sensor.

Ink supply system such as comprises: the ink gun of the composition supplying tank in the head tank containing photosensitive polymer combination of the present invention, supplying tubing, ink gun dead ahead, filtrator, piezo-electric type.The ink gun of piezo-electric type can drive as follows: can be preferably 320 × 320dpi ~ 4,000 × 4,000dpi (dots per inch (dotperinch)), be more preferably 400 × 400dpi ~ 1,600 × 1,600dpi, and then under the resolution being more preferably 720 × 720dpi, ejection is preferably 1pl ~ 100pl, is more preferably many sizes point (Multi Size Dot) of 8pl ~ 30pl.Moreover the dpi described in the present invention represents counting of every 2.54cm.

Coating film thickness is not particularly limited, and can be coated with, but preferably use in the scope of 0.5 μm ~ 10 μm with the thickness corresponding to purposes.

In the solvent removal step of (2), remove solvent in the above-mentioned film of coating of hanging oneself preferably by decompression (vacuum) and/or heating, thus form dry coating on substrate.Such as, the heat drying etc. utilizing heating plate can preferably be enumerated.The heating condition of solvent removal step is preferably and heats 30 seconds ~ about 300 seconds at 70 DEG C ~ 130 DEG C.When temperature and time is above-mentioned scope, the adherence of pattern is good and also can reduce residue.

Moreover the application step of (1) and the solvent removal step of (2) can be carried out according to the sequence, also can carry out, also alternately repeat simultaneously.Such as, can after the ink-jet application in the application step of (1) all terminates, carry out the solvent removal step of (2), also can first heat substrate, then one side carries out the ejection utilizing the photosensitive polymer combination of ink-jet application mode in the application step of (1), and one side carries out removal of solvents.

Wherein, after the ink-jet application be preferably in the application step of (1) all terminates, the solvent removal step of (2) is carried out.

In the step of exposure of (3), the mask be preferably across the pattern with regulation irradiates actinic ray to the substrate being provided with film.In described step, light acid producing agent decomposes and produces acid.Be coated with the catalyst action of the acid that sour decomposability gene contained in film component produces and be hydrolyzed, thus generating acidic group (such as carboxyl or phenolic hydroxyl group).

As utilizing photoactinic exposure light source, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, LED light source, excimer laser generation device etc. can be used, can preferably use g ray (436nm), i ray (365nm), h ray (405nm) etc. to have the actinic ray of wavelength of more than wavelength 300nm, below 450nm.In addition, optionally also irradiation light is adjusted by point optical filter such as long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter.

As exposure device, mirror surface projection can be used to aim at exposer (mirror projection aligner), stepper, scanner, the exposure machine of the various modes such as close induction type, contact, microlens array formula, laser explosure formula.

Having in the region of acid catalyst in generation, in order to accelerate said hydrolyzed reaction, can carry out exposing rear heating: postexposure bake (Post Exposure Bake) (hereinafter also referred to as " PEB ").By PEB, can promote from the sour carboxyl of decomposability base or the generation of phenolic hydroxyl group.Temperature when carrying out PEB is preferably more than 30 DEG C, less than 130 DEG C, is more preferably more than 40 DEG C, less than 110 DEG C, is particularly preferably more than 50 DEG C, less than 100 DEG C.

But, the energy of activation that sour decomposability base in the present invention decomposes due to acid is low, easy reason exposes the acid being derived from acid producing agent that produces and decomposes, and produce acidic group (such as carboxyl or phenolic hydroxyl group), therefore not must carry out PEB, also form erect image (positive image) by development.

In the development step of (4), be preferably and use alkaline-based developer to develop to the multipolymer with free acidic group.The region, exposure portion comprising the resin combination with the acidic group (such as carboxyl or phenolic hydroxyl group) be easily dissolved in alkaline-based developer is removed, forms erect image thus.

Containing alkali compounds in the developer solution preferably used in development step.As alkali compounds, such as, can use: the alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide; The alkali carbonate such as sodium carbonate, sal tartari class; The alkaline metal bicarbonate such as sodium bicarbonate, potassium bicarbonate class; The ammonium hydroxide classes such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, bursine; The aqueous solution of sodium silicate, sodium metasilicate etc.In addition, also the aqueous solution of adding the water-miscible organic solvents such as appropriate methyl alcohol or ethanol or surfactant in the aqueous solution to above-mentioned bases can be used as developer solution.

As preferred developer solution, can enumerate: 0.4 quality % aqueous solution of tetraethyl ammonium hydroxide, 0.5 quality % aqueous solution, 0.7 quality % aqueous solution or 2.38 quality % aqueous solution.

The pH of developer solution is preferably 10.0 ~ 14.0.

Development time is preferably 30 seconds ~ 500 seconds, and in addition, the method for development can be any one methods such as covering liquid method, infusion process.After development, 30 seconds ~ 300 second flow water cleanings can be carried out, and the pattern desired by being formed.

After development, also rinsing step can be carried out.In rinsing step, utilize the substrate after the cleaning developments such as pure water, thus accompanying developer solution is removed, and the residue that will develop is removed.ELUTION METHOD can use known method.Include, for example spray drip washing or dipping drip washing etc.

In the heat treatment step (toasting afterwards) of (5), by heating obtained erect image, and sour decomposability base can be made to carry out thermal decomposition and generate acidic group (such as carboxyl or phenolic hydroxyl group), and be cross-linked with bridging property base, crosslinking chemical etc., form cured film thus.Described heating is preferably and uses the heating arrangement such as heating plate or baking oven; in the temperature of regulation; such as, at 180 DEG C ~ 250 DEG C; with official hour; if on such as heating plate, then carry out the heating of 5 minutes ~ 90 minutes, if baking oven; then carry out the heating of 30 minutes ~ 120 minutes by carrying out cross-linking reaction, and the excellent diaphragm such as thermotolerance, hardness or interlayer dielectric can be formed.In addition, when heating, also can carry out in a nitrogen environment, promoting the transparency thus.When using plastic base, at 80 DEG C ~ 140 DEG C, preferably carry out the heating of 5 minutes ~ 120 minutes.

Also can front at heat treatment step (afterwards toast), toast with lower temperature after carry out heat treatment step (adding of middle baking procedure).When carrying out centre baking, being preferably and heating after 1 minute ~ 60 minutes at 90 DEG C ~ 150 DEG C, toasting after carrying out under the high temperature more than 200 DEG C.In addition, also centre can be toasted, rear baking is divided into the multistage in more than 3 stages and heats.By the design of baking, rear baking in the middle of this kind, the cone angle of adjustable pattern.These heating can use the known heating means such as heating plate, baking oven, infrared heater.

Moreover, can before rear baking, utilize actinic ray to carry out exposing again (post-exposure) to the figuratum substrate of formation comprehensively, then rear baking is carried out, acid is produced thus from the light acid producing agent be present in unexposed portion, and make it as promoting that the catalyzer of cross-linking step plays function, thus the sclerous reaction of film can be promoted.As preferred exposure when comprising post-exposure step, be preferably 100mJ/cm ²~ 3,000mJ/cm ², be particularly preferably 100mJ/cm ²~ 500mJ/cm ².

And then the cured film obtained from photosensitive polymer combination of the present invention also can be used as dry-etching resist (dryetching resist).When the cured film obtained carrying out thermmohardening by heat treatment step is used as dry-etching resist, the dry-etching process such as ashing, plasma etching, ozone etching can be carried out as etch processes.

(film)

Film of the present invention heat-treats obtained film to photosensitive polymer combination of the present invention.

Film of the present invention can be used as interlayer dielectric aptly.In addition, the film that preferably obtained by the manufacture method of thermal treatment thing of the present invention or the manufacture method of resin pattern of the present invention of film of the present invention.

According to photosensitive polymer combination of the present invention, even and if the interlayer dielectric that insulativity excellence has at high temperature carried out also having when toasting high transparent can be obtained.Use the interlayer dielectric of photosensitive polymer combination of the present invention to have high transparent, and cured film physical properties excellent, the purposes therefore for organic EL display or liquid crystal indicator, touch panel display device is useful.

(thermal treatment thing and manufacture method thereof)

Thermal treatment thing (hardening thing) of the present invention heat-treats obtained thermal treatment thing to photosensitive polymer combination of the present invention, and as mentioned above, its shape also can not be film, as long as arbitrary shape.

In addition, as long as thermal treatment thing of the present invention at least removes solvent at least partially and the hardening thing that rises of hardness in photosensitive polymer combination of the present invention, but be preferably and remove solvent from photosensitive polymer combination of the present invention, and the hardening thing carrying out thermmohardening and obtain.

There is no particular restriction for the manufacture method of thermal treatment thing of the present invention, preferably comprises the following steps (a) ~ step (c) at least successively.

A () utilizes ink-jet application mode ink-jet application photosensitive polymer combination of the present invention to be coated application step on substrate;

The implication of step (a) and step (b) is identical with above-mentioned application step and above-mentioned solvent removal step respectively, and preferred form is also identical.

Except the object of heat-treating is for except the resin combination eliminating solvent that obtains in step (b), step (c) is the step identical with above-mentioned heat treatment step, and the preferred form of the heating-up temperature in above-mentioned heat treatment step, heat time, heating means etc. is preferred too.

Thermal treatment thing (hardening thing) of the present invention or film can be used as the optical components such as lenticule, optical waveguide, anti-reflective film, LED sealing material and LED chip coating material aptly, or the observability reduction hardening thing of the distribution electrode used in touch-screen.

In addition; thermal treatment thing (hardening thing) of the present invention or film such as can be suitably used for planarization film in liquid crystal indicator or organic el device etc. as described later or interlayer dielectric, colored filter diaphragm, in order to the thickness of the liquid crystal layer in liquid crystal indicator to be remained the structure component etc. of fixing distance piece, MEMS (micro electro mechanical system) (Micro Electro Mechanical Systems, MEMS) element.

(liquid crystal indicator)

The feature of liquid crystal indicator of the present invention is to possess film of the present invention.

As liquid crystal indicator of the present invention, use except the planarization film that formed of photosensitive polymer combination of the present invention or interlayer dielectric except having, there is no particular restriction, can enumerate the known liquid crystal indicator adopting various structure.

Such as, as the concrete example of the TFT (Thin-Film Transistor) that liquid crystal indicator of the present invention possesses, can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to electrical characteristics excellence, preferably uses after therefore can combining with these TFT.

In addition, as the adoptable liquid crystal drive mode of liquid crystal indicator of the present invention, can enumerate: twisted-nematic (TwistedNematic, TN) mode, vertical orientated (Virtical Alignment, VA) (In-Place-Switching is switched in mode, face, IPS) mode, fringing field switch (Fringe Field Switching, FFS) mode, optical compensation curved (Optically CompensatedBend, OCB) mode etc.

In panel is formed, even if colorful optical filter array (Color Filter on Array, COA) liquid crystal indicator of mode, also can use cured film of the present invention, such as, can be used as organic insulating film (212) described in organic insulating film (115) described in Japanese Patent Laid-Open 2005-284291 publication or Japanese Patent Laid-Open 2005-346054 publication.

In addition, concrete aligned as the adoptable liquid crystal orientation film of liquid crystal indicator of the present invention, can enumerate friction orientation method, light orientation side etc.In addition, also obtain polymer orientation to support by polymer stabilizing orientation (Polymer Sustained Alignment, PSA) technology described in Japanese Patent Laid-Open 2003-149647 publication or Japanese Patent Laid-Open 2011-257734 publication.

In addition, photosensitive polymer combination of the present invention and film of the present invention are not limited to such use, can be used for various uses.Such as; except planarization film or interlayer dielectric, also can be suitably used for colored filter diaphragm or in order to the thickness of the liquid crystal layer in liquid crystal indicator to be remained in fixing distance piece or solid photographic element the lenticule etc. be arranged on colored filter.

Fig. 1 is the concept sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.Described color liquid crystal display arrangement 10 has the liquid crystal panel of back light unit 12 for the back side, and liquid crystal panel is configured with the element of the TFT16 corresponding with being configured in the 2 sheet glass substrates 14, all pixels between glass substrate 15 that are pasted with light polarizing film.Be formed in each element on glass substrate, by being formed at contact hole 18 in cured film 17 and the ito transparent electrode 19 of the tangible pixel electrode of distribution.The layer that ito transparent electrode 19 is provided with liquid crystal 20 and the RGB colored filter 22 being configured with black matrix".

As the light source of backlight, be not particularly limited, known light source can be used.Include, for example: multi-colored led, fluorescent light (cold-cathode tube), organic EL etc. of White LED, blue red green etc.

In addition, liquid crystal indicator also can be made into the device of 3D (stereopsis) type or the device of touch screen type.And then, also can be set to flexible type, and can be used as phase insulation film (520) described in the 2nd phase insulation film (48) described in Japanese Patent Laid-Open 2011-145686 publication or Japanese Patent Laid-Open 2009-258758 publication.

(organic EL display)

The feature of organic EL display of the present invention is to possess film of the present invention.

As organic EL display of the present invention, use except the planarization film that formed of photosensitive polymer combination of the present invention or interlayer dielectric except having, there is no particular restriction, can enumerate the known various organic EL display or liquid crystal indicator that adopt various structure.

Such as, as the concrete example of the TFT (Thin-Film Transistor) that organic EL display of the present invention possesses, can enumerate: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to electrical characteristics excellence, preferably uses after therefore can combining with these TFT.

Fig. 2 is the formation concept map of an example of organic EL display.Represent the constructed profile of the substrate in the organic EL display of bottom emission type, and there is planarization film 4.

Glass substrate 6 is formed the TFT1 of bottom gate polar form, and formation comprises Si under the state covering described TFT1 ₃n ₄dielectric film 3.Formed on the insulating film 3 after explanations are omitted hering illustrated contact hole, form via described contact hole the distribution 2 (being highly 1.0 μm) being connected to TFT1 on the insulating film 3.Distribution 2 is the lines in order to will be connected with TFT1 between TFT1 or by the organic EL formed in step thereafter.

And then, in order to make to form produced concavo-convex planarization by distribution 2, imbedding under the concavo-convex state produced by distribution 2, forming planarization layer 4 on the insulating film 3.

Planarization film 4 is formed the organic EL of bottom emission type.That is, the first electrode 5 comprising ITO is made to be connected to distribution 2 via contact hole 7 and to be formed on planarization film 4.In addition, the first electrode 5 is equivalent to the anode of organic EL.

Forming the dielectric film 8 of the shape of the periphery of covering first electrode 5, by arranging described dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and step thereafter can be prevented.

And then, although not shown in Fig. 2, but carry out evaporation successively to arrange hole transmission layer, organic luminous layer, electron transfer layer across desired pattern mask, then, whole of surface is formed the second electrode comprising Al, then carry out fitting sealing with glass for sealing plate by using ultraviolet ray hardening type epoxy resin, and obtain the organic EL display connecting the active array type in order to the TFT1 driven it on each organic EL.

The Resist patterns using photosensitive polymer combination of the present invention to be formed, due to photonasty and membrane property excellence, is therefore made dividing wall and is used as the structure component of MEMS element or is assembled rear use as a part for Mechanical Driven part by photosensitive polymer combination of the present invention.As this kind of MEMS element, include, for example: surface acoustic wave (Surface AcousticWave, SAW) part such as wave filter, bulk acoustic wave (Bulk Acoustic Wave, BAW) wave filter, gyro sensor (gyro sensor), the micro-shutter of display, imageing sensor, Electronic Paper, ink gun, biochip, sealant.Example has illustration in Jap.P. spy table 2007-522531 publication, Japanese Patent Laid-Open 2008-250200 publication, Japanese Patent Laid-Open 2009-263544 publication etc. more specifically.

Photosensitive polymer combination of the present invention is due to flatness or transparency excellence, therefore also can be used for being formed accumulation horizon (16) described in Fig. 2 of such as Japanese Patent Laid-Open 2011-107476 publication and planarization film (57), dividing wall (12) described in Fig. 4 (a) of Japanese Patent Laid-Open 2010-9793 publication and planarization film (102), accumulation horizon (221) described in Figure 10 of Japanese Patent Laid-Open 2010-27591 publication and the 3rd interlayer dielectric (216b), the 2nd interlayer dielectric (125) described in Fig. 4 (a) of Japanese Patent Laid-Open 2009-128577 publication and the 3rd interlayer dielectric (126), planarization film (12) described in Fig. 3 of Japanese Patent Laid-Open 2010-182638 publication and pixel separation dielectric film (14) etc.

(touch panel display device)

Touch panel display device of the present invention possesses the capacitive input device with film of the present invention.In addition, the feature of capacitive input device of the present invention is to have film of the present invention.

Capacitive input device of the present invention preferably has front panel, and at least has the key element of following (1) ~ following (5) in the noncontact side of above-mentioned front panel, and following (4) are thermal treatment thing of the present invention.

(1) mask layer

(2) multiple pad part extends formed multiple first transparent electrode patterns in a first direction via coupling part

(3) be electrically insulated with above-mentioned first transparent electrode pattern and be included in multiple second transparent electrode patterns direction that intersects with above-mentioned first direction extending formed multiple pad parts

(4) by insulation course that above-mentioned first transparent electrode pattern and above-mentioned second transparent electrode pattern are electrically insulated

(5) be electrically connected from least one of above-mentioned first transparent electrode pattern and above-mentioned second transparent electrode pattern and with above-mentioned first transparent electrode pattern and the different electric conductivity key element (conductive element) of above-mentioned second transparent electrode pattern

Capacitive input device of the present invention is preferably all or part of mode of the key element to cover above-mentioned (1) ~ above-mentioned (5) and then arranges protective clear layer, and being more preferably above-mentioned protective clear layer is cured film of the present invention.

First, the formation of capacitive input device is described.Fig. 3 is the sectional view of the formation representing capacitive input device.In figure 3, capacitive input device 30 comprises: front panel 31, mask layer 32, first transparent electrode pattern 33, second transparent electrode pattern 34, insulation course 35, electric conductivity key element 36 and protective clear layer 37.

Front panel 31 is made up of light-transmitting substrates such as glass substrates, the tempered glass etc. that can to use with the gorilla glass of healthy and free from worry (Corning) company (Gorilla Glass) be representative.In addition, in figure 3, the side being provided with each key element of front panel 31 is called noncontact face.In capacitive input device 30 of the present invention, finger etc. is contacted with the surface of contact (opposing face in noncontact face) of front panel 31 etc. and input.Below, sometimes front panel is called " base material ".

In addition, the noncontact face of front panel 31 is provided with mask layer 32.Mask layer 32 is patterns of the frame shape around the viewing area of the noncontact side being formed at touch-screen front panel, and it is in order to make lead-in wire etc. not in sight and be formed.

In capacitive input device of the present invention, as shown in Figure 4, the mode in the region (region in Fig. 4 beyond input face) covering a part for front panel 31 is provided with mask layer 32.And then, in front panel 31, as shown in Figure 4, can peristome 38 be set in a part.In peristome 38, the mechanical switch utilizing pressing can be set.

As shown in Figure 5, the surface of contact of front panel 31 is formed multiple first transparent electrode pattern 33, multiple second transparent electrode pattern 34, and insulation course 35, above-mentioned multiple first transparent electrode pattern 33 is that multiple pad part extends in a first direction via coupling part and formed, above-mentioned multiple second transparent electrode pattern 34 is electrically insulated with the first transparent electrode pattern 33, and be included on the direction that intersects with first direction and extend formed multiple pad parts, above-mentioned insulation course 35 is that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated.Above-mentioned first transparent electrode pattern 33, second transparent electrode pattern 34 and electric conductivity key element 36 described later such as can utilize the conductive metal oxide film of the light transmission such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide) to make.As this kind of metal film, can enumerate: ito film; The metal film of Al, Zn, Cu, Fe, Ni, Cr, Mo etc.; SiO ₂deng metal oxide film etc.Now, the thickness of each key element can be set to 10nm ~ 200nm.In addition, because making the ito film of amorphous become the ito film of polycrystalline by calcining, therefore also resistance can be reduced.In addition, above-mentioned first transparent electrode pattern 33, second transparent electrode pattern 34 and electric conductivity key element 36 described later also can use photosensitive transfer printing material to manufacture, and described photosensitive transfer printing material has the photosensitive polymer combination using above-mentioned conducting fibre.In addition, when utilizing ITO etc. to form first conductive pattern etc., can with reference to the paragraph 0014 ~ paragraph 0016 etc. of Jap.P. No. 4506785 publication.

In addition, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 can be opposition side with front panel 31 these two regions, face are arranged across the noncontact face of front panel 31 and mask layer 32.In figure 3, the figure that with front panel 31 be opposition side face this two region arrange of the second transparent electrode pattern across the noncontact face of front panel 31 and mask layer 32 is represented.

Fig. 5 is used to be described the first transparent electrode pattern 33 and the second transparent electrode pattern 34.Fig. 5 is the key diagram of the example representing the first transparent electrode pattern in the present invention and the second transparent electrode pattern.As shown in Figure 5, the first transparent electrode pattern 33 is that pad part 33a extends in a first direction via coupling part 33b and formed.In addition, the second transparent electrode pattern 34 is electrically insulated with the first transparent electrode pattern 33 by insulation course 35 and is included in the direction (second direction in Fig. 5) intersected with first direction and above extends the multiple pad parts formed.Herein, when formation the first transparent electrode pattern 33, using above-mentioned pad part 33a and coupling part 33b as integrally making, also can only make coupling part 33b, and using pad part 33a and the second transparent electrode pattern 34 as integrally making (patterning).When using pad part 33a and the second transparent electrode pattern 34 as when integrally making (patterning), as shown in Figure 5, each layer is formed as follows: a part and a part of pad part 33a of coupling part 33b are connected and the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by insulation course 35.

In figure 3, be opposition side with front panel 31 side, face is provided with electric conductivity key element 36 at mask layer 32.Electric conductivity key element 36 be electrically connected from least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 and with the first transparent electrode pattern 33 and the different key element of the second transparent electrode pattern 34.In figure 3, the figure that electric conductivity key element 36 is connected with the second transparent electrode pattern 34 is represented.

In addition, in figure 3, the mode each inscape all covered is provided with protective clear layer 37.Protective clear layer 37 can be formed in the mode of the part only covering each inscape.Insulation course 35 can be identical material with protective clear layer 37, also can be different materials.

< capacitive input device and possess the touch panel display device > of capacitive input device

The capacitive input device obtained by manufacture method of the present invention, and possess described capacitive input device as the touch panel display device of inscape can apply " up-to-date touch screen technology " (on July 6th, 2009 issue, Age of Technology (Techno Times) (share)), male two supervisions of three paddy, " technology of touch-screen and exploitation ", CMC publishes (2004, 12), flat-panel monitor international symposium 2009 (FPD International 2009Forum) T-11 gives a lecture teaching material, the formation disclosed in Cypress Semiconductor Co., Ltd (Cypress Semiconductor Corporation) application guide (Application Note) AN2292 etc.

< touch-screen and manufacture method > thereof

Touch-screen of the present invention is the touch-screen that all or part of of insulation course comprises the thermal treatment thing of resin combination of the present invention.In addition, touch-screen of the present invention preferably at least has transparency carrier, ITO electrode and insulation course.

Touch panel display device of the present invention preferably has the touch panel display device of touch-screen of the present invention.

In addition, the manufacture method of touch-screen of the present invention is the manufacture method of the touch-screen with transparency carrier, ITO electrode and insulation course, preferably comprise the steps: in the mode contacted with ITO electrode, utilize ink-jet application mode to be coated with the step of ink-jet application photosensitive polymer combination of the present invention; Above-mentioned resin combination loads the mask with the patterns of openings of regulation shape and carries out active energy ray and irradiate the step of carrying out exposing; To the step that the resin combination after exposure develops; And the step manufacturing insulation course is heated to the resin combination after development.

As the transparency carrier in touch-screen of the present invention, can preferably enumerate: glass substrate, quartz base plate, transparent resin substrate etc.

Above-mentioned in the mode contacted with ITO electrode, the ink-jet application utilizing ink-jet application mode to be coated with in the step of ink-jet application photosensitive polymer combination of the present invention can be carried out in the same manner as above-mentioned application step, and preferred form is also identical.In addition, in above-mentioned steps, as long as the contacting with ITO electrode at least partially of the photosensitive polymer combination of the present invention be coated with.

Above-mentioned on resin combination mounting there is the mask of the patterns of openings of regulation shape and carry out active energy ray and irradiate and carry out the step that exposes, can carry out in the same manner as above-mentioned step of exposure the step that the resin combination after exposure develops, preferred form is also identical.

Above-mentioned resin combination after development is heated to the step manufacturing insulation course and can carry out in the same manner as above-mentioned heat treatment step, preferred form is also identical.

In addition, as an example of the ITO electrode pattern in touch-screen of the present invention, the pattern shown in above-mentioned Fig. 5 can preferably be enumerated.

[embodiment]

Below, embodiment is enumerated to further illustrate the present invention.Only otherwise depart from purport of the present invention, then following the material shown in embodiment, use amount, ratio, contents processing, handling procedure etc. can be suitable for changing.Therefore, scope of the present invention is not limited to concrete example shown below.Moreover as long as in advance without special instruction, then " part ", " % " are quality criteria.

In following synthesis example, embodiment and comparative example, following symbol represents following compound respectively.

MATHF: methacrylic acid tetrahydrofuran-2-base ester (composite)

MAEVE: methacrylic acid 1-ethoxy ethyl ester (manufacturing with the pure pharmaceutical worker's industry (share) of light)

MACHOE: methacrylic acid 1-(cyclohexyloxy) ethyl ester (composite)

MATHP: methacrylic acid tetrahydrochysene-2H-pyrans-2-base ester (Xin Zhong village chemical industry (share) manufacture)

GMA: glycidyl methacrylate (manufacturing with the pure pharmaceutical worker's industry (share) of light)

OXE-30: methacrylic acid (3-Ethyloxetane-3-base) methyl esters (Osaka Organic Chemical Industry (share) manufacture)

NBMA: n-butoxy methyl acrylamide (the beautiful sun of Mitsubishi (share) manufacture)

MAA: methacrylic acid (manufacturing with the pure pharmaceutical worker's industry (share) of light)

HEMA: 2-hydroxyethyl methacrylate (manufacturing with the pure pharmaceutical worker's industry (share) of light)

MMA: methyl methacrylate (manufacturing with the pure pharmaceutical worker's industry (share) of light)

St: styrene (manufacturing with the pure pharmaceutical worker's industry (share) of light)

DCPM: methacrylic acid two ring pentyl ester (Hitachi changes into industry (share) manufacture)

V-601: dimethyl-2,2 '-azo two (propionic acid 2-methyl esters) (manufacturing with the pure pharmaceutical worker's industry (share) of light)

V-65:2,2 '-azo two (2,4-methyl pentane nitrile) (manufacturing with the pure pharmaceutical worker's industry (share) of light)

MEDG: diethylene glycol ethyl methyl ether (eastern nation chemical industry (share) manufactures, Ha Yisuo (Hisolve) EDM)

PGMEA: propylene glycol methyl ether acetate (Showa electrician (share) manufacture)

MDM: diethylene glycol dimethyl ether (eastern nation chemical industry (share) manufacture)

MDPOM: dimethyl ether (eastern nation chemical industry (share) manufacture)

EDM (MEDG): diethylene glycol ethyl methyl ether (eastern nation chemical industry (share) manufacture)

DPM: dipropylene glycol monomethyl ether (eastern nation chemical industry (share) manufacture)

EDE: diethylene glycol diethyl ether (eastern nation chemical industry (share) manufacture)

DM: diethylene glycol monomethyl ether (eastern nation chemical industry (share) manufacture)

BDM: diethylene glycol butyl methyl ether (eastern nation chemical industry (share) manufacture)

MTPOM: tripropylene glycol dimethyl ether (eastern nation chemical industry (share) manufacture)

MTM: TRIGLYME (eastern nation chemical industry (share) manufacture)

DB: diethylene glycol monobutyl ether (eastern nation chemical industry (share) manufacture)

EPH: ethyleneglycol monophenylether (eastern nation chemical industry (share) manufacture)

TM: triethylene glycol monomethyl ether (eastern nation chemical industry (share) manufacture)

BDB: dibutyl ethylene glycol ether (eastern nation chemical industry (share) manufacture)

BTM: triethylene glycol butyl methyl ether (eastern nation chemical industry (share) manufacture)

MPM: Polyethylene glycol dimethyl ether (eastern nation chemical industry (share) manufacture)

MTEM: tetraethyleneglycol dimethyl ether (eastern nation chemical industry (share) manufacture)

PM: poly glycol monomethyl ether (eastern nation chemical industry (share) manufacture)

MMM: glycol dimethyl ether (eastern nation chemical industry (share) manufacture)

IPDM: diethylene glycol isopropyl methyl ether (eastern nation chemical industry (share) manufacture)

THFA: tetrahydrofurfuryl alcohol (manufacture of Zi Bo Huaao Chemical Co., Ltd.)

PGDA: propylene-glycol diacetate (Daicel (Daicel) (share) manufactures)

1,3-BGDA:1,3-butylene glycol diacetate esters (Daicel (share) manufacture)

Isosorbide-5-Nitrae-BDDA:1,4-butylene glycol diacetate esters (Daicel (share) manufacture)

1,6-HDDA:1,6-hexanediol diacetate esters (Daicel (share) manufacture)

CHXA: adnoral acetate (Daicel (share) manufacture)

PGMEP: propylene glycol monomethyl ether propionate ((share) stretches greatly chemistry (share) manufacture)

BMGAC: ethylene glycol monomethyl ether acetate (Daicel (share) manufacture)

EDGAC: diethylene glycol monoethyl ether acetic acid esters (Daicel (share) manufacture)

BDGAC: butyl carbitol acetate (Daicel (share) manufacture)

DPMA: dipropylene glycol methyl ether acetic acid esters (Daicel (share) manufacture)

DPMNP: dipropylene glycol methyl-positive propyl ether (Daicel (share) manufacture)

DRA-150: glyceryl triacetate (Daicel (share) manufacture)

MB:3-methoxybutanol (Daicel (share) manufacture)

1,3-BG:1,3-butylene glycol (Daicel (share) manufacture)

PNP: Propylene glycol n-propyl ether (Daicel (share) manufacture)

PNB: propylene glycol n-butyl ether (Daicel (share) manufacture)

EDG: diethylene glycol monoethyl ether (Daicel (share) manufacture)

DPNP: dipropylene glycol n-propyl ether (Daicel (share) manufacture)

DPNB: dipropylene glycol n-butyl ether (Daicel (share) manufacture)

TPM: tripropylene glycol methyl ether (Daicel (share) manufacture)

TPNB: tripropylene glycol n-butyl ether (Daicel (share) manufacture)

MAK: methyl amyl ketone (long shallow industry (share) manufactures)

The synthesis > of <MTHF

First methacrylic acid (86g, 1mol) is cooled to 15 DEG C, then adds camphorsulfonic acid (4.6g, 0.02mol).2-dihydrofuran (71g, 1mol, 1.0 equivalents) is dripped in described solution.Stir after 1 hour, add saturated sodium bicarbonate (500mL), and utilize ethyl acetate (500mL) to extract, after utilizing magnesium sulfate to carry out drying, insolubles is filtered, then below 40 DEG C, reduced pressure concentration is carried out, decompression distillation is carried out to the yellow oil of residue, and obtains methacrylic acid tetrahydrofuran-2-base ester (MATHF) 125g (productive rate is 80%) as boiling point (bp.) 54 DEG C ~ 56 DEG C/3.5mmHg cut of colorless oil.

Moreover, be altered to except corresponding compound except by 2-dihydrofuran, synthesize MACHOE with the method identical with above-mentioned MATHF.

[synthesis of polymkeric substance C1]

In there-necked flask, add MEDG (89g), be warming up to 90 DEG C in a nitrogen environment.Last 2 hours in described solution and drip MAA (becoming the amount of the 9.5mol% in all monomer components), MATHF (becoming the amount of the 43mol% in all monomer components), GMA (being equivalent to the 47.5mol% in all monomer components), V-65 (relative to the total 100mol% of all monomer components, being equivalent to 4mol%) make these dissolve.Dropping terminates rear stirring 2 hours, then makes reaction terminate.Obtain polymkeric substance C1 thus.Moreover, MEDG and the ratio of the total amount of other compositions are set to 70: 30.That is, the polymer solution that solid component concentration is 30% is prepared.

Change as shown in following table the kind, polymerization initiator etc. of monomer that use, and synthesize other polymkeric substance.

[table 1]

The numerical value of the not additional especially unit in above-mentioned table 1 using mol% as unit.In addition, the numerical value of polymerization initiator is mol% when monomer component being set to 100mol%.

Solid component concentration calculates by following formula.

Solid component concentration: monomer mass/(monomer mass+solvent quality) × 100 (unit: quality %)

In addition, when using V-601 as initiating agent, temperature of reaction being set to 90 DEG C, when using V-65 as initiating agent, temperature of reaction being set to 70 DEG C.

In addition, the physics value of each solvent used in embodiment and comparative example is shown in table 2.

Moreover, about the boiling point of solvent, record with reference to known document.In addition, I/O value be according to " new edition organic conceptional diagram basis with application " (first Tian Shansheng, help rattan four youth, between this, kind husband shows, three altogether publish (2008)) record, use organic conceptional diagram reckoner (with reference to http://www.ecosci.jp/chem9/interaction.html) to calculate.In addition, surface tension is that the automatic surface tensiometer CBVP-Z using consonance interface science (share) to manufacture measures.

[table 2]

The preparation > of < dispersion liquid P

The dispersion liquid of following composition is concocted, and itself and zirconium oxide bead (0.3mm φ) 17,000 part are mixed, then use coating vibrating machine (Paint Shaker) to carry out dispersion in 12 hours.Leaching zirconium oxide bead (0.3mm φ), and obtain dispersion liquid P.

Titania (stone originates in industry (share) manufacture, trade name: TTO-51 (A), average primary particle diameter: 10nm ~ 30nm): 1,875 parts

Di Sipabike (DISPERBYK)-111 (Japanese Bi Ke chemistry (BYK-Chemie Japan) (share) manufacture) 30%PGMEA solution: 2,200 parts

Solvent PGMEA:3,425 parts

The preparation > of < photosensitive polymer combination

Carry out allocating with following composition, mix and after making uniform solution, use the tygon filtrator with the aperture of 0.2 μm to filter, and make the photosensitive polymer combination of embodiment 1.The solid constituent of the photosensitive polymer combination obtained is 17.0%, uses described photosensitive polymer combination, carries out various evaluation described later.Evaluation result is shown in table 3 described later.

Solvent EDE (B1): 307.5 parts

Alkali compounds I1 (following compound, Japan changes into industry (share) manufacture, CMTU): 0.02 part

Polymkeric substance C1:100.0 part

Light acid producing agent D1 (following compound): 1.9 parts

Thermal cross-linking agent F1 (following compound): 6.9 parts

Alkoxysilane compound containing trialkylsilyl group in molecular structure H1 (SHIN-ETSU HANTOTAI's chemical industry (share) manufactures for 3-glycidoxypropyltrimewasxysilane, KBM-403): 1.7 parts

Surfactant W1 (non-ionic surfactant containing perfluoroalkyl, F-554, Di Aisheng (share) manufacture): 0.08 part

Dispersion liquid P:181.7 part

Following compound L 1:0.2 part

< embodiment 2 ~ embodiment 27 and comparative example 1 ~ comparative example 16>

Except being altered to the solvent shown in following table 3, solid constituent, prepare photosensitive polymer combination respectively similarly to Example 1.Evaluation result is shown in table 3 described later.

< embodiment 28>

Carry out allocating with following composition, mix and after making uniform solution, use the tygon filtrator with the aperture of 0.2 μm to filter, and make the photosensitive polymer combination of embodiment 28.The solid constituent of the photosensitive polymer combination obtained is 17.0%, uses described photosensitive polymer combination, carries out various evaluation described later.Evaluation result is shown in table 7 described later.

Solvent EDE (B1): 307.5 parts

Polymkeric substance C2:100.0 part

Light acid producing agent D1 (following compound): 1.9 parts

Thermal cross-linking agent F2 (following compound): 6.9 parts

Dispersion liquid P:181.7 part

Following compound L 1:0.2 part

< embodiment 29 ~ embodiment 110>

Except being altered to the polymkeric substance shown in following table 4 ~ table 6, light acid producing agent, sensitizer, solvent, thermal cross-linking agent, surfactant and/or other adjuvants, prepare photosensitive polymer combination respectively similarly to Example 1.Moreover the addition of each component amount in table 4 ~ table 6 represents mass parts.Evaluation result is shown in table 7 ~ table 9 described later.

Represent in embodiment other than the above and comparative example that the details of the contracted notation of each compound used is as follows.

< polymkeric substance >

C1 ~ C10: according to the polymkeric substance synthesized by above-mentioned synthesis example

C11: Zhuan Chen Joncryl) 67 (acrylic resins of alkali-soluble, weight average molecular weight is 12,500, and acid number is 213mgKOH/g, and BASF AG manufactures)

< light acid producing agent >

D1: the structure (synthesis example is by aftermentioned) shown in following

[changing 27]

D2: the structure (synthesis example is by aftermentioned) shown in following

[changing 28]

D3: the structure (method synthesis described in the paragraph 0108 according to Jap.P. spy table 2002-528451 publication) shown in following

[changing 29]

D4:PAG-103 (BASF AG manufactures for trade name, the structure shown in following)

[changing 30]

D5:GSID-26-1, triarylsulfonium salt (BASF AG's manufacture)

[changing 31]

The synthesis > of <D1

In the suspension solution of beta naphthal (10g), chlorobenzene (30mL), add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g), react 2 hours after mixed liquor being heated to 40 DEG C.Under ice cooling, 4, in reactant liquor, drip the HCl aqueous solution (60mL) of 4N, then add ethyl acetate (50mL) to carry out separatory.Sal tartari (19.2g) is added in organic layer, react at 40 DEG C after 1 hour, the HCl aqueous solution (60mL) of adding 2N carries out separatory, after organic layer is concentrated, utilize diisopropyl ether (10mL) by crystallization more slurried (reslurry), then carry out filtering, dry and obtain ketonic compound (6.5g).

In the suspension solution of obtained ketonic compound (3.0g), methyl alcohol (30mL), add acetic acid (7.3g), 50 quality % aqueous hydroxylamine solutions (8.0g), and carry out heating backflow.After placing cooling, add water (50mL), separated out crystallization is filtered, after utilizing cold methanol to clean, in addition dry and obtain oxime compound (2.4g).

Obtained oxime compound (1.8g) is made to be dissolved in acetone (20mL), add triethylamine (1.5g), paratoluensulfonyl chloride (2.4g) under ice cooling, 4, be warming up to room temperature (25 DEG C) and react 1 hour afterwards.In reactant liquor, add water (50mL), after filtering separated out crystallization, utilize methyl alcohol (20mL) slurried again, then carry out filtering, dry and obtain compound (said structure) (2.3g) of D1.

Moreover, D1's ¹h-NMR spectrum (300MHz, CDCl ₃) be δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

The synthesis > of <D2

1-amino-beta naphthal hydrochloride (Tokyo changes into industry (share) manufacture) 4.0g is made to be suspended in 1-METHYLPYRROLIDONE (medicine essence pure with light) 16g, after adding sodium bicarbonate (manufacturing with the pure pharmaceutical worker's industry (share) of light) 3.4g, drip 4,4-dimethyl-3-side oxy pentanoic acid methyl esters (manufacturing with the pure pharmaceutical worker's industry (share) of light) 4.9g, and carry out heating in 2 hours with 120 DEG C in a nitrogen environment.After placing cooling, in reaction mixture, add water, ethyl acetate to carry out separatory, after utilizing magnesium sulfate to carry out drying to organic phase, carry out filtering, concentrating and obtain thick D2A.Utilize silicone tube column chromatography to refine thick D2A, and obtain the intermediate D2A of 1.7g.

D2A (1.7g) is mixed with P-xylene (6mL), adds p-toluenesulfonic acid monohydrate (manufacturing with the pure pharmaceutical worker's industry (share) of light) 0.23g and at 140 DEG C, carry out heating in 2 hours.After placing cooling, in reaction mixture, add water, ethyl acetate to carry out separatory, after utilizing magnesium sulfate to carry out drying to organic phase, carry out filtering, concentrating and obtain thick D2B.

Tetrahydrofuran (THF) (2mL) is mixed with all thick D2B, drip 2M hydrochloric acid/THF solution 6.0mL under ice cooling, 4, then drip isoamyl nitrite (manufacturing with the pure pharmaceutical worker's industry (share) of light) (0.84g), stir 2 hours after till being warming up to room temperature.In obtained reaction mixture, add water, ethyl acetate to carry out separatory, after utilizing water to clean organic layer, utilize magnesium sulfate to carry out drying, then carry out filtering, concentrating and obtain the thick D2C of intermediate.

Thick for all intermediates D2C is mixed with acetone (10mL), after adding triethylamine (manufacturing with the pure pharmaceutical worker's industry (share) of light) (1.2g), paratoluensulfonyl chloride (Tokyo changes into industry (share) manufacture) (1.4g) under ice cooling, 4, till being warming up to room temperature, stir 1 hour.In obtained reaction mixture, add water, ethyl acetate to carry out separatory, after utilizing magnesium sulfate to carry out drying to organic phase, carry out filtering, concentrating and obtain thick D2.After utilizing cold methanol that thick D2 is slurried again, carry out filtering, dry and obtain D2 (1.2g).

Moreover, D2's ¹h-NMR spectrum (300MHz, CDCl ₃) be δ=8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).

< thermal cross-linking agent >

F1:jER828 (bisphenol A type epoxy resin, Mitsubishi Chemical's holding (share) manufactures)

F2:jER157S65 (phenolic resin varnish type epoxy resin, Mitsubishi Chemical's holding (share) manufactures)

F3:jER1007 (bisphenol A type epoxy resin, Mitsubishi Chemical's holding (share) manufactures)

< sensitizer >

G1:DBA (9,10-dibutoxy anthracene, Kawasaki changes into industry (share) manufacture)

< alkoxysilane compound containing trialkylsilyl group in molecular structure >

H1:3-glycidoxypropyltrimewasxysilane (KBM-403, SHIN-ETSU HANTOTAI's chemical industry (share) manufactures)

< alkali compounds >

I1: the compound (Japan changes into industry (share) manufacture, CMTU) of following structure

[changing 32]

< surfactant >

W1: the non-ionic surfactant (F-554, Di Aisheng (share) manufacture) containing perfluoroalkyl

J1: Pi Aoning (Pionin) D-6112-W (the polystyrene-based phenylate of polyoxy alkylidene, this grease of bamboo (share) manufactures)

J2: Pi Aoning (Pionin) D-6512 (polyoxyethylene list styryl phenylate, this grease of bamboo (share) manufactures)

Other adjuvants of < >

L1: the compound (there is the heterogeneous ring compound of the nitrogen-atoms of more than 2) of following structure

L2: the compound (there is the heterogeneous ring compound of the nitrogen-atoms of more than 2) of following structure

L3: the compound (there is the heterogeneous ring compound of the nitrogen-atoms of more than 2) of following structure

L4: the compound (there is the heterogeneous ring compound of the nitrogen-atoms of more than 2) of following structure

L5: the compound (there is the heterogeneous ring compound of the nitrogen-atoms of more than 2) of following structure

[changing 33]

The evaluation > of < ink-jet ejection

Ink-jet coating apparatus: Di Matisi file printing machine DMP-2831 (Fujiphoto Di Matisi company manufactures, and driving voltage is 16V, and frequency is 5kHz)

Utilize said apparatus, the photosensitive polymer combination that glass substrate (trade name: XG, Corning Incorporated manufactures) the upper ink-jet application towards 50 100mm × 100mm obtains.After terminating towards the coating on 50 sheet glass substrates, these 16, jetting nozzle front end is all observed, and confirms the blocking of spray nozzle front end.In addition, confirm to have carried out being coated with the line described.Visual valuation is carried out by following benchmark.More than 3 is usage range.

5: spray nozzle clogging is 0 and does not exist to describe the bending of line.

4: spray nozzle clogging is 1 ~ 2 and does not exist to describe the bending of line.

3: spray nozzle clogging is 3 ~ 5 and does not exist to describe the bending of line.

2: spray nozzle clogging is 6 ~ 10 or there is the bending of description line.

1: spray nozzle clogging is more than 10 or there is the bending of description line.

The evaluation > of < drying property

In the glass substrate (trade name: XG of 100mm × 100mm, Corning Incorporated manufactures) on, the mode utilizing above-mentioned ink-jet coating apparatus to become 2.0 μm with dry film thickness is coated with obtained photosensitive polymer combination, and carries out 120 seconds dry (prebake conditions) with each temperature on hot plate and obtain coated film.Thereafter, utilize coated film described in finger contact, and confirm dry.Metewand is as described below.More than 3 is usage range.

5: dry prebake conditions temperature less than 80 DEG C.

4: dry more than 80 DEG C and at being 85 DEG C in prebake conditions temperature.

3: dry more than 85 DEG C and at being 90 DEG C in prebake conditions temperature.

2: dry more than 90 DEG C and at being 100 DEG C in prebake conditions temperature.

1: not dry at prebake conditions temperature 100 DEG C.

< developability (analyticity) evaluates >

At use hexamethyldisilazane (Hexamethyldisilazane, HMDS) glass substrate (trade name: XG of the 100mm × 100mm of process in 3 minutes has been carried out, Corning Incorporated manufactures) on, the mode utilizing above-mentioned ink-jet coating apparatus to become 2.0 μm with thickness is coated with obtained photosensitive polymer combination, and carries out on the heating plate of 90 DEG C 120 seconds dry (prebake conditions).

Secondly, ghi ray high-pressure mercury-vapor lamp exposure machine is used, with illumination 20mW/cm ², 200mJ/cm ²the mask with 1% ~ 60% GTG (gradation) being 1: 1 across line and space exposes.

Then, at 23 DEG C, utilize the KOH aqueous solution of 0.5% and utilize leaching to cover liquid method and carry out development in 15 seconds, and then utilize ultrapure water to carry out drip washing in 10 seconds.Then, heat 45 minutes at 220 DEG C and obtain pattern.Optical microscope is utilized to observe described pattern.

Described operation is started from the line of mask and the width 50 μm in space, and make reduced width 5 μm till 10 μm at every turn, make reduced width 1 μm when less than 10 μm at every turn, optimum exposure part the minimum widith of clearly pattern-making can be set to resolution.More than 3 is usage range.

5: resolution is less than 5 μm.

4: resolution is more than 5 μm and be less than 10 μm.

3: resolution is more than 10 μm and be less than 15 μm.

2: resolution is more than 15 μm and be less than 50 μm.

1: cannot pattern be formed under the line of mask and the width 50 μm in space.

The evaluation > of < mist degree (transparency)

In the glass substrate (trade name: XG of 100mm × 100mm, Corning Incorporated manufactures) on, the mode utilizing above-mentioned ink-jet coating apparatus to become 1.5 μm with dry film thickness is coated with obtained photosensitive polymer combination, and carries out on the heating plate of 80 DEG C 120 seconds dry (prebake conditions).And then, implement within 15 minutes, to heat (toasting afterwards) to coated film in the baking oven of 220 DEG C, for the mist degree after rear baking, utilize the NDH-5000 that Japanese electric look industry (share) manufactures, make face upwards, and measure mist degree (haze value) according to plastic products test method (JIS K7136JIS K7361ASTM D1003).

Moreover, so-called haze value, refer to by diffuse transmission light for full light therethrough light ratio (%) represented by value.Haze value is less, represents that the transparency is higher.

Metewand is as follows.More than 3 is usage range.

5: haze value is less than 0.5%.

4: haze value is more than 0.5%, less than 0.7%.

3: haze value is more than 0.7%, less than 1.0%.

2: haze value is more than 1.0%, less than 2.0%.

1: haze value is more than 2.0%.

< storage stability evaluates >

The keeping at 30 DEG C of obtained photosensitive polymer combination, after 7 days, is carried out the evaluation of developability and the evaluation of mist degree.Benchmark is the evaluation according to above-mentioned developability and mist degree.More than 3 is usage range.

5: at 30 DEG C, the developability of keeping after 7 days, haze value are 5.

4: at 30 DEG C, take care of the average out to more than 4 of the developability after 7 days and haze value, less than 5.

3: at 30 DEG C, take care of the average out to more than 3 of the developability after 7 days and haze value, less than 4.

2: at 30 DEG C, take care of the average out to more than 2 of the developability after 7 days and haze value, less than 3.

1: keeping developability and haze value average less than 2 after 7 days at 30 DEG C.

< comprehensive evaluation >

5: each evaluation is 5.

4: each evaluation is all more than 2 and each average out to more than 4 evaluated.

3: each evaluation all more than 2 and each evaluate average out to more than 3, less than 4.

2: each evaluation all more than 2 and each evaluate average out to more than 2, less than 3.

1: that respectively evaluates is average less than 2.

But, even if when 1 project has below 2 in each evaluation, also adopt and divide from comprehensive evaluation the value deducting 1 point of gained.More than 3 is usage range.

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

Ejection

Drying property

Developability

Storage stability

Mist degree

Comprehensively

Embodiment 28	5	5	5	5	5	5
							Embodiment 29	5	5	5	5	4	4
Embodiment 30	5	5	5	5	5	5
							Embodiment 31	5	5	5	5	5	5
Embodiment 32	5	5	5	5	4	4
							Embodiment 33	5	5	5	5	5	5
Embodiment 34	5	5	5	5	5	5
							Embodiment 35	5	5	5	5	4	4
Embodiment 36	5	5	5	5	5	5
							Embodiment 37	5	5	5	5	5	5
Embodiment 38	5	5	5	5	4	4
							Embodiment 39	5	5	5	5	5	5
Embodiment 40	5	5	5	5	5	5
							Embodiment 41	5	5	5	5	4	4
Embodiment 42	5	5	5	5	5	5
							Embodiment 43	5	5	5	5	5	5
Embodiment 44	5	5	5	5	4	4
							Embodiment 45	5	5	5	5	5	5
Embodiment 46	5	5	5	5	5	5
							Embodiment 47	5	5	5	5	4	4
Embodiment 48	5	5	5	5	5	5
							Embodiment 49	5	5	5	5	5	5
Embodiment 50	5	5	5	5	5	5
							Embodiment 51	5	5	5	5	4	4
Embodiment 52	5	5	5	5	4	4
							Embodiment 53	5	5	5	5	5	5
Embodiment 54	5	5	5	5	5	5
							Embodiment 55	5	5	5	5	5	5
Embodiment 56	5	5	5	5	5	5
							Embodiment 57	5	5	5	5	5	5
Embodiment 58	5	5	5	5	4	4
							Embodiment 59	5	5	5	5	4	4
Embodiment 60	5	5	5	5	4	4

[table 8]

	Ejection	Drying property	Developability	Storage stability	Mist degree	Comprehensively
							Embodiment 61	5	5	5	5	5	5

Embodiment 62	5	5	5	5	5	5
							Embodiment 63	5	5	5	5	5	5
Embodiment 64	5	5	5	5	5	5
							Embodiment 65	5	5	5	5	5	5
Embodiment 66	5	5	5	5	5	5
							Embodiment 67	5	5	5	5	5	5
Embodiment 68	5	5	5	5	5	5
							Embodiment 69	5	5	5	5	5	5
Embodiment 70	5	5	5	5	4	4
							Embodiment 71	5	5	5	5	4	4
Embodiment 72	5	5	5	5	4	4
							Embodiment 73	5	5	5	5	4	4
Embodiment 74	5	5	5	5	4	4
							Embodiment 75	5	5	5	5	4	4
Embodiment 76	5	5	5	5	5	5
							Embodiment 77	5	5	5	5	5	5
Embodiment 78	5	5	5	5	5	5
							Embodiment 79	5	5	5	5	5	5
Embodiment 80	5	5	5	5	5	5
							Embodiment 81	5	5	5	5	5	5
Embodiment 82	5	5	5	5	5	5
							Embodiment 83	5	5	5	5	5	5
Embodiment 84	5	5	5	5	5	5
							Embodiment 85	5	5	5	5	5	5
Embodiment 86	5	5	5	5	4	4
							Embodiment 87	5	5	5	5	4	4
Embodiment 88	5	5	5	5	4	4
							Embodiment 89	5	5	5	5	4	4
Embodiment 90	5	5	5	5	5	5
							Embodiment 91	5	5	5	5	5	5
Embodiment 92	5	5	5	5	5	5
							Embodiment 93	5	5	5	5	5	5

[table 9]

	Ejection	Drying property	Developability	Storage stability	Mist degree	Comprehensively
							Embodiment 94	5	5	5	5	5	5
Embodiment 95	5	5	5	5	5	5

Embodiment 96	5	5	5	5	5	5
							Embodiment 97	5	5	5	5	4	4
Embodiment 98	5	5	5	5	5	5
							Embodiment 99	5	5	5	5	4	4
Embodiment 100	5	5	5	5	5	5
							Embodiment 101	5	5	5	5	5	5
Embodiment 102	5	5	5	5	5	5
							Embodiment 103	5	5	5	5	4	4
Embodiment 104	5	5	5	5	5	5
							Embodiment 105	5	5	5	5	4	4
Embodiment 106	5	5	5	5	5	5
							Embodiment 107	5	5	5	5	4	4
Embodiment 108	5	5	5	5	5	5
							Embodiment 109	5	5	5	5	5	5
Embodiment 110	5	5	5	5	5	5

As clear and definite in the result according to above-mentioned table 3 and table 7 ~ table 9, ejection, drying property, the transparency, developability, the excellent storage stability of ink-jet application photosensitive polymer combination of the present invention, and excellent combination property.In contrast, known in the photosensitive polymer combination of comparative example, performance balance is not good enough.

(embodiment 111)

In active array type LCD described in Fig. 1 of Jap.P. No. 3321003 publication, form cured film 17 as follows as interlayer dielectric, and obtain the liquid crystal indicator of embodiment 111.That is, the photosensitive polymer combination of embodiment 1 is spun on substrate, after carrying out prebake conditions (90 DEG C/120 seconds) on hot plate, uses high-pressure mercury-vapor lamp to irradiate 45mJ/cm on mask ²(illumination is 20mW/cm ²) i ray (365nm), then utilize alkaline aqueous solution to carry out developing and forming pattern, and carry out the heating of 30 minutes at 230 DEG C, and form cured film 17 as interlayer dielectric.

Apply the result of driving voltage to obtained liquid crystal indicator, known its be show good display characteristic and the high liquid crystal indicator of reliability.

(embodiment 112)

Utilize following method to make the organic EL display (with reference to Fig. 2) using thin film transistor (TFT) (TFT).

Glass substrate 6 is formed the TFT1 of bottom gate polar form, and under the state covering described TFT1, forms the dielectric film 3 comprising Si3N4.Then, described dielectric film 3 is formed after explanations are omitted hering illustrated contact hole, form via described contact hole the distribution 2 (being highly 1.0 μm) being connected to TFT1 on the insulating film 3.Described distribution 2 is the lines in order to will be connected with TFT1 between TFT1 or by the organic EL formed in step thereafter.

And then, in order to make to form produced concavo-convex planarization by distribution 2, imbedding under the concavo-convex state produced by distribution 2, on dielectric film 3, form planarization film 4.Formation towards the planarization film 4 on dielectric film 3 coats on substrate by the photosensitive polymer combination of embodiment 2, after carrying out prebake conditions (90 DEG C/120 seconds) on hot plate, uses high-pressure mercury-vapor lamp to irradiate 45mJ/cm on mask ²(illumination is 20mW/cm ²) i ray (365nm), then utilize alkaline aqueous solution to carry out developing and forming pattern, and carry out the heating of 30 minutes at 230 DEG C.

Coating during photosensitive resin coating composition is good, in the cured film obtained, does not find the generation of gauffer or slight crack after exposure, development, calcining.And then the average jump of distribution 2 is 500nm, the thickness of made planarization film 4 is 2,000nm.

Then, obtained planarization film 4 is formed the organic EL of bottom emission type.First, the first electrode 5 comprising ITO is made to be connected to distribution 2 via contact hole 7 and to be formed on planarization film 4.Thereafter, painting erosion resistant agent, and carry out prebake conditions, the mask across desired pattern exposes, and then develops.Using described Resist patterns as mask, carry out pattern processing by using the Wet-type etching of ITO etchant.Thereafter, at 50 DEG C, use anticorrosive additive stripping liquid controlling (remover (Remover) 100, peace intelligence electronic material (AZ Electronic Materials) company manufactures) to be peeled off by above-mentioned Resist patterns.The first electrode 5 obtained in the above described manner is equivalent to the anode of organic EL.

Then, the dielectric film 8 of the shape of the periphery of covering first electrode 5 is formed.The photosensitive polymer combination of embodiment 2 is used for dielectric film 8, forms dielectric film 8 in the same way as described above.By arranging described dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and step thereafter can be prevented.

And then, in vacuum deposition apparatus, carry out evaporation successively to arrange hole transmission layer, organic luminous layer, electron transfer layer across desired pattern mask.Then, whole of surface forms the second electrode comprising Al.In evaporator, taking out obtained aforesaid substrate, being undertaken fitting sealing by using ultraviolet ray hardening type epoxy resin and glass for sealing plate.

As above, obtain the organic EL display connecting the active array type in order to the TFT1 driven it on each organic EL.Execute alive result via driving circuit, known its is manifest good display characteristic and the high organic EL display of reliability.

(embodiment 113)

Utilize the method for the following stated, and use the photosensitive polymer combination of high index of refraction of the present invention to make touch panel display device.

The formation > of < first transparent electrode pattern

[formation of transparent electrode layer]

The front panel of the intensive treatment glass (300mm × 400mm × 0.7mm) being formed with mask layer is in advance directed in vacuum chamber, uses SnO ₂containing ratio is the ITO target (indium: tin=95: 5 (mol ratios)) of 10 quality %, by direct current (DirectCurrent, DC) magnetic control sputtering plating (condition: the temperature of base material is 250 DEG C, argon pressure is 0.13Pa, oxygen pressure is 0.01Pa) form the ito thin film that thickness is 40nm, and obtain the front panel being formed with transparent electrode layer.The surface resistance of ito thin film is 80 Ω/.

Then, commercially available etching resist to be coated on ITO and to carry out drying, and forming etching resist layer.Exposed mask (having the quartzy exposed mask of the transparent electrode pattern) distance between face and described etching resist layer is set as 100 μm, with 50mJ/cm ²exposure (i ray) carry out pattern exposure after, utilize special developer solution to develop, and then at 130 DEG C, carry out the rear baking process of 30 minutes, and obtain the front panel being formed with transparent electrode layer and etching light photoresist layer pattern.

The front panel being formed with transparent electrode layer and etching light photoresist layer pattern is made to impregnated in add and have ITO etchant (hydrochloric acid, potassium chloride solution; Liquid temperature is 30 DEG C) etching bath in, carry out process in 100 seconds, the transparent electrode layer in region exposed not covered by etching resist layer dissolves to be removed, and obtains the front panel with the transparency electrode layer pattern with etching resist layer pattern.

Then, make the front panel with the transparency electrode layer pattern with etching resist layer pattern impregnated in special anticorrosive additive stripping liquid controlling, etching light photo-sensitive resin is removed, and obtains the front panel being formed with mask layer and the first transparent electrode pattern.

[formation of insulation course]

The photosensitive polymer combination of embodiment 1 to be coated on the front panel being formed with mask layer and the first transparent electrode pattern and to carry out drying (thickness is 1 μm, 90 DEG C, 120 seconds), and obtaining photosensitive polymer combination layer.Exposed mask (having the quartzy exposed mask of the insulation course pattern) distance between face and described photosensitive polymer combination layer is set as 30 μm, with 50mJ/cm ²exposure (i ray) carry out pattern exposure.

Then, at 23 DEG C, utilize the tetramethyl ammonium hydroxide aqueous solution of 2.38 quality % and utilize leaching to cover liquid method and carry out development in 15 seconds, and then utilize ultrapure water to carry out drip washing in 10 seconds.Then, at 220 DEG C, carry out the rear baking process of 45 minutes, and obtain the front panel being formed with mask layer, the first transparent electrode pattern, insulating layer pattern.

The formation > of < second transparent electrode pattern

[formation of transparent electrode layer]

DC magnetic control sputtering plating process (condition: the temperature of base material is 50 DEG C is carried out to the front panel till being formed to insulating layer pattern in the mode identical with the formation of above-mentioned first transparent electrode pattern, argon pressure is 0.13Pa, oxygen pressure is 0.01Pa), forming thickness is the ito thin film of 80nm, and obtains the front panel being formed with transparent electrode layer.The surface resistance of ito thin film is 110 Ω/.

In the mode identical with the formation of the first transparent electrode pattern, the front panel of the insulating layer pattern using commercially available etching resist acquisition to be formed with the first transparent electrode pattern, to utilize the photosensitive polymer combination of embodiment 82 to be formed, transparent electrode layer, etching Resist patterns (toasts process afterwards; 130 DEG C, 30 minutes).

And then, etch in the mode identical with the formation of the first transparent electrode pattern, and remove etching resist layer, obtain the front panel being formed with mask layer, the first transparent electrode pattern, the insulating layer pattern using the photosensitive polymer combination of embodiment 82 to be formed, the second transparent electrode pattern thus.

The formation > of the electric conductivity key element that < is different from the first transparent electrode pattern and the second transparent electrode pattern

In the mode identical with the formation of above-mentioned first transparent electrode pattern and the second transparent electrode pattern, the process of DC magnetic control sputtering plating is carried out to the front panel of the insulating layer pattern being formed with the first transparent electrode pattern, utilize the photosensitive polymer combination of embodiment 82 to be formed, the second transparent electrode pattern, and obtains the front panel being formed with aluminium (Al) film that thickness is 200nm.

In the mode identical with the formation of above-mentioned first transparent electrode pattern and the second transparent electrode pattern, the front panel of the insulating layer pattern using commercially available etching resist acquisition to be formed with the first transparent electrode pattern, to utilize the photosensitive polymer combination of embodiment 82 to be formed, the second transparent electrode pattern, etching Resist patterns (toasts process afterwards; 130 DEG C, 30 minutes).

And then, carry out etching (30 DEG C, 50 seconds) in the mode identical with the formation of the first transparent electrode pattern, and resist layer removal (45 DEG C, 200 seconds) will be etched, obtain the front panel being formed with mask layer, the first transparent electrode pattern, the insulating layer pattern utilizing the photosensitive polymer combination of embodiment 82 to be formed, the second transparent electrode pattern, the electric conductivity key element different from the first transparent electrode pattern and the second transparent electrode pattern thus.

The formation > of < protective clear layer

Be formed in the mode identical from the formation of insulation course with above-mentioned first transparent electrode pattern and the different electric conductivity key element of the second transparent electrode pattern till front panel on, the photosensitive polymer combination of coating Examples 60 also carries out drying (thickness is 1 μm, 90 DEG C, 120 seconds), and obtain photosensitive polymer combination film.And then, not across exposed mask with 50mJ/cm ²exposure (i ray) carry out preceding exposure, then carry out developing, post-exposure (1,000mJ/cm ²), rear baking process; and obtaining the front panel of the stacked insulation course (protective clear layer) utilizing the photosensitive polymer combination of embodiment 60 to be formed as follows, described mode is mode mask layer, the first transparent electrode pattern, the insulating layer pattern utilizing the photosensitive polymer combination of embodiment 82 to be formed, the second transparent electrode pattern, the electric conductivity key element different from the first transparent electrode pattern and the second transparent electrode pattern all covered.

The making > of < image display device (touch-screen)

The front panel that liquid crystal display cells manufactured by the method recorded in by Japanese Patent Laid-Open 2009-47936 publication manufactures before laminating, utilizes known method to make and possesses the image display device of capacitive input device as inscape.

The evaluation > of < front panel and image display device

First transparent electrode pattern, the second transparent electrode pattern and the electric conductivity key element electric conductivity separately different from both do not have problems, on the other hand, between first transparent electrode pattern and the second transparent electrode pattern, there is insulativity, as touch-screen, obtain good display characteristic.And then, the first transparent electrode pattern and the second transparent electrode pattern not easily in sight, obtain the image display device of display characteristic excellence.

[explanation of symbol]

1:TFT (thin film transistor (TFT))

2: distribution

3: dielectric film

4: planarization film

5: the first electrodes

6: glass substrate

7: contact hole

8: dielectric film

10: liquid crystal indicator

12: back light unit

14,15: glass substrate

16：TFT

17: cured film

18: contact hole

19:ITO transparency electrode

20: liquid crystal

22: colored filter

30: capacitive input device

31: front panel

32: mask layer

33: the first transparent electrode patterns

33a: pad part

33b: coupling part

34: the second transparent electrode patterns

35: insulation course

36: electric conductivity key element

37: protective clear layer

38: peristome

Claims

1. an ink-jet application photosensitive polymer combination, is characterized in that: comprise

(composition A) inorganic particulate,

(composition B) solvent,

(composition C) containing have the base that acidic group is protected by sour decomposability base Component units polymkeric substance and

(components D) light acid producing agent, and

It is more than 177 DEG C, less than 227 DEG C that described composition B contains boiling point, and inorganic value/organic value is the non-alcohol series solvent of more than 0.50, less than 1.00.

2. ink-jet application photosensitive polymer combination according to claim 1, wherein said non-alcohol series solvent is for being selected from least one solvent in the group that is made up of acidylate alkylene glycol monoalkyl ethers, acidylate two alkylene glycol monoalkyl ethers, two alkylene glycol dialkylether and three alkylene glycol dialkylether.

3. ink-jet application photosensitive polymer combination according to claim 1 and 2, wherein said composition A is metal oxide particle.

4. ink-jet application photosensitive polymer combination according to any one of claim 1 to 3, wherein said composition A is Titanium particles or Zirconia particles.

5. ink-jet application photosensitive polymer combination according to any one of claim 1 to 4, it also comprises (composition E) spreading agent.

6. ink-jet application photosensitive polymer combination according to any one of claim 1 to 5, it also comprises (composition F) thermal cross-linking agent.

7. a manufacture method for thermal treatment thing, is characterized in that: at least comprise step (a) ~ step (c),

A () application step, utilizes ink-jet application mode to coat on substrate by ink-jet application photosensitive polymer combination according to any one of claim 1 to 6;

B () solvent removal step, removes solvent in the resin combination be coated with; And

C () heat treatment step, heat-treats the resin combination eliminating solvent.

8. a resin pattern manufacture method, is characterized in that: at least comprise step (1) ~ step (5),

(1) application step, utilizes ink-jet application mode to coat on substrate by ink-jet application photosensitive polymer combination according to any one of claim 1 to 6;

(2) solvent removal step, removes solvent in the resin combination be coated with;

(3) step of exposure, utilizes actinic ray that the resin combination eliminating solvent is exposed into pattern-like;

(4) development step, utilizes aqueous developer solution to develop to the resin combination through exposure; And

(5) heat treatment step, heat-treats the resin combination through development.

9. a thermal treatment thing, it obtained by the manufacture method of thermal treatment thing according to claim 7.

10. a thermal treatment thing, it is heat-treated ink-jet application photosensitive polymer combination according to any one of claim 1 to 6 and is formed.

11. thermal treatment things according to claim 10, it is interlayer dielectric.

12. 1 kinds of liquid crystal indicators, it comprises the thermal treatment thing according to claim 10 or 11.

13. 1 kinds of organic electroluminescence display device and method of manufacturing same, it comprises the thermal treatment thing according to claim 10 or 11.

The manufacture method of 14. 1 kinds of touch-screens, it is the manufacture method of the touch-screen with transparency carrier, indium-tin oxide electrode and insulation course, comprises the steps:

In the mode contacted with described indium-tin oxide electrode, ink-jet application mode is utilized to be coated with the step of ink-jet application photosensitive polymer combination according to any one of claim 1 to 6;

Described resin combination loads the mask with the patterns of openings of regulation shape and carries out active energy ray and irradiate the step of carrying out exposing;

To the step that the resin combination after exposure develops; And

The step manufacturing insulation course is heated to the resin combination after development.

15. 1 kinds of touch-screens, all or part of of its insulation course comprises the thermal treatment thing of ink-jet application photosensitive polymer combination according to any one of claim 1 to 6.

16. 1 kinds of touch panel display devices, it comprises thermal treatment thing according to claim 10 or 11 or touch-screen according to claim 15.