CN103874961A - Positive photosensitive resin composition, method for producing cured product, method for producing resin pattern, cured product, and optical member - Google Patents

Abstract

The purpose of the present invention is to provide a positive photosensitive resin composition with which dissolution of unexposed portions during development can be prevented. The positive photosensitive resin composition of the present invention is characterized in comprising (component A) inorganic particles, (component B) a dispersant having acid groups, (component C) a solvent, (component D) a polymer comprising (a-1) structural units having groups that are eliminated in the presence of acid and/or heat and (a-2) structural units having crosslinkable groups, and (component E) a photoacid generator, wherein the acid value of component D is 50 mg KOH/g or less.

Description

Manufacture method, resin pattern manufacture method, hardening thing and the optical component of positive type photosensitive organic compound, hardening thing

Technical field

The present invention relates to manufacture method, resin pattern manufacture method, hardening thing and the optical component of a kind of positive type photosensitive organic compound, hardening thing.

Background technology

Due to the prosperity of solid-state imager or liquid crystal indicator, extensively utilize gradually organic material (resin) to make the optical components such as lenticule, optical waveguide, anti-reflective film.

For these optical components, studying particles such as adding titanium dioxide to realize high index of refraction (with reference to following patent documentation 1).

In addition, as existing negative light-sensitive resin combination, the known photosensitive polymer combination that has record in patent documentation 2～patent documentation 4.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2006-98985 communique

Patent documentation 2: Japanese Patent Laid-Open 2011-127096 communique

Patent documentation 3: Japanese Patent Laid-Open 2009-179678 communique

Patent documentation 4: Japanese Patent Laid-Open 2008-185683 communique

Summary of the invention

The problem that invention will solve

The object of the present invention is to provide a kind of positive type photosensitive organic compound of dissolving of the unexposed portion while suppressing to develop.

The technological means of dealing with problems

Above-mentioned problem of the present invention is that the method for recording by following <1> or <8>～<11> solves.Below, record in the lump the <2>～<7> as preferred implementation.

<1> positive type photosensitive organic compound, it is characterized in that containing: spreading agent, (composition C) solvent, (components D) that (composition A) inorganic particulate, (composition B) have acidic group contain polymkeric substance and (composition E) light acid producing agent that (a-1) has the structural unit of the base departing from by acid and/or heat and (a-2) have the structural unit of bridging property base, and the acid number of components D is below 50mg KOH/g;

<2> is as the positive type photosensitive organic compound that above-mentioned <1> recorded, and wherein composition A is metal oxide particle;

<3> is as the positive type photosensitive organic compound that above-mentioned <2> recorded, and wherein composition A is Titanium particles;

<4> is as positive type photosensitive organic compound that in above-mentioned <1> to <3>, any one is recorded, wherein composition B is the graft copolymer with carboxylic acid group, and acid number is more than 100mg KOH/g and below 190mg KOH/g;

<5> is as the positive type photosensitive organic compound that in above-mentioned <1> to <4>, any one is recorded, and it also contains (composition F) thermal cross-linking agent;

<6> is as positive type photosensitive organic compound that in above-mentioned <1> to <5>, any one is recorded, wherein the weight average molecular weight of composition B is 25, more than 000 and below 50,000;

<7> is as the positive type photosensitive organic compound that in above-mentioned <1> to <6>, any one is recorded, and it is optical component resin combination;

The manufacture method of a <8> hardening thing, it at least sequentially comprises step (a)～step (c):

(a) application step, will coat on substrate as the positive type photosensitive organic compound that in above-mentioned <1> to <7>, any one is recorded;

(b) solvent removal step is removed solvent in the resin combination being coated with;

(c) heat treatment step, heat-treats the resin combination of having removed solvent;

<9> resin pattern manufacture method, it at least sequentially comprises step (1)～step (5):

(1) application step, will coat on substrate as the positive type photosensitive organic compound that in above-mentioned <1> to <7>, any one is recorded;

(2) solvent removal step is removed solvent in the resin combination being coated with;

(3) step of exposure, exposes into the resin combination of having removed solvent to pattern-like by active ray;

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

(5) heat treatment step, to heat-treating through the resin combination developing;

<10> hardening thing, it is to obtain by the manufacture method of the hardening thing as above-mentioned <8> recorded or as the resin pattern manufacture method that above-mentioned <9> recorded;

<11> optical component, it is to obtain by the manufacture method of the hardening thing as above-mentioned <8> recorded or as the resin pattern manufacture method that above-mentioned <9> recorded.

The effect of invention

According to the present invention, can provide a kind of positive type photosensitive organic compound of dissolving of the unexposed portion while suppressing to develop.

Embodiment

Below, resin combination of the present invention is described in detail.

Moreover, in the present invention, representing that the record of " lower limit～upper limit " of numerical range represents " more than lower limit, below the upper limit ", the record of " upper limit～lower limit " represents " below the upper limit, more than lower limit ".The numerical range that, expression comprises the upper limit and lower limit.

In addition, in the present invention, " (composition A) inorganic particulate " etc., also referred to as " composition A " etc., will " (a-1) be had to the structural unit of the base departing from by acid and/or heat " etc. also referred to as " structural unit (a-1) " etc.

And then, in the statement of the base (atomic group) in this instructions, do not record the statement that is substituted and is unsubstituted not only comprise do not have substituent, and also comprise have substituent.For example so-called " alkyl ", not only comprises and does not have substituent alkyl in (alkyl being unsubstituted), also comprises and has substituent alkyl in (alkyl being substituted).

In addition, in the present invention, " quality % " and " quality % " are identical meanings, and " mass parts " is identical meanings with " mass parts ".

(positive type photosensitive organic compound)

Below, the each composition that forms positive type photosensitive organic compound is illustrated.

Positive type photosensitive organic compound of the present invention (below also referred to as " photosensitive polymer combination " or " resin combination ") is characterised in that: contain spreading agent, (composition C) solvent, (components D) that (composition A) inorganic particulate, (composition B) have acidic group and contain polymkeric substance and (composition E) light acid producing agent that (a-1) has the structural unit of the base departing from by acid and/or heat and (a-2) have the structural unit of bridging property base, and the acid number of components D is below 50mg KOH/g.

Positive type photosensitive organic compound of the present invention can preferably be used as eurymeric anti-corrosion agent composition.

Positive type photosensitive organic compound of the present invention preferably has the resin combination of the character of hardening by heat.

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

Positive type photosensitive organic compound of the present invention does not preferably contain the light acid producing agent of 1,2-quinone di-azido compound as induction active ray.1, although 2-quinone di-azido compound generates carboxyl by type (sequential type) photochemical reaction successively, its quantum yield must be below 1.

With respect to this; (composition E) the light acid producing agent using in the present invention is responded to active ray and is generated acid; this acid is the effect as catalyzer to the deprotection performance of the acidic groups through protection; therefore the acid generating by the effect of 1 light quantum contributes to repeatedly deprotection reaction; quantum yield exceedes 1; for example become the large value as 10 several side, can obtain high sensitivity as the result of so-called chemical amplification.

And then, positive type photosensitive organic compound of the present invention is lenticule, optical waveguide, anti-reflective film, light emitting diode (Light Emitting Diode preferably, LED) with the visibility reduction resin combination that seals the distribution electrode using in the optical components such as material and LED chip Tu Cai or touch-screen, more preferably lenticule resin combination.Moreover, the visibility reduction composition of the distribution electrode using in so-called touch-screen, refer to reduce the distribution electrode using in touch-screen visibility, be difficult for seeing the member composition of distribution electrode, for example can enumerate tin indium oxide (Indium Tin Oxide, ITO) interelectrode interlayer dielectric etc., positive type photosensitive organic compound of the present invention can be preferably used in this purposes.

Conventionally,, if eurymeric resist, through exposure,, because causing the disengaging base that contained polymkeric substance has to depart from the effect of light acid producing agent, is dissolved in developer solution, unexposed portion is formed as pattern.

The people such as the inventor find, the resin combination that contains inorganic particulate, spreading agent and have a polymkeric substance that departs from base and crosslinking group in use is during as the situation of eurymeric resist, there is following problem: due to the effect of inorganic particulate and spreading agent, dissolubility in developer solution uprises, and unexposed portion also shows dissolubility in developer solution.

The people such as the inventor study in detail, found that, by the positive type photosensitive organic compound that is set as containing composition A～composition E, unexposed portion improves the patience of developer solution, can optimize pattern formative (dissolving of the unexposed portion while suppressing to develop).

(composition A) inorganic particulate

Resin combination of the present invention contains inorganic particulate in order to regulate refractive index or transmitance.

Composition A preferably refractive index higher than comprising the refractive index of the resin combination of the material except this particle, particularly, the refractive index more preferably with the light of the wavelength of 400nm～750nm is more than 1.50 particle, and then preferably refractive index is more than 1.70 particle, particularly preferably is more than 1.90 particles.

Herein, the refractive index that what is called has the light of the wavelength of 400nm～750nm is more than 1.50, and the mean refractive index that refers to the light of the wavelength with above-mentioned scope is more than 1.50, is more than 1.50 without the refractive index of all light that make the wavelength with above-mentioned scope.In addition, mean refractive index is the value divided by the number gained of measuring point by the summation of the measured value of the refractive index of the each light to the wavelength with above-mentioned scope.

As the inorganic particulate with this kind of high index of refraction, high and there is for the aspect of transmitance preferably inorganic oxide particle, more preferably metal oxide particle with regard to the transparency.

Preferably contain 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, Bi, the equiatomic oxide particle of Te as transmitance and the high inorganic oxide particle of refractive index, more preferably titanium dioxide, zinc paste, zirconia, indium/tin-oxide or antimony/tin-oxide, and then titanium dioxide preferably, particularly preferably be titania.Titania particularly preferably is the rutile-type that refractive index is high.These inorganic particulates also can utilize organic material effects on surface to process to give dispersion stabilization.

With regard to the transparent viewpoint of resin combination, preferably 1nm～300nm of the average primary particle diameter of composition A, particularly preferably is 3nm～80nm.Herein, the average primary particle diameter of particle refers to by the arithmetic mean of the particle diameter gained of any 200 particles of determination of electron microscopy.In addition, in the time of the shape of particle aspheric situation, taking longest edge as diameter.

The content of the inorganic particulate in resin combination of the present invention is as long as consider that the desired refractive index of optical component or the transmitance etc. that obtain by resin combination suitably determine, with respect to the total solid composition of resin combination of the present invention, preferably be set as 5 quality %～80 quality %, be more preferably set as 10 quality %～70 quality %.

(composition B) has the spreading agent of acidic group

Resin combination of the present invention contains the spreading agent with acidic group.

In the present invention, the spendable spreading agent with acidic group can be enumerated: have the macromolecule dispersing agent (for example having the polyamide-amide of acidic group and salt, poly carboxylic acid and salt thereof, high molecular unsaturated acid ester, modified polyamine carbamate, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic acid series copolymer, naphthalene sulfonic acids Formalin condensation product) of acidic group and polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.

Macromolecule dispersing agent can further be categorized as straight chain shape macromolecule, terminal-modified type macromolecule, graft type macromolecule, block type polymer according to its structure.In addition, macromolecule dispersing agent preferably weight average molecular weight be more than 1,000.

In these, the spendable preferably macromolecule dispersing agent of spreading agent with acidic group in the present invention, more preferably graft type macromolecule dispersing agent.

The one that can be used alone of the spreading agent with acidic group, also use capable of being combined is two or more.

Composition B is the spreading agent with acidic group.Can infer, composition B plays a role as absorption base to inorganic particulate by having acidic group, the excellent dispersion of inorganic particulate.

Acidic group can be enumerated carboxylic acid group's (carboxyl), sulfonic group, phosphate, phenol hydroxyl etc., with regard to the viewpoint of the absorption affinity to inorganic particulate and dispersiveness, preferably select at least one in the group that free carboxylic acid group, sulfonic group and phosphate form, particularly preferably be carboxylic acid group.A kind of or the combination that acidic group in above-mentioned spreading agent can have separately these has two or more.

In addition, in the present invention, the spendable spreading agent with acidic group preferably has the graft copolymer of acidic group, more preferably has carboxylic acid group's graft copolymer.

And then the spendable spreading agent with acidic group preferably contains the graft copolymer of any represented structural unit of formula (1)～formula (4) in the present invention.

[changing 1]

(in formula (1)～formula (4), X ¹, X ², X ³, X ⁴and X ⁵independent hydrogen atom or any monovalent organic radical, the W of representing respectively ¹, W ², W ³and W ⁴independent oxygen atom or the NH of representing respectively, R is independent hydrogen atom or any monovalent organic radical of representing respectively, independent branch or straight-chain alkyl-sub-, the Y of representing of R ' difference ¹, Y ², Y ³and Y ⁴independent bivalence linking base, the Z of representing respectively ¹, Z ², Z ³and Z ⁴independent hydrogen atom or any monovalent organic radical of representing respectively, n, m, p and q are independently respectively 1～500 integer, j and k are independently respectively 2～8 integer)

In formula (1)～formula (4), X ¹, X ², X ³, X ⁴and X ⁵respectively independent hydrogen atom or any monovalent organic radical of representing, with regard to the viewpoint of the restriction of synthetic aspect, the preferably alkyl of hydrogen atom or carbon number 1～12, more preferably hydrogen atom or methyl, particularly preferably be methyl.

In formula (1)～formula (4), W ¹, W ², W ³and W ⁴independent oxygen atom or the NH of representing, particularly preferably is oxygen atom respectively.

In formula (3), R ' difference is independent represents the alkylidene (carbon number preferably 1～10, more preferably 2 or 3) of branch or straight chain, with regard to the viewpoint of dispersion stabilization, and preferably-CH ₂-CH (CH ₃the base of)-represented or-CH (CH ₃)-CH ₂-represented base.

In addition, about the R ' in formula (3), also can in a kind of composition B, mix the R ' that uses two or more different structures.

In formula (1)～formula (4), Y ¹, Y ², Y ³and Y ⁴independent is respectively bivalence linking base, and in structure aspects, there is no particular restriction.Specifically can enumerate following (Y-1)～concatenating group (Y-21) etc.In following structure, A refer to formula (1)～formula (4) in Y ¹, Y ², Y ³or Y ⁴the bond of left-end point base, B refer to formula (1)～formula (4) in and Y ¹, Y ², Y ³or Y ⁴the bond of right terminal groups.In structure shown in following, with regard to synthetic simplicity, more preferably (Y-2), (Y-13).

[changing 2]

In formula (1)～formula (4), Z ¹, Z ², Z ³and Z ⁴independent is respectively hydrogen atom or monovalence substituting group, and substituent structure is not particularly limited, and specifically can enumerate: alkyl, hydroxyl, alkoxy, aryloxy group, heteroaryloxy, alkylthio group ether, fragrant thioether group, assorted fragrant thioether group, amino etc.In these, especially with regard to improving dispersed viewpoint, Z ¹and Z ²the respectively preferably alkyl of carbon number 5～24, more preferably branch's alkyl of carbon number 5～24 or the cyclic alkyl of carbon number 5～24 independently.Z ³preferably hydroxyl, alkoxy or aryloxy group, more preferably hydroxyl.In addition, Z ⁴preferably hydrogen atom, hydroxyl or alkoxy, more preferably hydrogen atom.

In formula (1)～formula (4), n, m, p and q are independently respectively 1～500 integer, preferably 3～500 integer, more preferably 5～50 integer, and then 8～30 integer preferably.

In formula (1) and formula (2), j and k be independent 2～8 the integer that represents respectively, with regard to the viewpoint of dispersion stabilization, and preferably 4～6 integer, most preferably 5.

In formula (4), R represents hydrogen atom or any monovalent organic radical, is not particularly limited preferably hydrogen atom, alkyl, aryl, heteroaryl, more preferably hydrogen atom, alkyl in structure aspects.When the situation that is alkyl at above-mentioned R, abovementioned alkyl is straight chain-like alkyl, the branch-like alkyl of carbon number 3～20 or the cyclic alkyl of carbon number 5～20 of carbon number 1～20 preferably, the more preferably straight chain-like alkyl of carbon number 1～20, particularly preferably is the straight chain-like alkyl of carbon number 1～6.

In addition, about the R in formula (4), also can in a kind of composition B, contain the R that two or more structures is different.

With regard to the viewpoint of dispersion stabilization, the more preferably following formula of structural unit (1A) that above-mentioned formula (1) is represented or the represented structural unit of formula (2A).

[changing 3]

In formula (1A), X ¹, Y ¹, Z ¹and X in n and formula (1) ¹, Y ¹, Z ¹and n is identical meanings, preferable range is also identical.

In formula (2A), X ², Y ², Z ²and X in m and formula (2) ², Y ², Z ²and m is identical meanings, preferable range is also identical.

The content (referring to its total amount in the time of the situation of any the represented structural unit that contains multiple formula (1)～formula (4)) of any represented structural unit of formula (the 1)～formula (4) in composition B is with mass conversion, with respect to the gross mass of composition B, the preferably scope of 10 quality %～90 quality %, the more preferably scope of 30 quality %～70 quality %.If within the scope of this, the excellent dispersion of inorganic particulate, it is good that the developability while making photosensitive polymer combination becomes.

In addition, resin combination of the present invention can contain separately a kind of composition B, also can contain the composition B that two or more structures is different.

In addition, composition B preferably all contains any represented structural unit of formula (1)～formula (3) in any represented structural unit of formula (1)～formula (4), more preferably contain any represented structural unit of formula (1) or formula (2), and then preferably contain the represented structural unit of formula (1).

In addition, composition B more preferably at least contains any represented structural unit of formula (1)～formula (4) and has the graft copolymer of the structural unit of acidic group, and then preferably at least contains any represented structural unit of formula (1)～formula (4) and have the graft copolymer of carboxylic acid group's structural unit.

Wherein, composition B particularly preferably is any the represented structural unit that at least contains formula (1)～formula (4) and the graft copolymer with the structural unit of phthalic monoester structure.

The acid number of composition B is the scope more than 5.0mg KOH/g and below 200mg KOH/g preferably, the more preferably scope more than 100mg KOH/g and below 190mg KOH/g, and then the above and scope below 190mg KOH/g of 120mg KOH/g preferably, particularly preferably be the above and scope below 180mg KOH/g of 140mg KOH/g.If above-mentioned scope, the excellent dispersion of inorganic particulate, and the dissolving of unexposed portion can fully suppress to develop time.

There is no particular restriction for the assay method of the acid number of composition B, can measure by known method, can utilize the method identical with the assay method of the acid number of aftermentioned components D preferably to measure.

In addition, the acid number of composition B for example can calculate according to the average content of the acidic group in composition B.In addition, by making the content of the structural unit that contains acidic group of constituent B, can obtain the composition B with required acid number.

Pattern when suppressing to develop peel off and the viewpoint of developability with regard to, the weight average molecular weight of composition B is preferably more than 10,000 and 300, below 000, more preferably more than 15,000 and below 200,000, and then preferably 20, more than 000 and below 100,000, particularly preferably be 25, more than 000 and below 50,000.Moreover the weight average molecular weight of resin for example can be passed through gel permeation chromatography (Gel Permeation Chromatography, GPC) and measure.

The concrete example of composition B can preferably illustrate B-1 and the B-2 shown in following, can particularly preferably illustrate B-1.Moreover in following formula, x and y represent mass ratio, preferably x: y=40: 60～95: 5, more preferably 70: 30～90: 10.

[changing 4]

With respect to content 100 mass parts of composition A, preferably 50 mass parts～3 of the content of the composition B in resin combination of the present invention, 000 mass parts, more preferably 100 mass parts～2,000 mass parts, and then 150 mass parts～1 preferably, 500 mass parts.

(composition C) solvent

Resin combination of the present invention contains (composition C) solvent.

Resin combination of the present invention is preferably prepared into any composition of composition A and composition B and other various adjuvants described later is dissolved or dispersed in to the solution in (composition C) solvent.

(composition C) solvent using in resin combination of the present invention can use known solvent, 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 monoalky lether acetate esters, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ether, dipropylene glycol monoalky lether acetate esters, ester class, ketone, amide-type, lactone etc.

In above-mentioned solvent, preferably diethylene glycol ethyl methyl ether and/or propylene glycol methyl ether acetate, particularly preferably be propylene glycol methyl ether acetate.

The spendable solvent one that can be used alone in the present invention, also can and with two or more.

With respect to content 100 mass parts of components D, preferably 50 mass parts～3 of content of (composition C) solvent in resin combination of the present invention, 000 mass parts, more preferably 100 mass parts～2,000 mass parts, and then 150 mass parts～1 preferably, 500 mass parts.

(components D) contains the polymkeric substance that (a-1) has the structural unit of the base departing from by acid and/or heat and (a-2) have the structural unit of crosslinking group

Positive type photosensitive organic compound of the present invention contains (components D) and contains the polymkeric substance that (a-1) has the structural unit of the base (also referred to as " disengaging base ") departing from by acid and/or heat and (a-2) have the structural unit of crosslinking group.

In addition, the acid number of components D is below 50mg KOH/g, preferably below 45mg KOH/g, more preferably below 35mg KOH/g, and then preferably below 10mg KOH/g, particularly preferably be below 3mg KOH/g, most preferably below 1mg KOH/g.If above-mentioned scope, the dissolving of the unexposed portion can suppress to develop time.In addition, if the acid number of components D exceedes 50mg KOH/g, while development, cause in a large number the dissolving of unexposed portion, produce the deteriorated of pattern form.

The acid number of the components D in positive type photosensitive organic compound of the present invention be have depart from base structural unit (a-1) exist state under acid number.For example at structural unit (a-1) when having carboxyl through the situation of the structural unit of the base of sour decomposability base protection, before the acid number that departs from the components D after base departs from departs from certainly, rise.

There is no particular restriction for the assay method of acid number, can use known method, preferably measures by the following method.

There is no particular restriction for the assay method of the acid number in the present invention, can in known method, suitably select, for example, can enumerate titrimetry etc., can preferably enumerate the method by measure acid number with the titration of potassium hydroxide.

With regard to the viewpoint of the technique adaptive in the field of solid-state imager or liquid crystal indicator, the preferably polymkeric substance of sulfur atom-containing not of components D.

Components D is preferably except said structure unit (a-1) and structural unit (a-2), also contain the structural unit that (a-3) has alkali-soluble base, more preferably contain the structural unit that (a-3) has the structural unit of alkali-soluble base and (a-4) have aromatic rings.Above-mentioned alkali-soluble base is carboxylic acid group's (carboxyl) preferably.

In addition, components D also can contain above-mentioned monomeric unit (a-1)～monomeric unit (a-4) structural unit (a-5) in addition.

Moreover " structural unit " in the present invention not only comprises the monomeric unit being formed by monomer a part, also comprises the structural unit monomeric unit modification being formed by monomer a part being formed by high molecular weight reactive etc.

The weight average molecular weight (Mw) of components D is preferably more than 3,000, more preferably more than 5,000, and then preferably 10, more than 000, in addition, preferably 1,000, below 000, more preferably below 80,000, and then preferably below 60,000.If above-mentioned scope, can obtain good resolution.

Moreover weight average molecular weight is the value of the polystyrene conversion by gel permeation chromatography (GPC) mensuration.Preferably solvent uses tetrahydrofuran (Tetrahydrofuran, THF), and tubing string uses TSKgel Super HZ3000 and TSKgel Super HZM-M (being eastern Cao (thigh) manufactures) to measure.

Components D is acrylic acid series polymeric compounds preferably.

The resin that " acrylic acid series polymeric compounds " in the present invention is addition polymerization type, derive from the polymkeric substance of the monomeric unit of (methyl) acrylic acid or its ester for containing, also can contain the monomeric unit that derives from beyond the monomeric unit of (methyl) acrylic acid or its ester, for example, derive from the monomeric unit of phenylethylene or derive from the monomeric unit etc. of vinyl compound.In addition, components D also can contain the monomeric unit that derives from (methyl) acrylic acid monomeric unit and derive from (methyl) acrylate in the lump.

Moreover, in this manual, will " derive from the structural unit of (methyl) acrylic acid or its ester " also referred to as " acrylic acid series structural unit ".In addition, (methyl) acrylic acid is methacrylic acid and acrylic acid general name.

Below, each structural units such as structural unit (a-1), structural unit (a-2) are illustrated.

(a-1) have by the structural unit of acid and/or the hot base departing from

Components D at least contains (a-1) to be had by the structural unit of acid and/or the hot base departing from.

The above-mentioned base departing from by acid and/or heat can be the base departing from by acid, also can be the base departing from by heat, also can be by the sour and hot base departing from, preferably at least pass through the sour base departing from, pass through the sour base departing from or pass through the sour and hot base departing from.

The base at least departing from by acid for example can be enumerated the base through sour decomposability base protection.

With regard to the viewpoint of sensitivity and resolution, said structure unit (a-1) be structural unit (a-1-1) preferably, and this structural unit (a-1-1) has carboxyl or the phenol hydroxyl base through sour decomposability base protection.

Contain structural unit (a-1-1) in components D situation time, preferably alkali insoluble and said structure unit (a-1-1) in sour decomposability base become the resin of alkali-soluble while decomposing.

In addition, in the present invention so-called " alkali-soluble ", refer to the solution coat of this compound (resin) is heated 2 minutes on substrate and at 90 DEG C, (thickness 4 μ are m) more than 0.01 μ m/s to the dissolution velocity of 0.4 quality % tetramethyl ammonium hydroxide (the tetramethyl ammonium hydroxide) aqueous solution at 23 DEG C to the film of this compound (resin) forming thus, so-called " alkali is insoluble ", refer to the solution coat of this compound (resin) is heated 2 minutes on substrate and at 90 DEG C, (thickness 4 μ m) are less than 0.01 μ m/s to the dissolution velocity of 0.4 quality % tetramethyl ammonium hydroxide aqueous solution at 23 DEG C to the film of this compound (resin) forming therefrom, preferably be less than 0.005 μ m/s.

[thering is carboxyl or the phenol hydroxyl structural unit (a-1-1) through the base of sour decomposability base protection]

Components D preferably contains structural unit (a-1-1), and this structural unit (a-1-1) has carboxyl or the phenol hydroxyl base through sour decomposability base protection.

Contain structural unit (a-1-1) by components D, can be made into the resin combination of high sensitivity.There is carboxyl and compare through the structural unit of the base of sour decomposability base protection with thering is phenol hydroxyl through the structural unit of the base of sour decomposability base protection, have the feature faster of developing.Therefore,, in the time wanting the situation of rapid development, preferably there is the structural unit of carboxyl through the base of sour decomposability base protection.Otherwise, in the time wanting the situation of developing lentamente, preferably use and there is the structural unit of phenol hydroxyl through the base of sour decomposability base protection.

In addition, above-mentioned sour decomposability base particularly preferably is 1-ethoxyethyl group or tetrahydrofuran base, most preferably tetrahydrofuran base.

[thering is the structural unit (a-1-2) of carboxyl through the base of sour decomposability base protection]

-have the structural unit of carboxyl-

The structural unit with carboxyl for example can be enumerated: derive from the structural unit in unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids equimolecular with unsaturated carboxylic acid of at least 1 carboxyl etc.

Can use the compound as following enumerating in order to obtain the unsaturated carboxylic acid that there is the structural unit of carboxyl and use., unsaturated monocarboxylic for example can be enumerated: acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, cinnamic acid etc.In addition, unsaturated dicarboxylic for example can be enumerated: maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.In addition, also can be its acid anhydrides in order to obtain the unsaturated polybasic carboxylic acid that there is the monomeric unit of carboxyl and use.Specifically can enumerate maleic anhydride, itaconic anhydride, citraconic anhydride etc.In addition, unsaturated polybasic carboxylic acid also can be list (the 2-methacryloxy alkyl) ester of polybasic carboxylic acid, for example, can enumerate: mono succinate (2-acryloxy ethyl) ester, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.

For example, and then unsaturated polybasic carboxylic acid also can be list (methyl) acrylate of its two ends dicarboxyl polymkeric substance, can enumerate: ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates etc.

In addition, unsaturated carboxylic acid also can use acrylic acid-2-carboxylic ethyl ester, methacrylic acid-2-carboxylic ethyl ester, maleic acid mono alkyl ester, fumaric acid mono alkyl ester, 4-carboxyl styrene etc.

Wherein, with regard to the viewpoint of developability, in order to form the structural unit with carboxyl, preferably use the acid anhydrides of acrylic acid, methacrylic acid or unsaturated polybasic carboxylic acid etc., more preferably use acrylic or methacrylic acid.

The structural unit with carboxyl can comprise independent one, also can comprise two or more.

In addition, the structural unit that has a carboxyl also can be and makes to have the monomeric unit of hydroxyl and the structural unit of anhydride reaction gained.

Acid anhydrides can use known, 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.In these, with regard to the viewpoint of developability, preferably phthalic anhydride, tetrabydrophthalic anhydride or succinic anhydride.

With regard to the viewpoint of developability, acid anhydrides is with respect to preferably 10mol% (molar percentage)～100mol%, the more preferably 30mol%～100mol% of reaction rate of above-mentioned hydroxyl.

-have carboxyl through the structural unit (a-1-2) of the base of sour decomposability base protection-

What is called has the structural unit (a-1-2) of carboxyl through the base of sour decomposability base protection, preferably has the structural unit by below the sour decomposability base describing in detail being protected to the base that the carboxyl of the above-mentioned structural unit with carboxyl forms.

Acid decomposability base can use up to now as the sour decomposability base in KrF eurymeric resist, ArF eurymeric resist and known, is not particularly limited.In the past, as sour decomposability base, known to have as acetals such as the THP trtrahydropyranyl of the base relatively easily decomposing by acid be functional group, or be functional group as relative difficult by tributyl ester group, the tributyl carbonate group grade in an imperial examination tributyl of the sour base decomposing, and can use these bases.

In addition, this kind of acetal is that functional group or tributyl are that functional group also can the functional group who depart from occur by heat.

In these sour decomposability bases, with regard to the viewpoint of sensitivity and resolution, preferably there is the structural unit of the base forming with the form protection carboxyl of acetal.And then, in sour decomposability base, the base more preferably forming with the form protection carboxyl of the represented acetal of following formula (a1-1).Moreover, when the situation of the base forming at the form protection carboxyl for the represented acetal of following formula (a1-1), totally become-C of base (=O)-O-CR ¹r ²(OR ³) structure.Moreover, in " acetal " of the present invention, not only comprise the acetal of narrow sense, also comprise ketal.

[changing 5]

(in formula (a1-1), R ¹and R ²independent hydrogen atom or the alkyl of representing respectively.Wherein, by R ¹with R ²be except the situation of hydrogen atom.R ³represent alkyl.R ¹or R ²with R ³also can link and form cyclic ether.In addition, wave-like line part represents and the bond position of other structures)

In formula (a1-1), R ¹and R ²independent hydrogen atom or alkyl, the R of representing respectively ³represent alkyl, abovementioned alkyl can be any of straight chain shape, branch's chain, ring-type.Herein, R ¹and R ²both represent that the situation of hydrogen atom does not exist, R ¹and R ²at least one represent alkyl.

In formula (a1-1), at R ¹, R ²and R ³while representing the situation of alkyl, abovementioned alkyl can be any of straight chain shape, branch's chain or ring-type.

The alkyl of straight chain shape or branch's chain is carbon number 1～12 preferably, more preferably carbon number 1～6, and then carbon number 1～4 preferably.Specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the second butyl, tributyl, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.

Cyclic alkyl is carbon number 3～12 preferably, more preferably carbon number 4～8, and then carbon number 4～6 preferably.Cyclic alkyl for example can be enumerated: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl etc.

Abovementioned alkyl also can have substituting group, and substituting group can illustrate halogen atom, aryl, alkoxy.In the time having halogen atom as substituent situation, R ¹, R ², R ³become haloalkyl, in the time having aryl as substituent situation, R ¹, R ², R ³become aralkyl.

Halogen atom can illustrate fluorine atom, chlorine atom, bromine atoms, iodine atom, in these, and preferably fluorine atom or chlorine atom.

In addition, above-mentioned aryl is the aryl of carbon number 6～20 preferably, more preferably the aryl of carbon number 6～12.Specifically can illustrate phenyl, Alpha-Methyl phenyl, naphthyl etc.

Above-mentioned aralkyl is the aralkyl of carbon number 7～32 preferably, more preferably the aralkyl of carbon number 7～20.Specifically can illustrate benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc.

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

In addition, when the situation that is naphthenic base at alkyl, above-mentioned naphthenic base also can have the straight chain shape of carbon number 1～10 or the alkyl of branch's chain as substituting group, in the time that alkyl is the situation of alkyl of straight chain shape or branch's chain, also can have the naphthenic base of carbon number 3～12 as substituting group.

These substituting groups also can further replace through above-mentioned substituting group.

In formula (a1-1), at R ¹, R ²and R ³while representing the situation of aryl, above-mentioned aryl is carbon number 6～12 preferably, more preferably carbon number 6～10.Above-mentioned aryl also can have substituting group, and above-mentioned substituting group can preferably illustrate the alkyl of carbon number 1～6.Aryl can illustrate phenyl, tolyl, xylyl, cumenyl, 1-naphthyl etc.

In addition, R ¹, R ²and R ³also bond form ring with together with the carbon atom of these bonds mutually.R ¹with R ², R ¹with R ³or R ²with R ³the ring structure of the situation of bond for example can be enumerated: cyclobutyl, cyclopentyl, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc.Wherein, tetrahydrofuran base preferably.

Moreover, in formula (a1-1), preferably R ¹and R ²any one be hydrogen atom or methyl.

For the free radical polymerization monomer that forms the structural unit of (a1-1) the represented base that has formula and use can use commercially available product, also can use by known method synthetic.For example, as can be as shown in following by making (methyl) acrylic acid react and synthesize with vinethene under the existence of acid catalyst.

[changing 6]

R ¹¹represent hydrogen atom or alkyl, preferably hydrogen atom or methyl.

R ¹²and R ¹³as-CH (R ¹²) (R ¹³) with formula (a1-1) in R ²for identical meanings, R ¹⁴with the R in formula (a1-1) ¹for identical meanings, R ¹⁵with the R in formula (a1-1) ³for identical meanings, in addition, these preferable range is also identical.

Above-mentioned synthesizing also can make (methyl) acrylic acid and the copolymerization in advance of other monomers, reacts thereafter under the existence of acid catalyst with vinethene.

There is carboxyl and can illustrate following structural unit through the preferred concrete example of the structural unit (a-1-2) of the base of sour decomposability base protection.Moreover R represents hydrogen atom or methyl.

[changing 7]

[thering is the structural unit (a-1-3) of phenol hydroxyl through the base of sour decomposability base protection]

-have the structural unit of phenol hydroxyl-

The structural unit with phenol hydroxyl can be enumerated the structural unit in the resin that hydroxy styrenes is monomeric unit or novolaks system.Have in the structural unit of phenol hydroxyl, with regard to the viewpoint of the transparency, sensitivity, the preferably represented structural unit of formula (a1-2).

[changing 8]

(in formula (a1-2), R ²⁰represent hydrogen atom or methyl, R ²¹represent singly-bound or bivalence linking base, R ²²represent halogen atom or alkyl, a represents 1～5 integer, and b represents 0～4 integer, and a+b is below 5.Moreover, at the R existing more than 2 ²²situation time, these R ²²can be different also can be identical)

In formula (a1-2), R ²⁰represent hydrogen atom or methyl, preferably methyl.

In addition, the R in formula (a1-2) ²¹represent singly-bound or bivalence linking base.In the time being the situation of singly-bound, can improving sensitivity, and then can improve the transparency of cured film, therefore preferably.R ²¹bivalence linking base can illustrate alkylidene, R ²¹for the concrete example of alkylidene can be enumerated: methylene, ethylidene, propylidene, isopropylidene, sub-normal-butyl, isobutylidene, sub-tributyl, pentylidene, isoamylidene, sub-neopentyl, hexylidene etc.Wherein, R ²¹preferably singly-bound, methylene, ethylidene.In addition, above-mentioned bivalence linking base also can have substituting group, and substituting group can be enumerated halogen atom, hydroxyl, alkoxy etc.

In addition, a in formula (a1-2) represents 1～5 integer, with regard to the viewpoint of effect of the present invention or aspect easy to manufacture, and a preferably 1 or 2, more preferably a is 1.

In addition, about the bond position of the hydroxyl on phenyl ring, with R ²¹when the carbon atom of bond is benchmark (1), be preferably binding on 4.

R in formula (a1-2) ²²for the straight chain of halogen atom or carbon number 1～5 or the alkyl of branch's chain.Specifically can enumerate: fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, tributyl, amyl group, isopentyl, neopentyl etc.Wherein, with regard to aspect easy to manufacture, preferably chlorine atom, bromine atoms, methyl or ethyl.

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

-have phenol hydroxyl through the structural unit of the base of sour decomposability base protection-

Having phenol hydroxyl is the structural unit having by below the sour decomposability base describing in detail being protected to the base that the phenol hydroxyl of the structural unit with phenol hydroxyl forms through the structural unit of the base of sour decomposability base protection.

Acid decomposability base as above can use known, is not particularly limited.With regard to the viewpoint of the special storage stability with regard to sensitivity or resin combination, in sour decomposability base, also preferably there is the structural unit of the base forming with the form protection phenol hydroxyl of acetal.And then, with regard to the viewpoint of sensitivity, the base that in sour decomposability base, more preferably the form protection phenol hydroxyl with the represented acetal of above-mentioned formula (a1-1) forms.Moreover, when the situation of the base forming at the form protection phenol hydroxyl for the represented acetal of above-mentioned formula (a1-1), totally become-Ar-O-CR of base ¹r ²(OR ³) structure.Moreover Ar represents arlydene.

The preference of the acetal ester structure of protection phenol hydroxyl can illustrate R ¹=R ²=R ³=methyl or R ¹=R ²=methyl and R ³the combination of=benzyl.

In addition, for example can enumerate in order to form the free radical polymerization monomer that there is the structural unit of the base forming with the form protection phenol hydroxyl of acetal and use: 1-alkoxyalkyl protective, the THP trtrahydropyranyl protective of 4-hydroxy phenyl methacrylate etc. of the 1-alkoxyalkyl protective of the 1-alkoxyalkyl protective of hydroxy styrenes, the THP trtrahydropyranyl protective of hydroxy styrenes, Alpha-Methyl hydroxy styrenes, the THP trtrahydropyranyl protective of Alpha-Methyl-hydroxy styrenes, 4-hydroxy phenyl methacrylate.

The acetal protecting group of phenol hydroxyl is formula (a1-1) preferably.These can be used alone or are used in combination two or more.

The preferred concrete example of monomeric unit (a-1-3) can illustrate following structural unit, but the present invention is not limited to these structural units.Moreover the R in following structural unit represents hydrogen atom or methyl.

[changing 9]

[changing 10]

In addition, structural unit (a-1) preferably has carboxyl or phenol hydroxyl and feeds through 1-ethoxyethyl group or tetrahydrochysene furan the monomeric unit of the base of base protection.

With regard to the viewpoint of sensitivity, with respect to all monomeric units of components D, preferably 3mol%～the 70mol% of content of the monomeric unit of the formation structural unit (a-1) in components D, more preferably 10mol%～65mol%, and then 20mol%～60mol% preferably, particularly preferably be 35mol%～45mol%.

(a-2) there is the structural unit of crosslinking group

Components D at least contains (a-2) and has the structural unit of crosslinking group.

Above-mentioned crosslinking group, as long as for cause the base of sclerous reaction by heat treated, is not particularly limited.The embodiment preferably with the structural unit of crosslinking group can be enumerated: comprise choosing and freely have the structural unit of epoxy radicals and/or oxa-cyclobutyl and have at least one the structural unit in the group that the structural unit of ethene unsaturated group forms.Can enumerate more in detail following.

With regard to the viewpoint of storage stability or cured film characteristic, structural unit (a-2) preferably has the structural unit (a-2-1) of epoxy radicals and/or oxa-cyclobutyl.

< has structural unit (a-2-1) > of epoxy radicals and/or oxa-cyclobutyl

Components D preferably contains the structural unit (a-2-1) with epoxy radicals and/or oxa-cyclobutyl.Components D also can contain there is the structural unit of epoxy radicals and have oxa-cyclobutyl structural unit both.In addition, with regard to the transparent viewpoint of hardening thing, components D preferably contains the structural unit with oxa-cyclobutyl.

Have epoxide ring as long as have the base of epoxy radicals, there is no particular restriction, can preferably illustrate glycidyl, 3,4-epoxycyclohexyl methyl.

Have oxetanes ring as long as have the base of oxa-cyclobutyl, there is no particular restriction, can preferably illustrate (3-Ethyloxetane-3-yl) methyl.

Structural unit (a-2-1) as long as have at least one epoxy radicals or oxa-cyclobutyl in a monomeric unit, also can there is more than one epoxy radicals and more than one oxa-cyclobutyl, plural epoxy radicals or plural oxa-cyclobutyl, be not particularly limited, preferably there is the epoxy radicals and/or the oxa-cyclobutyl that add up to one～tri-, more preferably there is the epoxy radicals and/or the oxa-cyclobutyl that add up to one or two, and then preferably there is an epoxy radicals or oxa-cyclobutyl.

For the concrete example that forms the free radical polymerization monomer that has the structural unit of epoxy radicals and use for example can be enumerated: glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid-3, 4-epoxy butyl ester, methacrylic acid-3, 4-epoxy butyl ester, acrylic acid-6, 7-epoxy heptyl ester, methacrylic acid-6, 7-epoxy heptyl ester, α-ethylacrylate-6, 7-epoxy heptyl ester, adjacent vinyl benzyl glycidol ether, between vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether, the compound that contains ester ring type epoxy skeleton of recording in the paragraph 0031～paragraph 0035 of No. 4168443 communique of Jap.P. etc.

For the example that forms the free radical polymerization monomer that has the structural unit of oxa-cyclobutyl and use for example can be enumerated: (methyl) acrylate with oxa-cyclobutyl of recording in the paragraph 0011～paragraph 0016 of Japanese Patent Laid-Open 2001-330953 communique etc.

The example of the free radical polymerization monomer using in order to form structural unit (a-2-1) preferably contains the monomer of metacrylic acid ester structure, the monomer that contains acrylate structural.

In these monomers, more preferably can enumerate: (methyl) acrylate with oxa-cyclobutyl of recording in the compound that contains ester ring type epoxy skeleton of recording in the paragraph 0034～paragraph 0035 of glycidyl methacrylate, glycidyl acrylate, No. 4168443 communique of Jap.P. and the paragraph 0011～paragraph 0016 of Japanese Patent Laid-Open 2001-330953 communique.

With regard to the viewpoint of the heat-resisting transparency, particularly preferably be that to derive from any one structure list of acrylic acid (3-Ethyloxetane-3-yl) methyl esters and methacrylic acid (3-Ethyloxetane-3-yl) methyl esters towering.

Can be used alone one or be used in combination two or more of these structural units (a-2-1).

The preferred concrete example of structural unit (a-2-1) can illustrate following structural unit.

[changing 11]

< has structural unit (a-2-2) > of ethene unsaturated group

As thering is one of structural unit (a-2) of crosslinking group, can enumerate the structural unit (a-2-2) with ethene unsaturated group.

The above-mentioned structural unit (a-2-2) with ethene unsaturated group preferably has the structural unit of ethene unsaturated group on side chain, more preferably there is endways ethene unsaturated group, there is the structural unit of the side chain of carbon number 3～16, and then preferably there is the structural unit of the represented side chain of formula (a2-2-2).

[changing 12]

(in formula (a2-2-2), R ¹represent the bivalence linking base of carbon number 1～13, R ²and R ³independent hydrogen atom or the methyl of representing respectively)

R ¹as long as be the bivalence linking base of carbon number 1～13, the base that preferably comprises alkenylene, sub-cycloalkenyl group, arlydene or these are combined, in addition, also can contain the keys such as ester bond, ehter bond, amido link, amino-formate bond.In addition, bivalence linking base also can have the substituting group such as hydroxyl, carboxyl at an arbitrary position.

With respect to all monomeric units of components D, the preferably 5mol%～60mol% of content of the monomeric unit of the formation structural unit (a-2) in components D, more preferably 10mol%～55mol%, particularly preferably is 30mol%～50mol%.By contain structural unit (a-2) with aforementioned proportion, it is good that the physical property of cured film becomes.

(a-3) there is the structural unit of alkali-soluble base

Components D can contain (a-3) and have the structural unit of alkali-soluble base.

(a-3) structural unit that has an alkali-soluble base has the function of components D being given to alkali-soluble.Wherein, the acid number that in components D, the content of structural unit (a-3) is limited in components D becomes in the scope of the amount below 50mg KOH/g.If components D contains structural unit (a-3), components D is easily dissolved in aqueous slkali (developer solution) in the time developing, therefore the components D that contains structural unit (a-3) can easily be developed by developer solution.In addition, the monomer that contains alkali-soluble base is by using the crosslinked of crosslinking chemical or by for example, hardening with the intramolecular epoxy radicals or the reacting of oxetanyl (deriving from the base of said structure unit (a-2-1) etc.) that are positioned at components D, giving hardness to the hardening thing of gained.

For example there is alkali-soluble base in the structural unit (a-3) of alkali-soluble base, as long as for base used conventionally in the field of resist, can enumerate carboxyl, phenol hydroxyl etc.The typical example with the structural unit (a-3) of alkali-soluble base can be enumerated unsaturated carboxylic acid or its acid anhydrides, hydroxy styrenes or derivatives thereof etc., but is not limited to these.

Structural unit (a-3) can preferably use the above-mentioned structural unit that has the structural unit of carboxyl or have phenol hydroxyl.In these, particularly preferably be unsaturated carboxylic acid or its acid anhydrides.

Unsaturated carboxylic acid or its acid anhydrides for example can illustrate: the α such as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, maleic acid, fumaric acid, beta-unsaturated carboxylic acid and acid anhydrides thereof (maleic anhydride, itaconic anhydride etc.).In these, particularly preferably be acrylic acid, methacrylic acid.The structural unit (a-3) with alkali-soluble base can be used alone or be used in combination two or more.

Contain structural unit (a-3) in components D situation time, with respect to all monomeric units of components D, preferably 0.1mol%～the 14mol% of content of the monomeric unit of the formation structural unit (a-3) in components D, more preferably 0.1mol%～12mol%, particularly preferably is 0.1mol%～5mol%.By contain structural unit (a-3) with aforementioned proportion, it is good that developability becomes.

(a-4) there is the structural unit of aromatic rings

With regard to the viewpoint of refractive index, components D preferably contains the structural unit (a-4) with aromatic rings as said structure unit (a-1)～structural unit (a-3) structural unit in addition.

The monomer that forms said structure unit (a-4) for example can be enumerated phenylethylene, have (methyl) esters of acrylic acid etc. of aromatic rings.

In these, the structural unit that derives from cinnamic structural unit and derive from (methyl) benzyl acrylate can be preferably enumerated, the structural unit that derives from benzyl methacrylate can be more preferably enumerated.

Contain structural unit (a-4) in components D situation time, with respect to all monomeric units of components D, preferably 5mol%～the 35mol% of content of the monomeric unit of the formation structural unit (a-4) in components D, more preferably 10mol%～30mol%.By contain structural unit (a-4) with aforementioned proportion, it is good that the physical property of cured film becomes.

(a-5) other structural units

Components D also can, not hindering in the scope of effect of the present invention, contain said structure unit (a-1)～structural unit (a-4) structural unit (a-5) in addition.

The free radical polymerization monomer using in order to form structural unit (a-5) for example can be enumerated: the compound (wherein, by the monomer of above-mentioned formation structural unit (a-1)～structural unit (a-4) except) of recording in the paragraph 0021～paragraph 0024 of Japanese Patent Laid-Open 2004-264623 communique.

The free radical polymerization monomer using in order to form structural unit (a-5) can preferably illustrate: (methyl) acrylic acid two encircles (methyl) esters of acrylic acid that contains alicyclic structure of pentyl ester, (methyl) cyclohexyl acrylate, cyclohexyl acrylate and so on, (methyl) methyl acrylate, (methyl) acrylic acid-2-hydroxyl ethyl ester, styrene etc.

Wherein, particularly preferably be (methyl) acrylic acid-2-hydroxyl ethyl ester and/or (methyl) methyl acrylate.

In addition, also can enumerate the compound etc. of following record.

(methyl) acrylate monomer that contains polyoxy alkylidene chain for example can be enumerated: oxirane modification cresols acrylate (trade name: sub-Luo Nisi (Aronix) TO-901), oxirane modified acroleic acid dodecyl ester (trade name: sub-Luo Nisi (Aronix) TO-950), oxirane modified acroleic acid tridecyl ester (trade name: sub-Luo Nisi (Aronix) TO-951), 2-ethylhexyl polyethylene glycol acrylate (trade name: sub-Luo Nisi (Aronix) TO-946), 2-ethylhexyl polyethylene glycol acrylate (trade name: sub-Luo Nisi (Aronix) TO-947), 2-ethylhexyl polyethylene glycol acrylate (trade name: sub-Luo Nisi (Aronix) TO-948), 2-ethylhexyl polyethylene glycol acrylate (trade name: sub-Luo Nisi (Aronix) TO-949), more than for East Asia synthetic (thigh) manufactured,

Ethoxy-diethylene glycol acrylate (trade name: light acrylate (Light Acrylate) EC-A), methoxyl-triethylene glycol acrylate (trade name: light acrylate (Light Acrylate) MTG-A), methoxypolyethylene glycol acrylate (trade name: light acrylate (Light Acrylate) 130A), phenoxy group-polyethylene glycol acrylate (trade name: light acrylate (Light Acrylate) P-200A), nonyl phenyl-polyoxyethylene chain addition product acrylate (trade name: light acrylate (Light Acrylate) NP-4EA), nonyl phenyl-polyoxyethylene chain addition product acrylate (trade name: light acrylate (Light Acrylate) NP-8EA), it is more than common prosperity society chemistry (thigh) manufacture,

Polyethylene glycol acrylate (trade name: Blanc is (Blemmer) AE-350 not), polyethylene glycol methacrylate-styrene polymer (trade name: Blanc is (Blemmer) PE-90 not), polyethylene glycol methacrylate-styrene polymer (trade name: Blanc is (Blemmer) PE-200 not), polyethylene glycol methacrylate-styrene polymer (trade name: Blanc is (Blemmer) PE-350 not), methoxy poly (ethylene glycol) mono acrylic ester (trade name: Blanc is (Blemmer) AME-400 not), methoxy polyethylene glycol methacrylate-styrene polymer (trade name: Blanc is (Blemmer) PME-100 not), methoxy polyethylene glycol methacrylate-styrene polymer (trade name: Blanc is (Blemmer) PME-200 not), methoxy polyethylene glycol methacrylate-styrene polymer (trade name: Blanc is (Blemmer) PME-400 not), polypropylene glycol methacrylate (trade name: Blanc is (Blemmer) PP-500 not), polypropylene glycol methacrylate (trade name: Blanc is (Blemmer) PP-800 not), polyglycol polypropylene glycol methacrylate (trade name: Blanc is (Blemmer) 70PEP-370B not), polyglycol polytetramethylene glycol methacrylate (trade name: Blanc is (Blemmer) 50PET-800 not), octyloxy polyglycol polypropylene glycol monomethacrylate (trade name: Blanc is (Blemmer) 50POEP-800B not), octyloxy polyglycol polyoxy propylene glycol monomethyl acrylate (trade name: Blanc is (Blemmer) 50AOEP-800B not), it is more than Japanese grease (thigh) manufacture,

Methoxyl diethylene glycol methacrylate (trade name: NK ester (NK-ester) M-20G), methoxyl diethylene glycol methacrylate (trade name: NK ester (NK-ester) M-40G), methoxyl diethylene glycol methacrylate (trade name: NK ester (NK-ester) M-90G), phenoxy group diethylene glycol acrylate (trade name: NK ester (NK-ester) AMP-20G), above Wei Xinzhong village chemical industry (thigh) manufacture etc.

Components D can have independent a kind of structural unit (a-5), also can have two or more.

With respect to all monomeric units of components D, the preferably 0mo1%～40mol% of content of the monomeric unit of the formation structural unit (a-5) in components D.

In addition, contain structural unit (a-5) in components D situation time, with respect to all monomeric units of components D, preferably 1mol%～the 40mol% of content of the monomeric unit of the formation structural unit (a5) in components D, more preferably 5mol%～30mol%, particularly preferably is 10mol%～25mol%.

In addition, the method for each structural unit that imported ingredient D has can be polymerization, also can be high molecular weight reactive method, also can be also by these two kinds of methods.Components D can be used separately a kind of or be used in combination two or more in above-mentioned resin combination.

With respect to the total solid composition of resin combination, the content of the components D in resin combination of the present invention is 10 quality %～99 quality % preferably, more preferably 20 quality %～95 quality %, and then 25 quality %～90 quality % preferably.If content is this scope, it is good that the pattern formative while development becomes, and in addition, can obtain the hardening thing that refractive index is higher.Moreover the solid constituent amount of so-called resin combination, represents the amount except the volatile ingredients such as solvent.

Moreover, in resin combination of the present invention, also can be in the scope that does not hinder effect of the present invention resin beyond using ingredient B and components D.But the content of the resin beyond composition B and components D is preferably less than the content of composition B and the content of components D.

(composition E) light acid producing agent

Positive type photosensitive organic compound of the present invention preferably contains (composition E) light acid producing agent.

Composition E preferably responds to wavelength 300nm active ray above, preferably wavelength 300nm～450nm and acidic compound, to its chemical constitution unrestricted.In addition, about the light acid producing agent of directly not responding to active ray more than wavelength 300nm, as long as for by with sensitizer and with responding to active ray more than wavelength 300nm, acidic compound, also can preferably use with sensitizer combination.

It is the sour light acid producing agent below 4 that components D preferably produces pKa, and more preferably producing pKa is the sour light acid producing agent below 3.

The example of light acid producing agent can be enumerated: trichloromethyl-s-triazine, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound and oxime sulfonates compound etc.In these, with regard to the viewpoint of high sensitivity, preferably use oxime sulfonates compound.Can be used alone one or be used in combination two or more of these light acid producing agents.

These concrete examples can illustrate following compound.

Trichloromethyl-s-triazine can be enumerated: 2-(3-chlorphenyl) two (4, 6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl) two (4, 6-trichloromethyl)-s-triazine, 2-(4-methyl mercapto phenyl) two (4, 6-trichloromethyl)-s-triazine, 2-(4-methoxyl-β-styryl) two (4, 6-trichloromethyl)-s-triazine, 2-piperonyl two (4, 6-trichloromethyl)-s-triazine, 2-[2-(furans-2-yl) vinyl] two (4, 6-trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl) vinyl] two (4, 6-trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl] two (4, 6-trichloromethyl)-s-triazine or 2-(4-methoxyl naphthyl) two (4, 6-trichloromethyl)-s-triazine etc.

Er Fang Ji Iodonium salt can be enumerated: Er Ben Ji Iodonium trifluoroacetate, Er Ben Ji Iodonium fluoroform sulphonate, 4-methoxyphenyl Ben Ji Iodonium fluoroform sulphonate, 4-methoxyphenyl Ben Ji Iodonium trifluoroacetate, phenyl-4-(2 '-hydroxyl-1 '-myristyl oxygen base) Ben Ji Iodonium fluoroform sulphonate, 4-(2 '-hydroxyl-1 '-myristyl oxygen base) Ben Ji Iodonium hexafluoro antimonate or phenyl-4-(2 '-hydroxyl-1 '-myristyl oxygen base) Ben Ji Iodonium tosilate etc.

Triaryl matte salt can be enumerated: triphenylsulfonium fluoroform sulphonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyl diphenyl sulfonium fluoroform sulphonate, 4-methoxyphenyl diphenyl sulfonium trifluoroacetate, 4-thiophenyl phenyl diphenyl sulfonium fluoroform sulphonate or 4-thiophenyl phenyl diphenyl sulfonium trifluoroacetate etc.

Quarternary ammonium salt class can be enumerated: tetramethyl-ammonium butyl three (2,6-difluorophenyl) borate, tetramethyl-ammonium hexyl three (rubigan) borate, tetramethyl-ammonium hexyl three (3-trifluoromethyl) borate, benzyl dimethyl phenyl ammonium butyl three (2,6-difluorophenyl) borate, benzyl dimethyl phenyl ammonium hexyl three (rubigan) borate, benzyl dimethyl phenyl ammonium hexyl three (3-trifluoromethyl) borate etc.

Diazomethane derivative can be enumerated: two (cyclohexyl sulfonyl) diazomethane, two (tributyl sulfonyl) diazomethane, two (p-toluenesulfonyl) diazomethane etc.

Acid imide sulfonate derivatives can be enumerated: trimethyl fluoride sulfonyl oxygen base dicyclo [2.2.1] heptan-5-alkene-dicarboxyl acid imide, succimide trifluoromethane sulfonic acid ester, phthalimide trifluoromethane sulfonic acid ester, N-hydroxyl naphthalimide methanesulfonates, N-hydroxyl-5-norborene-2,3-dicarboxyl acid imide propane sulfonic acid ester etc.

With regard to the viewpoint of sensitivity, resin combination of the present invention preferably contains the oxime sulfonates compound with the represented oxime sulfonates structure of at least one following formula (1) as components D.Moreover wave-like line part represents the bond position with other chemical constitutions.

[changing 13]

There is the preferably represented compound of following formula (2) of oxime sulfonates compound of the represented oxime sulfonates structure of at least one above-mentioned formula (1).

R ^1A-C(R ^2A)=N-O-SO ₂-R ^3A (2)

In formula (2), R ^1Aalkoxy or the cyano group of the alkyl of expression carbon number 1～6, the halogenated alkyl of carbon number 1～4, phenyl, xenyl, naphthyl, 2-furyl, 2-thienyl, carbon number 1～4.At R ^1Aduring for the situation of phenyl, xenyl, naphthyl or anthryl, the substituting group of these bases in also can alkoxy and the group that nitro forms of alkyl, carbon number 1～4 through selecting free halogen atom, hydroxyl, carbon number 1～4 replaces.

In formula (2), R ^2Arepresent the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10, the halogenated alkyl of carbon number 1～5, the halogenated alkoxy of carbon number 1～5, the phenyl that can replace through W, the naphthyl that can replace through W or anthryl, dialkyl amido, morpholinyl or the cyano group that can replace through W.R ^2Awith R ^1Aalso bond and form 5 rings or 6 rings mutually, above-mentioned 5 rings or 6 rings also can with can there are 1 or 2 any substituent phenyl ring bonds.

In formula (2), R ^3Arepresent the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10, the halogenated alkyl of carbon number 1～5, the halogenated alkoxy of carbon number 1～5, the phenyl that can replace through W, the naphthyl that can replace through W or the anthryl that can replace through W.W represents the alkyl of halogen atom, cyano group, nitro, carbon number 1～10, alkoxy, the halogenated alkyl of carbon number 1～5 or the halogenated alkoxy of carbon number 1～5 of carbon number 1～10.

R ^1Athe alkyl of represented carbon number 1～6 also can be straight chain or branched chain alkyl, for example, can enumerate: methyl, ethyl, propyl group, isopropyl, normal-butyl, the second butyl, tributyl, n-pentyl, isopentyl, n-hexyl or 2-ethyl-butyl.

R ^1Athe halogenated alkyl of represented carbon number 1～4 for example can be enumerated: chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl.

R ^1Athe alkoxy of represented carbon number 1～4 can be enumerated methoxy or ethoxy.

At R ^1Awhile representing the situation of phenyl, xenyl, naphthyl or anthryl, for example, for example, substituting group in also can for example, alkoxy (methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy) and the group that nitro forms of alkyl (methyl, ethyl, propyl group, isopropyl, normal-butyl, the second butyl, tributyl), carbon number 1～4 through selecting free halogen atom (fluorine atom, chlorine atom, bromine atoms, iodine atom), hydroxyl, carbon number 1～4 of these bases replaces.

R ^2Athe concrete example of the alkyl of represented carbon number 1～10 can be enumerated: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the second butyl, tributyl, n-pentyl, isopentyl, the second amyl group, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc.

R ^2Athe concrete example of the alkoxy of represented carbon number 1～10 can be enumerated: methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, n-pentyloxy, n-octyloxy, n-decyloxy etc.

R ^2Athe concrete example of the halogenated alkyl of represented carbon number 1～5 can be enumerated: trifluoromethyl, pentafluoroethyl group, perfluor n-pro-pyl, perfluor normal-butyl, perfluor n-pentyl etc.

R ^2Athe concrete example of the halogenated alkoxy of represented carbon number 1～5 can be enumerated: trifluoromethoxy, five fluorine ethoxys, perfluor positive propoxy, perfluor n-butoxy, perfluor n-pentyloxy etc.

R ^2Athe concrete example of the represented phenyl that can replace through W can be enumerated: o-tolyl, between tolyl, p-methylphenyl, adjacent ethylphenyl, between ethylphenyl, to ethylphenyl, to (n-pro-pyl) phenyl, to (isopropyl) phenyl, to (normal-butyl) phenyl, to (isobutyl) phenyl, to (the second butyl) phenyl, to (tributyl) phenyl, to (n-pentyl) phenyl, to (isopentyl) phenyl, to (the 3rd amyl group) phenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, O-ethoxyl base, m-oxethyl phenyl, to ethoxyl phenenyl, to (positive propoxy) phenyl, to (isopropoxy) phenyl, to (n-butoxy) phenyl, to (isobutoxy) phenyl, to (the second butoxy) phenyl, to (the 3rd butoxy) phenyl, to (n-pentyloxy) phenyl, to (isoamoxy) phenyl, to (the 3rd amoxy) phenyl, rubigan, to bromophenyl, to fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromo phenyl, 2,4-difluorophenyl, 2,4,6-dichlorophenyl, 2,4,6-tribromo phenyl, 2,4,6-trifluorophenyl, five chlorophenyl, penta-bromophenyl, pentafluorophenyl group, to xenyl etc.

R ^2Athe concrete example of the represented naphthyl that can replace through W can be enumerated: 2-methyl isophthalic acid-naphthyl, 3-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 5-methyl isophthalic acid-naphthyl, 6-methyl isophthalic acid-naphthyl, 7-methyl isophthalic acid-naphthyl, 8-methyl isophthalic acid-naphthyl, 1-methyl-2-naphthyl, 3-methyl-2-naphthyl, 4-methyl-2-naphthyl, 5-methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl, 8-methyl-2-naphthyl etc.

R ^2Athe concrete example of the represented anthryl that can replace through W can be enumerated: 2-methyl isophthalic acid-anthryl, 3-methyl isophthalic acid-anthryl, 4-methyl isophthalic acid-anthryl, 5-methyl isophthalic acid-anthryl, 6-methyl isophthalic acid-anthryl, 7-methyl isophthalic acid-anthryl, 8-methyl isophthalic acid-anthryl, 9-methyl isophthalic acid-anthryl, 10-methyl isophthalic acid-anthryl, 1-methyl-2-anthryl, 3-methyl-2-anthryl, 4-methyl-2-anthryl, 5-methyl-2-anthryl, 6-methyl-2-anthryl, 7-methyl-2-anthryl, 8-methyl-2-anthryl, 9-methyl-2-anthryl, 10-methyl-2-anthryl etc.

R ^2Arepresented dialkyl amido can be enumerated: dimethylamino, diethylamino, dipropyl amino, dibutylamino, diphenyl amino etc.

R ^3Athe concrete example of the alkyl of represented carbon number 1～10 can be enumerated: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the second butyl, tributyl, n-pentyl, isopentyl, the second amyl group, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc.

R ^3Athe concrete example of the alkoxy of represented carbon number 1～10 can be enumerated: methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, n-pentyloxy, n-octyloxy, n-decyloxy etc.

R ^3Athe concrete example of the halogenated alkyl of represented carbon number 1～5 can be enumerated: trifluoromethyl, pentafluoroethyl group, perfluor n-pro-pyl, perfluor normal-butyl, perfluor n-pentyl etc.

R ^3Athe concrete example of the halogenated alkoxy of represented carbon number 1～5 can be enumerated: trifluoromethoxy, five fluorine ethoxys, perfluor positive propoxy, perfluor n-butoxy, perfluor n-pentyloxy etc.

R ^3Athe concrete example of the represented phenyl that can replace through W can be enumerated: o-tolyl, between tolyl, p-methylphenyl, adjacent ethylphenyl, between ethylphenyl, to ethylphenyl, to (n-pro-pyl) phenyl, to (isopropyl) phenyl, to (normal-butyl) phenyl, to (isobutyl) phenyl, to (the second butyl) phenyl, to (tributyl) phenyl, to (n-pentyl) phenyl, to (isopentyl) phenyl, to (the 3rd amyl group) phenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, O-ethoxyl base, m-oxethyl phenyl, to ethoxyl phenenyl, to (positive propoxy) phenyl, to (isopropoxy) phenyl, to (n-butoxy) phenyl, to (isobutoxy) phenyl, to (the second butoxy) phenyl, to (the 3rd butoxy) phenyl, to (n-pentyloxy) phenyl, to (isoamoxy) phenyl, to (the 3rd amoxy) phenyl, rubigan, to bromophenyl, to fluorophenyl, 2,4-dichlorophenyl, 2,4-dibromo phenyl, 2,4-difluorophenyl, 2,4,6-dichlorophenyl, 2,4,6-tribromo phenyl, 2,4,6-trifluorophenyl, five chlorophenyl, penta-bromophenyl, pentafluorophenyl group, to xenyl etc.

R ^3Athe concrete example of the represented naphthyl that can replace through W can be enumerated: 2-methyl isophthalic acid-naphthyl, 3-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 5-methyl isophthalic acid-naphthyl, 6-methyl isophthalic acid-naphthyl, 7-methyl isophthalic acid-naphthyl, 8-methyl isophthalic acid-naphthyl, 1-methyl-2-naphthyl, 3-methyl-2-naphthyl, 4-methyl-2-naphthyl, 5-methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl, 8-methyl-2-naphthyl etc.

R ^3Athe concrete example of the represented anthryl that can replace through W can be enumerated: 2-methyl isophthalic acid-anthryl, 3-methyl isophthalic acid-anthryl, 4-methyl isophthalic acid-anthryl, 5-methyl isophthalic acid-anthryl, 6-methyl isophthalic acid-anthryl, 7-methyl isophthalic acid-anthryl, 8-methyl isophthalic acid-anthryl, 9-methyl isophthalic acid-anthryl, 10-methyl isophthalic acid-anthryl, 1-methyl-2-anthryl, 3-methyl-2-anthryl, 4-methyl-2-anthryl, 5-methyl-2-anthryl, 6-methyl-2-anthryl, 7-methyl-2-anthryl, 8-methyl-2-anthryl, 9-methyl-2-anthryl, 10-methyl-2-anthryl etc.

The concrete example of the alkyl of the represented carbon number 1～10 of W, alkoxy, the halogenated alkyl of carbon number 1～5 and the halogenated alkoxy of carbon number 1～5 of carbon number 1～10 can be enumerated: with as R ^2Aor R ^3Athe concrete example of the alkyl of represented carbon number 1～10, the alkoxy of carbon number 1～10, the halogenated alkyl of carbon number 1～5 and the halogenated alkoxy of carbon number 1～5 and enumerate identical.

R ^2Awith R ^1Aalso bond and form 5 rings or 6 rings mutually.

At R ^2Awith R ^1Amutually bond and while forming the situation of 5 rings or 6 rings, above-mentioned 5 rings or 6 rings can be enumerated carbon-ring type base and hetero ring type cyclic group, for example, also can be cyclopentane, cyclohexane, cycloheptane, pyrroles, furans, thiophene, imidazoles, oxazole, thiazole, pyrans, pyridine, pyrazine, morpholine, piperidines or piperazine ring.Above-mentioned 5 rings or 6 rings also can with can there is any substituent phenyl ring bond, its example can be enumerated: naphthane, dihydroanthracene, indenes, benzodihydropyran, fluorenes, dibenzo piperazine is muttered or thioxanthene (thioxanthene) ring system.Above-mentioned 5 rings or 6 rings also can contain carbonyl, and its example can be enumerated: cyclohexadienone (cyclohexadienone), naphthalenone (naphthalenone) and anthrone ring system.

One of preferred implementation of the represented compound of above-mentioned formula (2) is the represented compound of following formula (2-1).The represented compound of formula (2-1) is the R in formula (2) ^2Awith R ^1Abond and form the compound of 5 rings.

[changing 14]

(in formula (2-1), R ^3Awith the R in formula (2) ^3Afor identical meanings, X represents alkyl, alkoxy or halogen atom, and t represents 0～3 integer, in the time that t is 2 or 3, multiple X can be identical also can be different)

Preferably straight chain shape or the branch's chain-like alkyl of carbon number 1～4 of alkyl that X is represented.Preferably straight chain shape or the branch's chain alkoxy of carbon number 1～4 of alkoxy that X is represented.Preferably chlorine atom or the fluorine atom of halogen atom that X is represented.

T preferably 0 or 1.In formula (2-1), particularly preferably be following compound: t and be 1, X is methyl, the position of substitution of X is ortho position, and R ^3Afor the straight chain-like alkyl, 7 of carbon number 1～10,7-dimethyl-2-oxa-norborny methyl or to toluyl groups.

The concrete example of the represented oxime sulfonates compound of formula (2-1) can be enumerated following compound (i), compound (ii), compound (iii), compound (iv) etc., these compounds one that can be used alone, also can and with two or more.Compound (i)～compound (iv) can be used as commercially available product and obtains.

In addition, also can use with the light acid producing agent combination of other kinds.

[changing 15]

One of preferred implementation of the represented compound of formula (2) is:

R ^1Arepresent alkyl, trifluoromethyl, phenyl, chlorphenyl, dichlorophenyl, methoxyphenyl, 4-xenyl, naphthyl or the anthryl of carbon number 1～4;

R ^2Arepresent cyano group;

R ^3Arepresent the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10, the halogenated alkyl of carbon number 1～5, the halogenated alkoxy of carbon number 1～5, the phenyl that can replace through W, the naphthyl that can replace through W or the anthryl that can replace through W, W represents the alkyl of halogen atom, cyano group, nitro, carbon number 1～10, alkoxy, the halogenated alkyl of carbon number 1～5 or the halogenated alkoxy of carbon number 1～5 of carbon number 1～10.

The also represented compound of following formula (2-2) preferably of the represented compound of formula (2).

[changing 16]

In formula (2-2), R ^4Arepresent halogen atom, hydroxyl, the alkyl of carbon number 1～4, alkoxy or the nitro of carbon number 1～4, L represents 0～5 integer.R ^3Arepresent the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10, the halogenated alkyl of carbon number 1～5, the halogenated alkoxy of carbon number 1～5, the phenyl that can replace through W, the naphthyl that can replace through W or the anthryl that can replace through W, W represents the alkyl of halogen atom, cyano group, nitro, carbon number 1～10, alkoxy, the halogenated alkyl of carbon number 1～5 or the halogenated alkoxy of carbon number 1～5 of carbon number 1～10.

R in formula (2-2) ^3Apreferably 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, particularly preferably be methyl, ethyl, n-pro-pyl, normal-butyl or p-methylphenyl.

R ^4Arepresented halogen atom is fluorine atom, chlorine atom or bromine atoms preferably.

R ^4Apreferably methyl or ethyl of the alkyl of represented carbon number 1～4.

R ^4Athe preferably methoxy or ethoxy of alkoxy of represented carbon number 1～4.

L preferably 0～2, particularly preferably is 0～1.

In the represented compound of formula (2), the preferred form of the compound comprising in the represented compound of formula (2-2) is following form: in formula (2), and R ^1Arepresent phenyl or 4-methoxyphenyl, R ^2Arepresent cyano group, R ^3Arepresent methyl, ethyl, n-pro-pyl, normal-butyl or 4-tolyl.

The also represented compound of following formula (1-2) preferably of the represented compound of above-mentioned formula (1).

[changing 17]

(in formula (1-2), R ¹represent alkyl, aryl or heteroaryl, R ²independent hydrogen atom, alkyl, aryl or halogen atom, the R of representing respectively ⁶respectively independent halogen atom, alkyl, alkoxy, sulfonic group, amino-sulfonyl or the alkoxy sulfonyl of representing, X represents O or S, n represent 1 or 2, m represent 0～6 integer)

In resin combination of the present invention, with respect to content 100 mass parts of components D, (composition E) light acid producing agent preferably uses 0.1 mass parts～10 mass parts, more preferably uses 0.5 mass parts～10 mass parts.

(composition F) thermal cross-linking agent

Resin combination of the present invention preferably contains (composition F) thermal cross-linking agent.By adding (composition F) thermal cross-linking agent, can be made into firmly cured film.Moreover the composition F in the present invention is set as beyond components D.

It is crosslinking chemical, the crosslinking chemical that contains alkoxy methyl that thermal cross-linking agent can preferably illustrate blocked isocyanate, have the epoxy resin of epoxy radicals or have (methyl) acrylic resin of carboxyl etc.In these, particularly preferably be the epoxy resin with epoxy radicals.

The concrete example with the epoxy resin of epoxy radicals can be enumerated: have bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, aliphatic epoxy resin of epoxy radicals etc.

In these, particularly preferably be have epoxy radicals bisphenol A type epoxy resin, have epoxy radicals aliphatic epoxy resin, there is the phenol novolak type epoxy resin of epoxy radicals.

With respect to content 100 mass parts of components D, the addition of composition F is 0.05 mass parts～50 mass parts preferably, more preferably 0.5 mass parts～10 mass parts, and then 0.5 mass parts～5 mass parts preferably.

Other compositions of < >

Resin combination of the present invention also can contain other compositions beyond mentioned component A～composition F.

Other compositions, with regard to the viewpoint of sensitivity, preferably add (composition G) sensitizer or (composition H) development accelerant.

And then, resin combination of the present invention is with regard to the viewpoint of substrate adhesion, preferably contain (composition I) and connect airtight modifying agent, with regard to the viewpoint of liquid storage stability, preferably contain (composition J) alkali compounds, with regard to the viewpoint of coating, preferably contain (composition K) interfacial agent (fluorine is interfacial agent, silicone-based interfacial agent etc.).

And then, optionally can in resin combination of the present invention, add (composition L) antioxidant, (composition M) plasticiser, (composition N) hot radical and produce the known adjuvant such as antiprecipitant of agent, (composition O) thermal acid generator, (composition P) acid proliferation generator, ultraviolet light absorber, tackifier and organic or inorganic.

Other compositions that can contain resin combination of the present invention below, are illustrated.

(composition G) sensitizer

In resin combination of the present invention, with the combination of above-mentioned (composition E) light acid producing agent in, can add (composition G) sensitizer to promote its decomposition.

Sensitizer absorbs active ray or radioactive ray and becomes excited state.The sensitizer that becomes excited state contacts with light acid producing agent, produces the effects such as electronics transfer, energy transfer, heating.Thus, light acid producing agent generation chemical change and decomposing, generates acid.

The example of preferred sensitizer can be enumerated: belong to following compounds and in the scope of 350nm～450nm, have the compound of absorbing wavelength.

The polynuclear aromatic same clan (for example pyrene (pyrene), perylene (perylene), triphenylene (triphenylene), anthracene (anthracene)), dibenzo piperazine class (for example luciferin (fluorescein) of muttering, eosin, erythrosine, rhodamine B, rose-red), xanthone (for example xanthone, thioxanthone, dimethyl thia anthrone, diethyl thioxanthone), cyanine class (for example thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (for example merocyanine, carbonyl merocyanine), if red cyanines (rhodacyanine) class, oxygen class, thiazide (for example thionine (thionine), methylene blue, toluidine blue), acridine (for example acridine orange, chloroflavin, acridine yellow), acridine ketone (for example acridone, 10-butyl-2-chloro-acridine ketone), Anthraquinones (for example anthraquinone), side's sour cyanines (squarylium) class (for example sour cyanines in side), styrene base class, basicity styrene base class, Coumarins (for example 7-diethylamino-4-methylcoumarin).In these sensitizers, particularly preferably be anthracene class, acridine ketone, Coumarins, basicity styrene base class.

Sensitizer also can use commercially available product, also can synthesize by known synthetic method.

With regard to having the viewpoint of sensitivity, the transparency concurrently, with respect to (composition E) light acid producing agent 100 mass parts, the addition of sensitizer is 20 mass parts～300 mass parts preferably, particularly preferably are 30 mass parts～200 mass parts.

(composition H) development accelerant

Resin combination of the present invention preferably contains (composition H) development accelerant.

(composition H) development accelerant can use any compound with development accelaration effect, preferably there is the compound that selects at least one structure in the group that free carboxyl group, phenol hydroxyl and alkylene oxide group form, more preferably there is the compound of carboxyl or phenol hydroxyl.Have through the carboxyl of acid dissociation base protection or the compound of phenol hydroxyl also particularly preferably.

In addition, the molecular weight of (composition H) development accelerant preferably 100～2,000, more preferably 150～1,500, particularly preferably be 150～1,000.

About the example of development accelerant, there is compound of recording in the methyl ether of the polyglycol enumerated, polyglycol of alkylene oxide group and Japanese patent laid-open 9-222724 communique etc.

There is enumerating of carboxyl: the compound of recording in Japanese Patent Laid-Open 2000-66406 communique, Japanese patent laid-open 9-6001 communique, Japanese patent laid-open 10-20501 communique, Japanese patent laid-open 11-338150 communique etc.

There is enumerating of phenol hydroxyl: the compound of recording in Japanese Patent Laid-Open 2005-346024 communique, Japanese patent laid-open 10-133366 communique, Japanese patent laid-open 9-194415 communique, Japanese patent laid-open 9-222724 communique, Japanese patent laid-open 11-171810 communique, Japanese Patent Laid-Open 2007-121766 communique, Japanese patent laid-open 9-297396 communique, Japanese Patent Laid-Open 2003-43679 communique etc.In these, preferably phenyl ring number is the phenolic compounds of 2～10, and more preferably phenyl ring number is the phenolic compounds of 2～5.The particularly preferred phenoloid disclosing as dissolution accelerator in Japanese patent laid-open 10-133366 communique of enumerating.

(composition H) development accelerant one that can be used alone, also can and with two or more.

With regard to the viewpoint of sensitivity and residual film ratio, with respect to content 100 mass parts of components D, preferably 0.1 mass parts～30 mass parts of addition of (composition H) development accelerant in resin combination of the present invention, more preferably 0.2 mass parts～20 mass parts, most preferably 0.5 mass parts～10 mass parts.

(composition I) connects airtight modifying agent

Resin combination of the present invention preferably contains (composition I) and connects airtight modifying agent.

Spendable in resin combination of the present invention (composition I) connects airtight modifying agent compound that to be the inorganics that makes to become substrate silicon compounds such as (, the metals such as gold, copper, aluminium) such as silicon, monox, silicon nitrides improve with the adhesion of dielectric film.Specifically can enumerate silane coupling agent, mercaptan based compound etc.The silane coupling agent that connects airtight modifying agent as (the composition I) that use in the present invention is the object that is modified as with interface, is not particularly limited, and can use known.

Preferred silane coupling agent for example can be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyl tri-alkoxy silicon alkane, γ-glycidoxypropyl alkyl-dialkoxysilanes, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl alkyl-dialkoxysilanes, γ-chloropropyl trialkoxy silane, γ-sulfydryl propyl trialkoxy silane, β-(3,4-epoxycyclohexyl) ethyl trialkoxy silane, vinyl trialkyl oxysilane.

In these, more preferably γ-glycidoxypropyl trialkoxy silane and γ-methacryloxypropyl trialkoxy silane, and then γ-glycidoxypropyl trialkoxy silane preferably.

These one or be used in combination two or more of can be used alone.

With respect to content 100 mass parts of components D, (the composition I) in resin combination of the present invention connects airtight preferably 0.1 mass parts～20 mass parts of content of modifying agent, more preferably 0.5 mass parts～10 mass parts.

(composition J) alkali compounds

Resin combination of the present invention preferably contains (composition J) alkali compounds.

(composition J) alkali compounds can be used in chemically amplified photo resist agent any choice for use.For example can enumerate: the quarternary ammonium salt of fatty amine, aromatic amine, hetero ring type amine, hydroxide level Four ammonium and carboxylic acid etc.

Fatty amine for example can be enumerated: trimethylamine, diethylamine, triethylamine, di-n-propylamine, Tri-n-Propylamine, two n-amylamines, tri-n-amyl amine, diethanolamine, triethanolamine, dicyclohexyl amine, dicyclohexyl methylamine etc.

Aromatic amine for example can be enumerated: aniline, benzylamine, DMA, diphenylamine etc.

Hetero ring type amine for example can be enumerated: pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl 4-phenyl pyridine, 4-dimethylaminopyridine, imidazoles, benzimidazole, 4-methylimidazole, 2-Phenylbenzimidazole, 2, 4, 5-triphenyl imidazoles, nicotine, niacin, Nicotinic Acid Amide, quinoline, oxine, pyrazine, pyrazoles, pyridazine, purine, Pyrrolizidine, piperidines, piperazine, morpholine, 4-methyl morpholine, 1, 5-diazabicyclo [4.3.0]-5-nonene, 1, 8-diazabicyclo [5.3.0]-7-hendecene etc.

Hydroxide level Four ammonium for example can be enumerated: tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide four-normal-butyl ammonium, hydroxide four-n-hexyl ammonium etc.

The quarternary ammonium salt of carboxylic acid for example can be enumerated: tetramethyl-ammonium acetate, tetramethyl-ammonium benzoate, four-normal-butyl ammonium acetate, four-normal-butyl ammonium benzoate etc.

The spendable alkali compounds one that can be used alone in the present invention, also can and with two or more.

With respect to content 100 mass parts of components D, preferably 0.001 mass parts～1 mass parts of content of (composition J) alkali compounds in resin combination of the present invention, more preferably 0.002 mass parts～0.2 mass parts.

(composition K) interfacial agent (fluorine is interfacial agent, silicone-based interfacial agent etc.)

Resin combination of the present invention preferably contains (composition K) interfacial agent (fluorine is interfacial agent, silicone-based interfacial agent etc.).

Interfacial agent can be enumerated the multipolymer (3) that contains structural unit A and structural unit B shown in following as preference.The weight average molecular weight (Mw) of this multipolymer is preferably more than 1,000 and below 10,000, more preferably more than 1,500 and below 5,000.Weight average molecular weight is the value of the polystyrene conversion by gel permeation chromatography (GPC) mensuration.

[changing 18]

In multipolymer (3), R ²¹and R ²³independent hydrogen atom or methyl, the R of representing respectively ²²represent the straight-chain alkyl-sub-of carbon number more than 1 and below 4, R ²⁴represent hydrogen atom or the alkyl of carbon number more than 1 and below 4, L represents the alkylidene of carbon number more than 3 and below 6, p and q are the quality percentage that represents polymerization ratio, numerical value more than p represents 10 quality % and below 80 quality %, numerical value more than q represents 20 quality % and below 90 quality %, r represents the integer more than 1 and below 18, and n represents the integer more than 1 and below 10.

L in structural unit B is the represented alkylidene of following formula (4) preferably.

[changing 19]

In formula (4), R ²⁵represent the alkyl of carbon number more than 1 and below 4, with regard to intermiscibility and to regard to the aspect of the wetting quality of applied, the preferably alkyl of carbon number more than 1 and below 3, the more preferably alkyl of carbon number 2 or 3.

In addition, p and q and (p+q) preferably p+q=100, i.e. 100 quality %.

Fluorine is interfacial agent, the example of silicone-based interfacial agent specifically can be enumerated: clear No. 62-36663 of Japanese Patent Laid-Open, clear No. 61-226746 of Japanese Patent Laid-Open, clear No. 61-226745 of Japanese Patent Laid-Open, clear No. 62-170950 of Japanese Patent Laid-Open, clear No. 63-34540 of Japanese Patent Laid-Open, No. 7-230165, Japanese patent laid-open, No. 8-62834, Japanese patent laid-open, No. 9-54432, Japanese patent laid-open, No. 9-5988, Japanese patent laid-open, the interfacial agent of recording in each communiques such as No. 2001-330953, Japanese Patent Laid-Open, also can use commercially available interfacial agent.Spendable commercially available interfacial agent for example can be enumerated: Ai Futuo (Eftop) EF301, Ai Futuo (Eftop) EF303, (manufacturing for Mitsubishi Materials electronics changes into (thigh) above), Fu Luode (Fluorad) FC430, Fu Luode (Fluorad) FC431 (being that Sumitomo 3M (thigh) manufactures above), Mei Jiafa (Megafac) F171, Mei Jiafa (Megafac) F780F, Mei Jiafa (Megafac) F173, Mei Jiafa (Megafac) F176, Mei Jiafa (Megafac) F189, Mei Jiafa (Megafac) R08 (being that Di Aisheng (DIC) (thigh) manufactures above), Sha Fulong (Surflon) S-382, Sha Fulong (Surflon) SC01, Sha Fulong (Surflon) 102, Sha Fulong (Surflon) 103, Sha Fulong (Surflon) 104, Sha Fulong (Surflon) 105, Sha Fulong (Surflon) 106 (being Asahi Glass (thigh) manufacture above), the fluorine such as Pohle Floex (PolyFox) series (manufacture of Ou Nuofa (OMNOVA) company) are interfacial agent or silicone-based interfacial agent.In addition, polysiloxane polymer KP-341 (SHIN-ETSU HANTOTAI's chemical industry (thigh) manufacture) also can be used as silicone-based interfacial agent.

These interfacial agents can be used alone one or mix use two or more.In addition, also can and with fluorine be interfacial agent and silicone-based interfacial agent.

With respect to content 100 mass parts of components D, the addition of (composition K) interfacial agent (fluorine is interfacial agent, silicone-based interfacial agent etc.) in resin combination of the present invention is preferably below 10 mass parts, more preferably 0.01 mass parts～10 mass parts, and then 0.01 mass parts～1 mass parts preferably.

(composition L) antioxidant

Resin combination of the present invention also can contain (composition L) antioxidant.By adding (composition L) antioxidant, can prevent the painted of cured film, maybe can reduce by the thickness due to decomposition and reduce.

As (composition L) antioxidant, can contain known antioxidant.This kind of antioxidant for example can be enumerated: phosphorous antioxidant, hydrazides class, hindered amine are that antioxidant, sulphur are that antioxidant, phenol are antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxy amine derivatives etc.In these, with regard to the viewpoint reducing with regard to painted, the thickness of cured film, particularly preferably being phenol is antioxidant.These one that can be used alone, also can mix use two or more.

Phenol is that the commercially available product of antioxidant for example can be enumerated: Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-80 (above for Ai Dike (ADEKA) (thigh) manufactures), Yi Jialesi (Irganox) 1098 (Japanese vapour bar (Ciba Japan) (thigh) is manufactured).

With respect to the total solid composition of resin combination, the content of (composition L) antioxidant is 0.1 quality %～6 quality % preferably, and more preferably 0.2 quality %～5 quality %, particularly preferably is 0.5 quality %～4 quality %.By being set within the scope of this, can obtain the sufficient transparency of formed film, and pattern form time sensitivity also become good.

In addition, also can be added in resin combination of the present invention various ultraviolet light absorbers or metal passivator etc. of recording in " the new expansion of polymeric additive (daily magazine industry newspaper office (thigh)) " as adjuvant in addition of antioxidant.

(composition M) plasticiser

Resin combination of the present invention also can contain (composition M) plasticiser.

(composition M) plasticiser for example can be enumerated: dibutyl phthalate, dioctyl phthalate, phthalic acid two-dodecyl ester, polyglycol, glycerine, dimethyl glyceryl phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerine etc.

With respect to content 100 mass parts of components D, preferably 0.1 mass parts～30 mass parts of content of (composition M) plasticiser in resin combination of the present invention, more preferably 1 mass parts～10 mass parts.

(composition N) hot radical produces agent

Resin combination of the present invention also can contain (composition N) hot radical and produce agent, in the time of the situation of the ethene unsaturated compound as containing the compound with ethene unsaturated double-bond, preferably contain (composition N) hot radical and produce agent.Hot radical produces agent and can use known hot radical to produce agent.

Hot radical produces agent for producing free radical by heat energy, causes or promote the compound of the polyreaction of polymerizable compound.Produce agent by adding hot radical, the cured film of gained becomes more tough sometimes, and thermotolerance, solvent resistance improve.

Preferred hot radical produces agent and can enumerate: aromatic series ketone, salt compound, organic peroxide, sulphur compound, six aryl united imidazoles, ketoxime ester compounds, boric acid ester compound, azine (azinium) compound, metallocene compound, active ester compound, the compound with carbon halogen bond, azo based compound, bibenzyl derivative etc.

(composition N) hot radical produces the agent one that can be used alone, also can and with two or more.

With regard to the viewpoint promoting with regard to film physical property, in the time that the content of components D is set as to 100 mass parts, (composition N) hot radical in resin combination of the present invention produces preferably 0.01 mass parts～50 mass parts of content of agent, more preferably 0.1 mass parts～20 mass parts, most preferably 0.5 mass parts～10 mass parts.

(composition O) thermal acid generator

Resin combination of the present invention also can contain (composition O) thermal acid generator.

So-called thermal acid generator, refer to the acidic compound by heat, preferably thermal decomposition point is the compound of the scope of 130 DEG C～250 DEG C, more preferably 150 DEG C～220 DEG C, for example, for by the sour compound that heats low nucleophilicities such as producing sulfonic acid, carboxylic acid, disulfonyl imines.

The acid producing is the sulfonic acid below by force to 2 of pKa or the alkyl carboxylic acid replacing through electron withdrawing group or aryl carboxylic acid, the disulfonyl imines etc. that replaces through electron withdrawing group similarly preferably.Electron withdrawing group can be enumerated: the haloalkyl such as halogen atom, trifluoromethyl, nitro, the cyano group such as fluorine atom.

In addition, in the present invention, also preferably use and do not produce in fact acid by the irradiation of exposure light, pass through heat and acidic sulphonic acid ester.Thermal acid generator's molecular weight preferably 230～1,000, more preferably 230～800.

With respect to content 100 mass parts of components D, the content of thermal acid generator in resin combination is 0.5 mass parts～20 mass parts preferably, particularly preferably is 1 mass parts～15 mass parts.

(composition P) acid proliferation generator

Resin combination of the present invention, in order to improve sensitivity, can use (composition P) acid proliferation generator.In the present invention, acid proliferation generator used is to react and the further compound that produces acid, makes the acid concentration rising in reaction system by acid catalyst, and for not there is not the compound stably existing under sour state.This kind of compound increases more than one acid by primary first-order equation, react post therefore be accompanied by the carrying out of reaction, but because produced acid self can be brought out selfdecomposition, so place produce sour intensity preferably acid ionization constant pKa below 3, particularly preferably be below 2.

The concrete example of acid proliferation generator can be enumerated: the compound of recording in the paragraph 0203～paragraph 0223 of Japanese patent laid-open 10-1508 communique, the paragraph 0016～paragraph 0055 of Japanese patent laid-open 10-282642 communique and the 39th page of the 12nd row～47 of Jap.P. JP-A 9-512498 communique page the 2nd row.

In the present invention, spendable acid proliferation generator can be enumerated: utilize the acid that produced by acid producing agent and decompose, producing the pKa such as dichloroacetic acid, trichloroacetic acid, methane-sulforic acid, benzene sulfonic acid, trifluoromethanesulfonic acid, phenyl-phosphonic acid is the sour compound below 3.

With regard to the viewpoint of the dissolving contrast of exposure portion and unexposed portion, with respect to (composition E) light acid producing agent 100 mass parts, the content of acid proliferation generator in resin combination is preferably set as 10 mass parts～1,000 mass parts, is more preferably set as 20 mass parts～500 mass parts.

(manufacture method of positive type photosensitive organic compound)

There is no particular restriction for the manufacture method of positive type photosensitive organic compound of the present invention, preferably comprise the following steps: (composition A) inorganic particulate, (composition B) are there is to spreading agent and (composition C) solvent of acidic group, obtain the step of dispersion liquid; And interpolation (components D) contains the polymkeric substance of structural unit and the step of (composition E) light acid producing agent that (a-1) has the structural unit of the base departing from by acid and/or heat and (a-2) have crosslinking group in above-mentioned dispersion liquid.

In addition, in the manufacture method of positive type photosensitive organic compound of the present invention, preferably in advance composition A～composition C is mixed, and make dispersion liquid.

There is no particular restriction in the order by merging of composition A～composition C, three kinds can be mixed simultaneously, also can first any two be mixed, and add wherein remaining one.In addition, also can be by composition A with the potpourri of solvent, mix with the potpourri of solvent with composition B.

The solvent using when the preparation of above-mentioned dispersion liquid for example, except above-mentioned (composition C) solvent, also can be enumerated: the alcohols 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 etc.

These solvents can be used alone one or mix use two or more.

There is no particular restriction for the mixed method of composition A～composition E and other compositions, can preferably prepare in the following manner: use the mixing arrangements such as bowl mill, rod mill, ball mill, coating oscillator, homogenizer, three rollers to mix, disperse.

In addition, in the time using inorganic particulate, composition B and solvent to prepare in advance the situation of dispersion liquid, with regard to the viewpoint of dispersiveness, dispersion stabilization, composition B is with respect to the preferably scope of 0.1 quality %～90 quality % of content of the total solid composition of above-mentioned dispersion liquid, the more preferably scope of 5 quality %～80 quality %, and then the scope of 10 quality %～75 quality % preferably.

In addition, the interpolation of components D and composition E is also not particularly limited, for example can be by components D and composition E directly simultaneously or be added into successively in above-mentioned dispersion liquid, also can by components D and composition E respectively with solvent, and be added in above-mentioned dispersion liquid.

In addition, about the mixing period of the composition beyond composition A～composition E, there is no particular restriction, can in the stage of above-mentioned dispersion liquid, mix, and also can after the above-mentioned dispersion liquid of preparation, mix, and mixes after preferably preparing above-mentioned dispersion liquid.

(manufacture method of hardening thing)

The manufacture method of hardening thing of the present invention is as long as be the manufacture method that uses the hardening thing of positive type photosensitive organic compound of the present invention, and there is no particular restriction, preferably at least sequentially comprises the method for step (a)～step (c).In addition, there is no particular restriction for the shape of the hardening thing obtaining by the manufacture method of hardening thing of the present invention, can as comprised the steps, as the method for (a)～step (c) be membranaceous hardening thing, also can be arbitrary shape, is the hardening thing of pattern-like as also can be as described later.

(a) positive type photosensitive organic compound of the present invention is coated to the application step on substrate

(b) remove the solvent removal step of solvent in the resin combination being coated with

(c) heat treatment step of the removed resin combination of solvent being heat-treated

Below each step is sequentially described.

< application step (step (a)) >

The manufacture method of hardening thing of the present invention preferably comprises that positive type photosensitive organic compound of the present invention is coated the application step on substrate by (a).

In step (a), preferably positive type photosensitive organic compound of the present invention is coated on set substrate, by reducing pressure and/or heating (prebake conditions) and remove solvent, form thus required dry coating.

In the present invention, spendable baseplate material can be enumerated: silicon, silicon dioxide, silicon nitride, aluminium oxide, glass, glass-ceramic, gallium arsenide, indium phosphide, copper, aluminium, nickel, iron, steel, copper-silicon alloy, indium-tin-oxide coating glass; The organic film such as polyimide and polyester; Any substrate of the pattered region that contains metal, semiconductor and insulating material etc., but be not limited to these.Depending on situation difference, sometimes, in order before coating resin composition, absorbed hygroscopic water to be removed, can on substrate, implement baking procedure.Coating process to substrate is not particularly limited, for example, can use the methods such as slot coated method, spray-on process, roller rubbing method, method of spin coating.In the time of the situation of large substrate, wherein slot coated method preferably.So-called large substrate herein, refers to that each limit is the big or small substrate more than 1m and below 5m.

< solvent removal step (step (b)) >

The manufacture method of hardening thing of the present invention preferably comprises that (b) removes the solvent removal step of solvent in the resin combination being coated with.

In step (b), preferably in the above-mentioned film being coated with, remove solvent by decompression (vacuum) and/or heating, on substrate, form dry coating.Preferably 70 DEG C～120 DEG C of heating conditions, about 30 second～300 seconds.

Resin pattern manufacture method of the present invention is because shape is controlled good, therefore the thickness that can be preferably used for after removal of solvents is thick film pattern manufacture more than 4 μ m.Thickness after removal of solvents is 4 μ m～500 μ m preferably, particularly preferably are 4 μ m～100 μ m.

< heat treatment step (step (c)) >

The manufacture method of hardening thing of the present invention preferably comprises the heat treatment step (baking procedure) that the resin combination to having removed solvent is heat-treated.By heat-treating, can form cured film.

Preferably 180 DEG C～250 DEG C of heat treatment temperatures (baking temperature), heat treatment time preferably 30 minutes～150 minutes.

For example; contain in use (a-1-1) have carboxyl or phenol hydroxyl through the monomeric unit of the base of sour decomposability base protection with the polymkeric substance of monomeric unit (a-2-1) with epoxy radicals and/or oxa-cyclobutyl during as the situation of components D; by in above-mentioned heat treatment step; make the sour decomposability base thermal decomposition in monomeric unit (a-1-1) and generate carboxyl or phenol hydroxyl; crosslinked with epoxy radicals and/or oxa-cyclobutyl, can form cured film.

In addition, in the time using the situation of (composition F) thermal cross-linking agent, preferably in above-mentioned heat treatment step, make (composition F) thermal cross-linking agent also carry out heat cross-linking.

(resin pattern manufacture method)

As long as resin pattern manufacture method of the present invention is for being used the resin pattern manufacture method of positive type photosensitive organic compound of the present invention, and there is no particular restriction, preferably at least sequentially comprises the method for step (1)～step (5).

(1) positive type photosensitive organic compound of the present invention is coated to the application step on substrate

(2) remove the solvent removal step of solvent in the resin combination being coated with

(3) by active ray, the resin combination of having removed solvent is exposed into the step of exposure of pattern-like

(4) by aqueous developer solution to the resin combination development step of developing through exposure

(5) to the heat treatment step of heat-treating through the resin combination developing

Below each step is sequentially described.

< application step (step (1)) >

Resin pattern manufacture method of the present invention preferably comprises that positive type photosensitive organic compound of the present invention coated the application step on substrate by (1).

Step (1) is the step identical with above-mentioned steps (a), and preferred implementation is also identical.

< solvent removal step (step (2)) >

Resin pattern manufacture method of the present invention preferably comprises the solvent removal step of removing solvent in (2) oneself resin combination being coated with.

Step (2) is the step identical with above-mentioned steps (b), and preferred implementation is also identical.

< step of exposure (step (3)) >

Resin pattern manufacture method of the present invention preferably comprises that (3) utilize active ray the resin combination of having removed solvent to be exposed into the step of exposure of pattern-like.

In step (3), irradiate the active ray of set pattern to being provided with the substrate of dry coating.Exposure can be carried out across mask, also can directly draw set pattern.

The active ray of the wavelength more than active ray can preferably use and have wavelength 300nm and below 450nm.While utilizing active ray to expose, can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, laser generator, LED light source etc.

In the time using the situation of mercury vapor lamp, can preferably use there is g line (436nm), i line (365nm), h line (405nm) equiwavelength's active ray.Mercury vapor lamp is compared with laser, preferred with regard to being suitable for the aspect of large-area exposure.

In the time using the situation of laser, can suitably select wavelength and there is no particular restriction that ground uses various laser.For example, solid (yttrium aluminum garnet (Yttrium Aluminum Garnet, YAG)) in laser, can use 343nm, 355nm, in excimer laser, can use 351nm (XeF), and then can use 375nm, 405nm in semiconductor laser.Wherein, with regard to the aspect such as stability, cost, more preferably 355nm or 405nm.Laser can once or several times irradiate in film.

Laser is compared with mercury vapor lamp, preferred with regard to following aspect: easily focus on, and without the mask forming for pattern in step of exposure, can reduce costs.

In the present invention, there is no particular restriction for spendable exposure device, and commercially available product can be used this holder of Cali (Callisto) (V science and technology (V-Technology) (thigh) manufacture), AEGIS (V science and technology (V-Technology) (thigh) manufacture) or DF2200G (Dainippon Screen Manufacturing Co manufacture (thigh) manufacture) etc.In addition, also can preferably use above-mentioned device in addition.

Point optical filter that optionally also can pass through as long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter in addition, is adjusted light irradiation.

In addition, can be after above-mentioned step of exposure, before development step, optionally carry out PEB (heat treated after exposure).Carry out PEB situation temperature preferably 30 DEG C above and below 130 DEG C, more preferably 40 DEG C above and below 110 DEG C, particularly preferably be 50 DEG C above and below 90 DEG C.

< development step (step (4)) >

Resin pattern manufacture method of the present invention preferably comprises that (4) utilize aqueous developer solution to the development step of developing through the resin combination of exposure.

In step (4), use aqueous developer solution to develop.

Aqueous developer solution is alkaline-based developer preferably.In alkaline-based developer, spendable alkali compounds for example 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 can use and in the aqueous solution of above-mentioned bases, be added with the water-miscible organic solvent such as methyl alcohol or ethanol of appropriate amount or the aqueous solution of interfacial agent as developer solution.

The pH value of developer solution preferably 10.0～14.0.

Development time is 30 second～180 seconds preferably, and in addition, the method for development can be any of the liquid method of covering, infusion process, shower method etc.After development, the flowing water that preferably carried out for 10 second～90 seconds cleans and forms required pattern.

In addition, resin pattern manufacture method of the present invention also can be between step (4) and step (5), comprise the step of exposure again of utilizing active ray to expose again to forming figuratum substrate, but preferably do not comprise this step of exposure again.

Exposure in step of exposure is as long as by the method identical with above-mentioned step of exposure again, and in above-mentioned step of exposure again, preferably the side of the film that is formed with resin combination to substrate is carried out blanket exposure.

The preferred exposure of step of exposure is 100mJ/cm again ²～1,000mJ/cm ².

< heat treatment step (step (5)) >

Resin pattern manufacture method of the present invention preferably comprises the heat treatment step (baking procedure) to heat-treating through the resin combination developing.By heat-treating, can form cured film.

Step (5) replaces and having removed the resin combination of solvent except using through the resin combination through developing of above-mentioned steps (4), is the step identical with above-mentioned steps (c), and preferred implementation is also identical.

(transfer materials)

Positive type photosensitive organic compound of the present invention can preferably be used as transfer materials.Particularly, for example can be preferably as being arranged at resin combination on temporary transient supporter and being transferred on the substrate of display device or on semiconductor substrate the transfer materials using.

In the time forming the situation of resin pattern with positive type photosensitive organic compound of the present invention as transfer materials, resin pattern manufacture method of the present invention preferably sequentially comprises the following steps (1 ')～step (6 ').

Positive type photosensitive organic compound of the present invention is coated the application step on temporary transient supporter by (1 ')

(2 ') remove the solvent removal step of solvent in the resin combination being coated with

The resin combination of having removed solvent is transferred to the step on substrate (permanent support body) by (3 ')

(4 ') expose into the resin combination of institute's transfer printing by active ray the step of exposure of pattern-like

(5 ') by aqueous developer solution to the resin combination development step of developing through exposure

(6 ') are to the heat treatment step of heat-treating through the resin combination developing

< application step (step (1 ')) >

Resin pattern manufacture method of the present invention preferably comprises (1 ') coats the application step on substrate by positive type photosensitive organic compound of the present invention.

Step (1 '), except using the temporary transient supporter shown in following to replace substrate, is the step identical with above-mentioned steps (a), and preferred implementation is also identical.

Temporary transient supporter can use the known material such as polyester, polystyrene.Wherein, with regard to the viewpoint of cost, thermotolerance, dimensional stability, the polyethylene terephthalate preferably extending through twin shaft.

The thickness of above-mentioned temporary transient supporter is 15 μ m～200 μ m preferably, more preferably 30 μ m～150 μ m.

< solvent removal step (step (2 ')) >

Resin pattern manufacture method of the present invention preferably comprises (2 ') removes the solvent removal step of solvent in the resin combination being coated with.

Step (2 ') is the step identical with above-mentioned steps (b), and preferred implementation is also identical.

< transfer step (step (3 ')) >

Resin pattern manufacture method of the present invention preferably comprises (3 ') is transferred to the step on substrate (permanent support body) by the resin combination of having removed solvent.

Above-mentioned transfer step preferably comprises: the step that the resin combination of having removed solvent is fitted in to the step on substrate (permanent support body) and the resin combination on being attached at substrate and removes temporary transient supporter.

Having removed the resin combination of solvent and the laminating of substrate for example can carry out in the following manner: utilize through roller or the flat board of heating and/or pressurization and carry out crimping or add thermo-compressed.

Specifically can enumerate laminating machine and the laminating method in Japanese patent laid-open 7-110575 communique, Japanese patent laid-open 11-77942 communique, Japanese Patent Laid-Open 2000-334836 communique, Japanese Patent Laid-Open 2002-148794 communique, recorded, with regard to the viewpoint of few foreign, preferably use the method for recording in Japanese patent laid-open 7-110575 communique.

There is no particular restriction for the removal method of temporary transient supporter, for example, can remove in the following manner: the adhesive roller etc. that makes to have adhesive coating contacts with temporary transient supporter, and the resin combination that is certainly attached at substrate is peeled off temporary transient supporter.About peeling off of temporary transient supporter, particularly also can be with continuous coiling formula and peel off peeling off continuously of temporary transient supporter, or the gripping of one chip is from the end of the outstanding temporary transient supporter of separated substrate and peeled off.

About the stripping means of above-mentioned temporary transient supporter, as peeling off continuously, can preferably enumerate Japanese Patent Laid-Open 2006-297879 communique, peel off as monolithic, can preferably enumerate the method for recording in Japanese Patent Laid-Open 2007-320678 communique.

< step of exposure (step (4 ')) >

Resin pattern manufacture method of the present invention preferably comprises (4 ') exposes into the resin combination of institute's transfer printing by active ray the step of exposure of pattern-like.

Step (4 ') replaces and having removed the resin combination of solvent except using through the resin combination through transfer printing of above-mentioned steps (3 '), is the step identical with above-mentioned steps (3), and preferred implementation is also identical.

< development step (step (5 ')) >

Resin pattern manufacture method of the present invention preferably comprises (5 ') by aqueous developer solution to the development step of developing through the resin combination of exposure.

Step (5 ') is the step identical with above-mentioned steps (4), and preferred implementation is also identical.

< heat treatment step (step (6 ')) >

Resin pattern manufacture method of the present invention preferably comprises (6 ') to the heat treatment step of heat-treating through the resin combination developing.By heat-treating, can form cured film.

Step (6 ') is the step identical with above-mentioned steps (5), and preferred implementation is also identical.

The resin pattern manufacture method that forms the situation of resin pattern with resin combination of the present invention as transfer materials also can be with reference to Japanese Patent Laid-Open 2010-72589 communique etc.

(hardening thing, optical component)

Hardening thing of the present invention is as long as forming positive type photosensitive organic compound sclerosis of the present invention, and there is no particular restriction, the hardening thing of preferably manufacturing by manufacture method or the resin pattern manufacture method of hardening thing of the present invention.

In addition, hardening thing of the present invention can preferably be used as the optical components such as lenticule, optical waveguide, anti-reflective film.In addition, hardening thing of the present invention also can preferably be used as the visibility reduction member of the distribution electrode using in touch-screen.Wherein, particularly preferably be as lenticule.

[embodiment]

Then, by embodiment to the present invention's more specifically explanation in addition.But the present invention is not limited to the examples.Moreover as long as no special instructions, " part " and " % " is quality criteria.

The assay method > of < acid number

The acid number of polymkeric substance is to measure by the titration with potassium hydroxide.

The preparation > of < dispersion liquid D1

By the dispersion liquid blending of following composition, itself and zirconium oxide bead (0.3mm φ) 17,000 mass parts are mixed, use coating oscillator to carry out disperseing for 12 hours.By zirconium oxide bead (0.3mm φ) isolated by filtration, obtain dispersion liquid D1.

Titania (the former industry of stone (thigh) is manufactured, trade name: TTO-51 (C), average primary particle diameter: 10nm～30nm): 1,875 part

Compound 1 (following compound, Mw=30,000, acid number: 180mg KOH/g, 30%PGMEA solution): 2,200 parts

Solvent PGMEA (propylene glycol methyl ether acetate): 3,425 parts

[changing 20]

The preparation > of < dispersion liquid D2～dispersion liquid D11

Except TTO-51 (C) and compound 1 are changed to respectively in table 1, record, similarly obtain respectively dispersion liquid D2～dispersion liquid D11 with the preparation of dispersion liquid D1.

[table 1]

Dispersion liquid	Inorganic particulate	Spreading agent
			D1	TTO-51(C)	Compound 1
D2	TTO-51(C)	Compound 2
			D3	TTO-51(C)	Compound 3
D4	TTO-51(C)	Compound 4
			D5	TTO-55(C)	Compound 1
D6	TTO-55(C)	Compound 2
			D7	RC-100	Compound 1
D8	RC-100	Compound 2
			D9	TTO-51(C)	Compound 5
D10	TTO-55(C)	Compound 5
			D11	RC-100	Compound 5

Moreover the abbreviation using in the dispersion liquid of recording in table 1 as shown below.Moreover the copolymerization ratio that the lower right corner of the parantheses [] of compound 1～compound 5 is recorded is mass percent.In addition, the numeral repeat number that the lower right corner of parantheses () is recorded.

TTO-55 (C): titania, the former industry of stone (thigh) is manufactured, average primary particle diameter: 30nm～50nm

RC-100: zirconium dioxide, first rare element chemistry industry (thigh) is manufactured, D ₅₀: 1.5 μ m～4 μ m

Compound 2: following compound, Mw=30,000, acid number: 140mg KOH/g, 30%PGMEA solution

Compound 3: following compound, Mw=30,000, acid number: 100mg KOH/g, 30%PGMEA solution

Compound 4: following compound, Mw=30,000, acid number: 105mg KOH/g, 30%PGMEA solution

Compound 5: following compound, Mw=30,000, acid number: 60mg KOH/g, 30%PGMEA solution

[changing 21]

[changing 22]

The synthetic > of < polymkeric substance

In following synthesis example, following abbreviation represents respectively following compound.

V-601: dimethyl-2,2 '-azo two (2 Methylpropionic acid ester)

PGMEA: propylene glycol methyl ether acetate

The synthetic > of < polymer P 1

By methacrylic acid tetrahydrofuran-2-base ester (0.38 molar equivalent),

Methacrylic acid (0.12 molar equivalent) and

Methacrylic acid (3-Ethyloxetane-3-yl) methyl esters (0.50 molar equivalent) add up to 100 parts and

The mixed solution of propylene glycol methyl ether acetate (PGMEA) (120 parts) flows down and is heated to 70 DEG C at nitrogen.One side stirs this mixed solution, simultaneously with 3.5 hours dropping radical polymerization initiator V-601 (dimethyl-2,2 '-azo two (2 Methylpropionic acid ester)), manufacture 12.0 parts with the pure pharmaceutical worker's industry of light (thigh)) and the mixed solution of PGMEA (80 parts).After dropping finishes, at 70 DEG C, react 2 hours, obtain thus the PGMEA solution of polymer P 1.And then add PGMEA and solid component concentration is adjusted into 40 quality %.

The weight average molecular weight (Mw) of passing through gel permeation chromatography (GPC) mensuration of the polymer P 1 of gained is 15,000.Acid number is 45mg KOH/g.

The synthetic > of < polymer P 2～polymer P 15

The synthetic middle each monomer using of polymer P 1 is changed to the monomer of the each structural unit of formation of recording in table 2, and the use amount of monomer that forms each structural unit is changed to and recorded in table 2, in addition, similarly distinguish synthetic polymer P2～polymer P 15 with synthesizing of polymer P 1.The addition of radical polymerization initiator V-601 is that the mode that becomes respectively in table 2 molecular weight of recording with each polymkeric substance is adjusted respectively.

Moreover the amount of recording in table 2 is mol ratio, represent the copolymerization ratio of the structural unit that derives from each monomer of recording in kind hurdle.In addition, in table 2, "-" represents not use this monomeric unit.

In addition, the abbreviation in table 2 is as follows.

MAEVE: methacrylic acid-1-ethoxy ethyl ester

MATHF: methacrylic acid tetrahydrofuran-2-base ester

OXE-30: methacrylic acid (3-Ethyloxetane-3-yl) methyl esters (Osaka organic chemistry industry (thigh) manufacture)

BzMA: benzyl methacrylate

HEMA: 2-hydroxyethyl methacry-late

MAA: methacrylic acid

MMA: methyl methacrylate

GMA: glycidyl methacrylate

St: styrene

(embodiment 1)

The preparation > of < positive type photosensitive organic compound

Mix and make after uniform solution with following composition allotment, using the tygon filtrator processed in the aperture (pore size) with 0.2 μ m to filter, the positive type photosensitive organic compound of Preparation Example 1.

Propylene glycol monomethyl ether: 140 parts

The 0.5%PGMEA solution of 1,5-diazabicyclo [4.3.0]-5-nonene: 18 parts

The 0.2%PGMEA solution of triphenyl imidazoles: 5 parts

Polymer P 1:225 part

α-(tolysulfonyl oxygen base imino group) phenylacetonitrile: 3 parts

JER157S65 (Mitsubishi Chemical's (thigh) manufactures, epoxide equivalent: 200g/eq～220g/eq): 3 parts

3-glycidoxypropyltrimewasxysilane (KBM-403, SHIN-ETSU HANTOTAI's chemical industry (thigh) is manufactured): 3 parts

The 2.0%PGMEA solution of following compound W-3: 5 parts

Dispersion liquid D1:600 part

[changing 23]

The residual film ratio of the unexposed portion of < is evaluated >

The mode that becomes 1.0 μ m with thickness utilizes spin coater the photosensitive polymer combination of gained to be coated on to the glass substrate (trade name: XG of 100mm × 100mm, healthy and free from worry (Corning) company manufactures) upper, on the hot plate of 90 DEG C, be dried (prebake conditions) 120 seconds.

Then, utilize 0.5% tetramethyl ammonium hydroxide aqueous solution to cover 15 seconds of liquid Faxian shadow by immersion at 23 DEG C, and then utilize 10 seconds of ultrapure water shower., further measure thickness, obtain thus that (1.0 μ are m) residual film ratio after 100% development with respect to thickness originally thereafter.Moreover metewand is as follows.

1: the residual film ratio after development is more than 90%.

2: the residual film ratio after development is more than 80% and is less than 90%.

3: the residual film ratio after development is less than 80%.

Below, evaluation result is shown in Table 3.

< resolution is evaluated >

Become the mode of 1.2 μ m with thickness, utilize spin coater that the photosensitive polymer combination of gained is coated and used hexamethyldisilazane (Hexamethyldisilazane, HMDS) carried out the glass substrate (trade name: XG of 100mm × 100mm that 3min processes, healthy and free from worry (Corning) company manufactures) upper, on the hot plate of 90 DEG C, be dried (prebake conditions) 120 seconds.

Then, using ghi line high-pressure mercury-vapor lamp exposure machine, is 20mW/cm in illumination ²condition under with 300mJ/cm ²be 1: 1 and expose with the mask of 1%～60% GTG across line and gap.

Then, utilize 0.5% tetramethyl ammonium hydroxide aqueous solution to cover 15 seconds of liquid Faxian shadow by immersion at 23 DEG C, and then utilize 10 seconds of ultrapure water shower.Then at 220 DEG C, heat 45 minutes and obtain pattern.Utilize optical microscope to observe this pattern.

Beginning aforesaid operations from the line of mask and the width in gap 50 μ m, till width being decreased to 10 μ m gradually taking 5 μ m as unit, below 10 μ m, reduce gradually width taking 1 μ m as unit, using the minimum widith of the ideally pattern-making of the suitableeest exposure part as resolution.

1: resolution is below 10 μ m.

2: resolution exceedes 10 μ m and is below 50 μ m.

3: in the situation of the line of mask and the width in gap 50 μ m, cannot form pattern.

The evaluation > of < transmissivity

The mode that becomes 1.0 μ m with thickness utilizes spin coater the photosensitive polymer combination of gained to be coated to the glass substrate (trade name: XG of 100mm × 100mm, healthy and free from worry (Corning) company manufactures) upper, on the hot plate of 90 DEG C, be dried (prebake conditions) 120 seconds.And then, utilize the baking oven of 220 DEG C to implement 45 minutes heat treated (baking afterwards) to coated film, utilize the MCPD-3000 that large tomb electronics (thigh) is manufactured to measure the spectrum after rear baking, evaluate the transmissivity of 400nm according to following metewand.

The transmissivity of 1:400nm is more than 90%.

The transmissivity of 2:400nm is more than 85% and is less than 90%.

The transmissivity of 3:400nm is less than 85%.

The evaluation > of <ITO visibility

In the glass substrate (trade name: XG of 100mm × 100mm, healthy and free from worry (Corning) company manufactures) on be pre-formed the pattern of ITO, the mode that becomes 1.0 μ m with thickness utilizes spin coater to be coated with the photosensitive polymer combination of gained, is dried (prebake conditions) 120 seconds on the hot plate of 90 DEG C.

Then, using ghi line high-pressure mercury-vapor lamp exposure machine, is 20mW/cm in illumination ²condition under with 300mJ/cm ²the whole face of substrate is exposed.

Then, at 220 DEG C, heat 45 minutes and the desciccator diaphragm of photonasty group resin combination is set on ITO pattern.Utilize optical microscope to observe the substrate of gained, compare when photosensitive polymer combination not being set on ITO pattern, carry out the evaluation of visibility.Moreover metewand is to be more difficult for seeing that the pattern of ITO is better.

1: pattern that almost can't see ITO.

2: the pattern of visible ITO faintly.

3: the pattern of obviously visible ITO.

The evaluation > of < refractive index

Use spinner that the photosensitive polymer combination of gained is coated on silicon wafer substrate, at 80 DEG C, be dried 120 seconds, form thus the film of thickness 0.5 μ m.Use extra-high-pressure mercury vapour lamp with 300mJ/cm ²(utilizing i line to measure), to this base board to explosure, utilizes thereafter baking oven 220 DEG C of points of lower heating 60 minutes.

Use ellipsometer VUV-VASE (Japanese J.A. Warren (J.A.Woollam Japan) (thigh) manufacture), measure the refractive index of the cured film under 589nm.Refractive index is got over Gao Yuejia, more preferably more than 1.70.

(embodiment 2～embodiment 32 and comparative example 1～comparative example 17)

In embodiment 2～embodiment 32 and comparative example 1～comparative example 17, dispersion liquid and components D (polymkeric substance) are changed to respectively and recorded in table 3, in addition, prepare similarly to Example 1 positive type photosensitive organic compound, carry out each evaluation.

[table 3]

Claims (11)

1. a positive type photosensitive organic compound, is characterized in that, comprises:

(composition A) inorganic particulate;

(composition B) has the spreading agent of acidic group;

(composition C) solvent;

(components D) contains the polymkeric substance that (a-1) has the structural unit of the base departing from by acid and/or heat and (a-2) have the structural unit of bridging property base; And

(composition E) light acid producing agent; And

The acid number of described components D is below 50mg KOH/g.

2. positive type photosensitive organic compound according to claim 1, wherein, described composition A is metal oxide particle.

3. positive type photosensitive organic compound according to claim 2, wherein, described composition A is Titanium particles.

4. according to the positive type photosensitive organic compound described in any one in claims 1 to 3, wherein, described composition B is the graft copolymer with carboxylic acid group, and acid number is more than 100mg KOH/g and below 190mg KOH/g.

5. according to the positive type photosensitive organic compound described in any one in claim 1 to 4, it also contains (composition F) thermal cross-linking agent.

6. according to the positive type photosensitive organic compound described in any one in claim 1 to 5, wherein, the weight average molecular weight of described composition B is more than 25,000 and below 50,000.

7. according to the positive type photosensitive organic compound described in any one in claim 1 to 6, it is optical component resin combination.

8. a manufacture method for hardening thing, is characterized in that, at least sequentially comprises step (a)～step (c):

(a) application step, will coat on substrate according to the positive type photosensitive organic compound described in any one in claim 1 to 7;

(b) solvent removal step is removed solvent in the described resin combination being coated with;

(c) heat treatment step, heat-treats the described resin combination of having removed solvent.

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

(1) application step, will coat on substrate according to the positive type photosensitive organic compound described in any one in claim 1 to 7;

(2) solvent removal step is removed solvent in the described resin combination being coated with;

(3) step of exposure, exposes into the described resin combination of having removed solvent to pattern-like by active ray;

(4) development step, by aqueous developer solution to through exposure described resin combination develop;

(5) heat treatment step, to heat-treating through the described resin combination developing.

10. a hardening thing, it is to obtain by the manufacture method of hardening thing according to claim 8 or resin pattern manufacture method according to claim 9.

11. 1 kinds of optical components, it is to obtain by the manufacture method of hardening thing according to claim 8 or resin pattern manufacture method according to claim 9.